JP2012173677A - Phase difference film and method for manufacturing the same, elongated polarizing plate, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phase difference film where no streak failure occurs and optical property in a width direction rarely fluctuates in an environmental endurance test, a method for manufacturing the phase difference film as an elongated stretched film, and an elongated polarizing plate and a liquid crystal display device provided with the stretched film.SOLUTION: A phase difference film is provided with a hard coat layer and has the following features: (1) the direction of a slow phase axis of the phase difference film differs from a longitudinal direction and a width direction of the film and is between the two directions; (2) in-plane phase difference value Ro measured under a prescribed condition is within a specific range; and (3) when the phase difference film is preserved in a prescribed high temperature and high humidity environment for many hours and the in-plane phase difference value Ro in the horizontal direction of the phase difference film after preservation is measured under the same condition as said measurement, a difference between the maximum value and the minimum value of variation value with the in-plane phase difference value Ro before preservation as reference is within a specific range.

Description

  The present invention relates to a retardation film, a method for producing the same, a long polarizing plate provided with the retardation film, and a liquid crystal display device.

  More specifically, the present invention relates to a retardation film in which no streak failure occurs and there is almost no variation in optical characteristics in the width direction in an environmental durability test (test), and a manufacturing method for manufacturing the retardation film as a long stretched film. . The present invention also relates to a long polarizing plate and a liquid crystal display device provided with the stretched film.

  A stretched film formed by stretching a resin film is used as an optical material such as a component of a display device by utilizing its optical anisotropy. For example, in a liquid crystal display device, the stretched film may be used as a retardation film for optical compensation such as anti-coloring and viewing angle expansion, or the stretched film and a polarizer may be bonded together to be used as a polarizing plate. It has been known. In general, a polarizing plate and a retardation film used in a liquid crystal display device are used in a rectangular shape. May be required. In such a liquid crystal display device, the in-plane slow axis of the retardation film and the transmission axis of the polarizer need to be arranged at a desired angle.

  Since the conventional retardation film is produced by longitudinal stretching or transverse stretching, the slow axis in the plane is in principle 0 ° or 90 ° with respect to the longitudinal direction of the film, so that the desired film In order to make the angle, it was performed by a batch method in which film pieces cut at a specific angle from a long stretched film roll were bonded one by one, but there were many problems with productivity and loss of chips. It was.

  On the other hand, a method for producing a long retardation film that is stretched obliquely at a desired angle and can be freely controlled in a direction in which the slow axis is neither 0 ° nor 90 ° with respect to the longitudinal direction of the film Have been proposed (see, for example, Patent Documents 1 to 3). By using a stretched film with such a slow axis inclined, productivity can be improved dramatically because roll-to-roll bonding is possible instead of conventional batch bonding. Loss is also greatly reduced.

  However, as a problem, there is a streak that does not appear in the stretched film but appears remarkably by applying and curing the surface-treated layer.

  In addition, when the film is stretched in an oblique direction, the stretching ratios at both ends are different, so that when the environmental durability test (test) is performed, the variation value of the optical characteristics varies in the width direction of the film. These problems cause the display quality to deteriorate significantly when the display device is provided with the film.

  However, the techniques disclosed in Patent Documents 1 to 3 cannot solve the problem of fluctuations in optical characteristics in streak failures and environmental durability tests (tests) in the width direction, and are retardation films by oblique stretching. It was a problem to be solved.

JP 2003-248117 A JP 2007-94007 A JP 2008-238514 A

  The present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is a phase difference in which no streak failure occurs and there is almost no fluctuation in the optical characteristics in the lateral direction in an environmental durability test (test). It is to provide a film and to provide a production method for producing the retardation film as a long stretched film. Moreover, it is providing the elongate polarizing plate and liquid crystal display device with which the said stretched film was comprised.

  The above-mentioned problem according to the present invention is solved by the following means.

  1. A retardation film provided with a hard coat layer, wherein (1) the direction of the slow axis of the retardation film is different from the long direction and the width direction of the film, and exists between both directions, 2) The in-plane retardation value Ro measured at a measurement wavelength of 590 nm at a temperature of 23 ° C. and a relative humidity of 55% RH is in the range of 120 to 170 nm, and (3) the retardation film is heated to a temperature of 60 ° C. and a relative humidity. When the in-plane retardation value Ro in the transverse direction is measured under the same conditions as the above measurement for the retardation film after storage in an environment of 90% RH for 500 hours, the in-plane retardation value before storage A retardation film, wherein a difference between a maximum value and a minimum value of fluctuation values based on Ro is in a range of 1 to 10 nm.

  2. 2. The retardation film according to item 1, wherein the hard coat layer is formed using a resin containing an active energy ray-curable resin.

  3. 3. The retardation film according to item 1 or 2, wherein the hard coat layer is formed using a coating solution containing an acrylate ester having three or four acryloyl groups.

  4). 4. The retardation film according to item 3, wherein the amount of solvent contained in the coating solution is less than 10% by mass.

  5). The retardation film according to item 3 or 4, wherein the solvent contained in the coating solution is ethanol or methanol.

  6). The retardation film according to item 3 or 4, wherein the coating liquid does not contain an organic solvent.

  7). The retardation film contains a cellulose ester having a substitution degree of acetyl group in the range of 2.0 to 2.6, according to any one of items 1 to 6 above. The retardation film described.

  8). It is a manufacturing method of the retardation film which manufactures the retardation film as described in any one of said 1st term to 7th term, Comprising: It exists in the range of 10-45 degrees with respect to the conveyance direction of a long film. After stretching in an oblique direction so as to have an in-plane slow axis at an angle of, the gripping means causes both ends of the long film to be at an angle in the range of −90 to −70 ° with respect to the transport direction, and A method for producing a retardation film, wherein the film is stretched at a stretching ratio in the range of 0 to 20%.

  9. A long polarizing plate formed by laminating the retardation film according to any one of items 1 to 7 on at least one surface of a long polarizer. .

  10. The sheet-like film formed by cutting the retardation film according to any one of Items 1 to 7 or the long polarizing plate according to Item 9 is cut. A liquid crystal display device comprising a formed sheet polarizing plate.

  11. 11. The liquid crystal display device according to item 10, wherein the liquid crystal display device is a stereoscopic image display device.

  According to the above-mentioned means of the present invention, there is provided a retardation film in which no streak failure is caused and there is almost no variation in the optical characteristics in the width direction in an environmental durability test (test), and the retardation film is elongated. The manufacturing method manufactured as a stretched film can be provided. Moreover, the elongate polarizing plate and liquid crystal display device which were equipped with the said stretched film can be provided.

Schematic diagram of obliquely stretched tenter according to the present invention Schematic showing the track (rail pattern) of the rail of the tenter used in the manufacturing method of the present invention Schematic diagram of the stretching equipment used in the examples Schematic diagram of the stretching equipment used in the examples Schematic diagram of a 3D image display device (system with one polarizing plate for glasses) Schematic diagram of liquid 3D image display device (system with two polarizing plates for glasses)

  The retardation film of the present invention is a retardation film provided with a hard coat layer, and (1) the direction of the slow axis of the retardation film is different from the long direction and the width direction of the film, Exists in both directions, (2) the in-plane retardation value Ro measured at a measurement wavelength of 590 nm at a temperature of 23 ° C. and a relative humidity of 55% RH is in the range of 120 to 170 nm, and (3) the phase difference When the film was stored for 500 hours in an environment at a temperature of 60 ° C. and a relative humidity of 90% RH, and the in-plane retardation value Ro in the transverse direction was measured under the same conditions as the measurement for the retardation film after storage, The difference between the maximum value and the minimum value of the fluctuation value based on the in-plane retardation value Ro before storage is in the range of 1 to 10 nm. This feature is a technical feature common to the inventions according to claims 1 to 11.

  As an embodiment of the present invention, it is preferable that the hard coat layer is a hard coat layer formed using a resin containing an active energy ray-curable resin from the viewpoint of manifesting the effects of the present invention. Furthermore, it is preferable that the hard coat layer is formed using a coating solution containing an acrylate ester having three or four acryloyl groups.

  When the hard coat layer is formed using a coating solution, the amount of solvent contained in the coating solution is preferably less than 10% by mass. Moreover, it is preferable that the solvent which the said coating liquid contains is ethanol or methanol. On the other hand, it is also preferable that the coating solution does not contain (water and) an organic solvent.

  In this invention, it is preferable that the said retardation film contains the cellulose ester which has an acetyl group substitution degree in the range of 2.0-2.6.

  As a method for producing a retardation film for producing the retardation film of the present invention, the retardation film is inclined so as to have an in-plane slow axis at an angle within a range of 10 to 45 ° with respect to the conveying direction of the long film. After extending | stretching, the aspect which extends | stretches the both ends of the said elongate film with the angle | corner in the range of -90-70 degree with respect to a conveyance direction, and the extending | stretching rate in the range of 0-20% with a holding means. It is preferable that it is a manufacturing method.

  The retardation film of the present invention can be laminated on at least one surface of a long polarizer to form a long polarizing plate.

  The sheet-like film formed by cutting the retardation film or the sheet-like polarizing plate formed by cutting the long polarizing plate can be suitably used for a liquid crystal display device. In particular, the liquid crystal display device is preferably a stereoscopic image display device.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

(Outline of retardation film of the present invention)
The retardation film of the present invention is a retardation film provided with a hard coat layer.

  In addition, the following requirements are satisfied.

(1) The direction of the slow axis of the retardation film is different from the long direction and the width direction of the film, and exists between both directions.
(2) The in-plane retardation value Ro measured at a measurement wavelength of 590 nm at a temperature of 23 ° C. and a relative humidity of 55% RH is in the range of 120 to 170 nm, and
(3) The retardation film is stored in an environment at a temperature of 60 ° C. and a relative humidity of 90% RH for 500 hours. When Ro is measured, the difference between the maximum value and the minimum value of the fluctuation value based on the in-plane retardation value Ro before storage is in the range of 1 to 10 nm.

  The retardation film of the present invention can be used as a λ / 4 plate as described later.

  The average thickness of the retardation film of the present invention is preferably 20 to 80 μm, more preferably 30 to 60 μm, and particularly preferably 30 to 40 μm from the viewpoint of mechanical strength and the like.

  Moreover, since the thickness unevenness in the width direction affects the availability of winding, it is preferably 3 μm or less, and more preferably 2 μm or less.

<Film base>
As the film substrate, thermoplastic resins using various resins are mainly used. Here, the “thermoplastic resin” refers to a resin that becomes soft when heated to the glass transition temperature or melting point and can be molded into a desired shape.

  Polycarbonate, polyester, polyethersulfone, polyarylate, polyimide, polyolefin, etc. can be used as a resin for a general retardation film (optical film). Also, cellulose terephthalate such as polyethylene terephthalate, polyimide, polymethyl methacrylate, polysulfone, polyethylene, polyvinyl chloride, alicyclic olefin polymer, acrylic polymer, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, etc. may be used. Good. In particular, cellulose esters such as cellulose diacetate, cellulose triacetate, and cellulose acetate propionate, acrylic polymers having a lactone ring structure, and the like are more preferable. These raw materials may be used alone or in combination with different thermoplastic resins. When mixed and used, a mixture of cellulose ester and acrylic polymer is more preferable.

  In the present invention, it is preferable that the film according to the present invention contains a resin having a positive intrinsic birefringence value. The “resin having a positive intrinsic birefringence value” refers to a resin having an increased refractive index in the stretched direction. Examples of the resin having a positive intrinsic birefringence value include cellulose acylate resins, cyclic olefin resins, and polycarbonate resins.

  The resin used as a raw material includes colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, antioxidants, lubricants, solvents, and other compounding agents. It may be appropriately blended.

  The film may be a single layer film or a multilayer film.

  As the film, a raw film is mainly used, but it may be a film in which any one of longitudinal stretching, lateral stretching, and oblique stretching has already been carried out alone or multiple times.

<Cellulose ester>
Although the retardation film of this invention can be produced using various resin base materials, it is preferable that it is an aspect containing a cellulose ester. Therefore, hereinafter, the retardation film of the present invention may be referred to as a cellulose ester film.

  The cellulose ester that can be used in the present invention is at least selected from cellulose (di, tri) acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose phthalate. One type is preferred.

  Among these, particularly preferable cellulose esters include cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.

  As a substitution degree of the mixed fatty acid ester, when having an acyl group having 2 to 4 carbon atoms as a substituent, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group or butyryl group is Y, A cellulose ester that simultaneously satisfies the following formulas (I) and (II) is preferred. That is, the retardation film of the present invention preferably contains a cellulose ester having an acetyl group substitution degree in the range of 2.0 to 2.6.

Formula (I): 2.0 ≦ X + Y ≦ 3.0
Formula (II): 2.0 ≦ X ≦ 2.6
Furthermore, the cellulose ester used in the present invention preferably has a weight average molecular weight Mw / number average molecular weight Mn ratio of 1.5 to 5.5, particularly preferably 2.0 to 5.0, Preferably it is 2.5-5.0, More preferably, the cellulose ester of 3.0-5.0 is used preferably.

  The cellulose ester raw material cellulose used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferred. A cotton linter is preferably used from the viewpoint of peelability during film formation. The cellulose ester made from these can be mixed suitably or can be used independently.

  For example, the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.

  In the present invention, 1 g of cellulose ester is added to 20 ml of pure water (electric conductivity of 0.1 μS / cm or less, pH 6.8), and the pH when stirred in a nitrogen atmosphere at 25 ° C. for 1 hr is 6 to 6. 7. It is preferable that the electric conductivity is 1 to 100 μS / cm.

  In addition, cellulose ester is industrially synthesized using sulfuric acid as a catalyst, but this sulfuric acid is not completely removed, and the remaining sulfuric acid causes various decomposition reactions during melt film formation, and is obtained. In order to affect the quality of the cellulose ester film, the residual sulfuric acid content in the cellulose ester used in the present invention is preferably in the range of 0.1 to 40 ppm in terms of elemental sulfur. These are considered to be contained in the form of salts. If the residual sulfuric acid content exceeds 40 ppm, the deposit on the die lip during heat melting increases, such being undesirable. Moreover, since it becomes easy to fracture | rupture at the time of slitting at the time of hot drawing or after hot drawing, it is not preferable. A smaller amount is preferable, but if it is less than 0.1, it is not preferable because the load of the cellulose ester washing process becomes too large, and it is not preferable because it may easily break. This is not well understood, although an increase in the number of washings may affect the resin. Furthermore, the range of 0.1-30 ppm is preferable. The residual sulfuric acid content can be similarly measured by ASTM-D817-96.

  Further, the total residual acid amount including other (such as acetic acid) residual acids is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less.

  For washing cellulose ester, in addition to water, a poor solvent such as methanol or ethanol, or, as a result, a mixed solvent of a poor solvent and a good solvent can be used as long as it is a poor solvent. Organic impurities can be removed.

  In order to improve the heat resistance, mechanical properties, optical properties, etc. of cellulose ester, it can be dissolved in a good solvent of cellulose ester and then reprecipitated in a poor solvent to remove low molecular weight components and other impurities of cellulose ester. it can. Furthermore, another polymer or a low molecular weight compound may be added after the cellulose ester reprecipitation treatment.

  Moreover, it is preferable that the cellulose ester used by this invention is a thing with few bright spot foreign materials when it is made into a film. A bright spot foreign material is an arrangement in which two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is placed between them, light from the light source is applied from one side, and the cellulose ester film is applied from the other side. This is the point where the light from the light source appears to leak when observed. At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used. The cause of bright spot foreign matter is considered to be one of the causes of unacetylated or low acetylated cellulose contained in the cellulose ester. Use a cellulose ester with little bright spot foreign matter and filter the melted cellulose ester or cellulose ester solution. In at least one of the later stage of synthesis of cellulose ester and the process of obtaining a precipitate, the bright spot foreign matter can be removed once again in the solution state via the filtration step. Since the molten resin has a high viscosity, the latter method is more efficient.

  In addition, unless the effect of this invention is impaired, thermoplastic resins other than the said cellulose acetate can also be used together for the retardation film of this invention.

  General thermoplastic resins include polyethylene (PE), high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS). Polyvinyl acetate (PVAc), Teflon (registered trademark) (polytetrafluoroethylene, PTFE), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), and the like can be used.

  When strength and resistance to breakage are particularly required, polyamide (PA), nylon, polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE, PPO), polybutylene terephthalate (PBT) ), Polyethylene terephthalate (PET), glass fiber reinforced polyethylene terephthalate (GF-PET), cyclic polyolefin (COP), and the like.

  Furthermore, when high heat distortion temperature and long-term use characteristics are required, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polysulfone, polyethersulfone, amorphous polyarylate, liquid crystal polymer, polyether Ether ketone, thermoplastic polyimide (PI), polyamideimide (PAI), or the like can be used.

  In addition, it is possible to perform the kind of resin and the combination of molecular weight according to the use of this invention.

  The retardation film of the present invention may be appropriately mixed with polymer components other than the cellulose ester described later. The polymer component to be mixed is preferably one having excellent compatibility with the cellulose ester, and the transmittance when formed into a film is preferably 80% or more, more preferably 90% or more, and further preferably 92% or more.

<Additives>
Additives added to the dope include plasticizers, ultraviolet absorbers, retardation adjusters, antioxidants, deterioration inhibitors, peeling aids, surfactants, dyes, fine particles, and the like. In the present invention, additives other than fine particles may be added during the preparation of the cellulose ester solution, or may be added during the preparation of the fine particle dispersion. It is preferable to add a plasticizer, an antioxidant, an ultraviolet absorber, or the like that imparts heat and moisture resistance to the polarizing plate used in the liquid crystal image display device. The additive will be described below.

(Compound represented by Formula A (1))
A compound represented by the following formula A (1) and a reference compound that are preferably used in the present invention are described below, but the present invention is not limited thereto.

In General Formula A (1), R _{1 to} R ₈ each independently represent a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ are the same as each other. Or different. In addition, R described in the following table represents any one of R _{1 to} R ₈ . As the substituent for the alkylcarbonyl group and the arylcarbonyl group, substituents such as a phenyl group and an alkoxy group included in the alkylcarbonyl group and the arylcarbonyl group shown in the following table are preferable.

  (Synthesis Example: Synthesis of Compound Used in the Present Invention)

A four-headed colben equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube was mixed with 34.2 g (0.1 mol) of sucrose, 180.8 g (0.8 mol) of benzoic anhydride, 379. 7 g (4.8 mol) was charged, the temperature was raised while bubbling nitrogen gas from a nitrogen gas introduction tube with stirring, and an esterification reaction was carried out at 70 ° C. for 5 hours. Next, the inside of the Kolben was depressurized to 4 × 10 ² Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 × 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off. Then, 1 L of toluene and 300 g of a 0.5% by mass aqueous sodium carbonate solution were added, and the mixture was stirred at 50 ° C. for 30 minutes and then allowed to stand to separate a toluene layer. Finally, 100 g of water is added to the collected toluene layer, and after washing with water at room temperature for 30 minutes, the toluene layer is separated, and toluene is distilled off at 60 ° C. under reduced pressure (4 × 10 ² Pa or less). A mixture of A-1, A-2, A-3, A-4 and A-5 was obtained. When the obtained mixture was analyzed by HPLC and LC-MASS, A-1 was 7% by mass, A-2 was 58% by mass, A-3 was 23% by mass, A-4 was 9% by mass, A-5. Was 3% by mass. A part of the obtained mixture was purified by column chromatography using silica gel to obtain A-1, A-2, A-3, A-4 and A-5 having a purity of 100%, respectively. .

  The total average substitution degree of the compound represented by the general formula A (1) added to the retardation film of the present invention is 6.1 to 6.9, and the range of the substitution degree is 4.0 to 8. 0.0 is preferred. The substitution degree distribution may be adjusted to the desired substitution degree by adjusting the esterification reaction time or mixing compounds having different substitution degrees.

(Plasticizer)
It is preferable to add a compound known as a so-called plasticizer to the retardation film of the present invention for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor permeability, adjusting retardation, and the like. For example, phosphoric acid esters and carboxylic acid esters are preferably used.

  The plasticizer is preferably contained in the cellulose ester film in an amount of 1 to 40% by mass, particularly 1 to 30% by mass.

  Examples of phosphate esters include triphenyl phosphate, tricresyl phosphate, phenyl diphenyl phosphate, and the like.

  Examples of the carboxylic acid ester include phthalic acid ester and citric acid ester. Examples of the phthalic acid ester include dimethyl phthalate, diethyl phosphate, dioctyl phthalate and diethyl hexyl phthalate. Mention may be made of tributyl. Other examples include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and triacetin. Alkylphthalylalkyl glycolates are also preferably used for this purpose. The alkyl in the alkylphthalylalkyl glycolate is an alkyl group having 1 to 8 carbon atoms. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl glycolate, Ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, propyl phthalyl ethyl glycolate, methyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl Phthalyl ethyl glycolate, propyl phthalyl butyl glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl Collate, octyl phthalyl methyl glycolate, octyl phthalyl ethyl glycolate and the like can be mentioned, such as methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, Octyl phthalyl octyl glycolate is preferably used. These alkyl phthalyl alkyl glycolates may be used in combination of two or more.

  Moreover, it is also preferable to use the citrate plasticizer represented by the following general formulas (1) to (3) described in Japanese Patent No. 3793184 as a plasticizer.

  Polyhydric alcohol esters are also preferably used.

  The polyhydric alcohol used in the retardation film of the present invention is represented by the following general formula (4).

General formula (4): R _{< 1 >} -(OH) _n
However, R ₁ represents an n-valent organic group, n represents a positive integer of 2 or more, and an OH group represents an alcoholic and / or phenolic hydroxyl group (hydroxyl group).

  The polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

  Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane- Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.

  Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

  As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.

  Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.

  Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.

  Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. The aromatic monocarboxylic acid which has, or those derivatives can be mentioned. Benzoic acid is particularly preferable.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.

  Although the specific compound of the polyhydric alcohol ester plasticizer used for this invention is shown below, this invention is not limited to this.

  It is preferable that these compounds are contained so that it may become 1-30 mass% with respect to a cellulose ester, Preferably it is 1-20 mass%. In order to suppress bleeding out during stretching and drying, a compound having a vapor pressure at 200 ° C. of 1400 Pa or less is preferable.

  These compounds may be added together with the cellulose ester or the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.

  Furthermore, in this invention, it is preferable to use the aromatic terminal ester plasticizer represented by following General formula (5).

General formula (5): B- (GA) n-GB
(In the formula, B is a benzene monocarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
In general formula (5), a benzene monocarboxylic acid residue represented by B and an alkylene glycol residue, an oxyalkylene glycol residue or an aryl glycol residue represented by G, an alkylene dicarboxylic acid residue or aryl dicarboxylic group represented by A It is composed of an acid residue and can be obtained by a reaction similar to that of a normal polyester plasticizer.

  Examples of the benzene monocarboxylic acid component of the aromatic terminal ester plasticizer used in the present invention include, for example, benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, There are normal propyl benzoic acid, aminobenzoic acid, acetoxybenzoic acid and the like, and these can be used as one kind or a mixture of two or more kinds, respectively.

  Examples of the alkylene glycol component having 2 to 12 carbon atoms of the aromatic terminal ester plasticizer used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, , 3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2, 2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1 , 5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3 There are hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, etc., and these glycols are used as one kind or a mixture of two or more kinds. used.

  Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal ester include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like. It can be used as a mixture of two or more.

  Examples of the aryl glycol component having 6 to 12 carbon atoms of the aromatic terminal ester include hydroquinone, resorcin, bisphenol A, bisphenol F, and bisphenol, and these glycols are used as one kind or a mixture of two or more kinds. it can.

  Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are used as one kind or a mixture of two or more kinds. Examples of the aryl dicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, 1,5 naphthalene dicarboxylic acid, and 1,4 naphthalene dicarboxylic acid.

  The aromatic terminal ester plasticizer has a number average molecular weight of preferably 300 to 2000, more preferably 500 to 1500. The acid value is 0.5 mgKOH / g or less, the hydroxyl (hydroxyl) value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl (hydroxyl) value is 15 mgKOH / g or less. Is preferred.

<Acid value of hydroxyl terminal ester, hydroxyl value>
The acid value means the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxyl group present at the molecular end) contained in 1 g of the sample. The acid value and hydroxyl (hydroxyl group) value are measured according to JIS K0070 (1992).

  Hereinafter, the synthesis example of the aromatic terminal ester plasticizer used for this invention is shown.

<Sample No. 1 (Aromatic terminal ester sample)>
Into a reaction vessel, 820 parts (5 moles) of phthalic acid, 608 parts (8 moles) of 1,2-propylene glycol, 610 parts (5 moles) of benzoic acid and 0.30 parts of tetraisopropyl titanate as a catalyst are charged all at once. While stirring in an air stream, a reflux condenser was attached to reflux excess monohydric alcohol, and heating was continued at 130 to 250 ° C. until the acid value became 2 or less, and water produced was continuously removed. Next, the distillate is removed under reduced pressure of 6.65 × 10 ³ Pa to 4 × 10 ² Pa or less at 200 to 230 ° C., followed by filtration to obtain an aromatic terminal ester having the following properties. It was.

Viscosity (25 ° C., mPa · s); 19815
Acid value: 0.4
<Sample No. 2 (Aromatic terminal ester sample)>
A sample was used except that 500 parts (3.5 moles) of adipic acid, 305 parts (2.5 moles) of benzoic acid, 583 parts (5.5 moles) of diethylene glycol, and 0.45 parts of tetraisopropyl titanate as a catalyst were used in the reaction vessel. No. In the same manner as in No. 1, an aromatic terminal ester having the following properties was obtained.

Viscosity (25 ° C., mPa · s); 90
Acid value: 0.05
<Sample No. 3 (Aromatic terminal ester sample)>
Sample No. except that 410 parts (2.5 moles) of phthalic acid, 610 parts (5 moles) of benzoic acid, 737 parts (5.5 moles) of dipropylene glycol and 0.40 parts of tetraisopropyl titanate as the catalyst were used in the reaction vessel. . In the same manner as in No. 1, an aromatic terminal ester plasticizer having the following properties was obtained.

Viscosity (25 ° C., mPa · s); 43400
Acid value: 0.2
Although the specific compound of the aromatic terminal ester plasticizer used for this invention below is shown, this invention is not limited to this.

  The content of the aromatic terminal ester plasticizer used in the present invention is preferably 1 to 20% by mass, and particularly preferably 3 to 11% by mass in the cellulose ester film.

(Polyester polyol)
The polyester polyol used in the present invention is a polymer having a hydroxyl group (hydroxyl group) at the end that can be obtained by a condensation reaction between a dibasic acid or an ester-forming derivative thereof and glycol. The ester-forming derivatives referred to here are esterified products of dibasic acids, dibasic acid chlorides, and anhydrides of dibasic acids.

  The polyester polyol is obtained by dehydration condensation reaction of aromatic dibasic acid and glycol, addition of glycol to aromatic anhydride dibasic acid and dehydration condensation reaction, or by alcohol removal of esterified product of aromatic dibasic acid and glycol. It can be obtained by a condensation reaction.

  As the aromatic dibasic acid or an ester-forming derivative thereof, an aromatic dicarboxylic acid having 10 to 16 carbon atoms or an ester-forming derivative thereof can be used. For example, a benzene ring structure, a naphthalene ring structure, Dicarboxylic acids having an aromatic ring structure such as anthracene ring structure and ester-forming derivatives thereof can be used. For example, orthophthalic acid having a substituent, isophthalic acid having a substituent, terephthalic acid having a substituent, substituted Group-containing phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6 -Anthracene dicarboxylic acid and the like, esterified products thereof, acid chlorides, 1,8-naphtha Etc. can be mentioned acid anhydrides Njikarubon acid, they may have a substituent on the aromatic ring, it can be used in combination used or two or more of these alone. 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid and esterified products thereof, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and esterified products thereof are preferable, and 2,6-naphthalenedicarboxylic acid and esterified products thereof are particularly preferable.

  The average number of carbon atoms of the dibasic acid of the polyester polyol means the number of carbon atoms of the dibasic acid when the polyester polyol is polymerized using a single dibasic acid. When the polyester polyol is polymerized using, it means the sum of the products of the carbon number of each dibasic acid and the molar fraction of the dibasic acid.

  In the present invention, it is important that the average number of carbon atoms of the dibasic acid used as a raw material for the polyester polyol is in the range of 10 to 16. If the average carbon number of the dibasic acid is 10 or more, the retardation is excellent. If the average carbon number is 16 or less, the compatibility with the cellulose ester is remarkably excellent. As a dibasic acid, Preferably the average of carbon number is 10-14, More preferably, the average of carbon number is 10-12.

  If the average carbon number is 10 to 16, the aromatic dibasic acid having 10 to 16 carbon atoms and the other dibasic acid can be used in combination.

  The dibasic acid that can be used in combination is preferably a dicarboxylic acid having 4 to 9 carbon atoms or an ester-forming derivative thereof. For example, succinic acid, glutaric acid, adipic acid, maleic acid, succinic anhydride, maleic anhydride, orthophthalic acid Examples thereof include acids, isophthalic acid, terephthalic acid, phthalic anhydride and the like, esterified products, and acid chlorides thereof.

  Examples of the glycol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol Etc. can be used alone or in combination of two or more, among which ethylene glycol, diethylene glycol, 1,2-propylene glycol, 2-methyl 1,3-propanediol are preferred, more preferably ethylene glycol, diethylene glycol, 1,2- Russia is propylene glycol.

  The polyester polyol used in the present invention comprises the dibasic acid or an ester-forming derivative thereof and a glycol, if necessary, in the presence of an esterification catalyst, for example, within a temperature range of 180 to 250 ° C. It can be produced by an esterification reaction in a well-known and conventional manner for a time.

  In conducting the esterification reaction, a solvent such as toluene or xylene may be used, but a method using no solvent or glycol used as a raw material as a solvent is preferable.

  As the esterification catalyst, for example, tetraisopropyl titanate, tetrabutyl titanate, p-toluenesulfonic acid, dibutyltin oxide and the like can be used. The esterification catalyst is preferably used in an amount of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of dibasic acids or their ester-forming derivatives.

  The molar ratio in reacting the dibasic acid or their ester-forming derivative with glycol must be such that the terminal group of the polyester becomes a hydroxyl group (hydroxyl group), and therefore the dibasic acid or their ester formation. The glycol is 1.1 to 10 moles per mole of the functional derivative. Preferably, glycol is 1.5 to 7 moles with respect to 1 mole of dibasic acid or an ester-forming derivative thereof, and more preferably with respect to 1 mole of dibasic acid or an ester-forming derivative thereof. 2-5 moles of glycol.

  On the other hand, the carboxyl group terminal in the polyester polyol lowers the humidity stability, so the content is preferably low. Specifically, the acid value is preferably 5.0 or less, more preferably 1.0 or less, and particularly preferably 0.5 or less.

  The acid value as used herein refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid (carboxyl group present in the sample) contained in 1 g of the sample. The acid value is measured according to JIS K0070.

  The polyester polyol preferably has a hydroxyl (hydroxyl) value (OHV) in the range of 35 mg / g to 220 mg / g. The hydroxyl (hydroxyl group) value as used herein refers to the number of milligrams of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group (hydroxyl group) when OH groups contained in 1 g of a sample are acetylated. . Acetic anhydride is used to acetylate OH groups in the sample, and unused acetic acid is titrated with a potassium hydroxide solution, and obtained from the difference from the initial titration value of acetic anhydride.

  The polyester polyol preferably has a hydroxyl group (hydroxyl group) content of 70% or more. When the hydroxyl group (hydroxyl group) content is low, the compatibility between the polyester polyol and the cellulose ester is lowered. For this reason, the hydroxyl group (hydroxyl group) content is preferably 70% or more, more preferably 90% or more, and most preferably 99% or more.

  In the present invention, a compound having a hydroxyl group (hydroxyl group) content of 50% or less is not included in the hydroxyl group (hydroxyl group) polyester polyol because one of the end groups is substituted with a group other than the hydroxyl group (hydroxyl group). .

The hydroxyl group (hydroxyl group) content can be determined by the following formula (A). Formula (A): Y / X × 100 = hydroxyl group (hydroxyl group) content (%)
X: hydroxyl value (OHV) of the polyester polyol
Y: 1 / (number average molecular weight (Mn)) × 56 × 2 × 1000
The polyester polyol preferably has a number average molecular weight within a range of 300 to 3,000, and more preferably has a number average molecular weight of 350 to 2,000.

  Moreover, it is preferable that the dispersion degree of the molecular weight of the polyester polyol used for this invention is 1.0-3.0, and it is still more preferable that it is 1.0-2.0. If the degree of dispersion is within the above range, a polyester polyol having excellent compatibility with the cellulose ester can be obtained. The polyester polyol preferably contains 50% or more of a component having a molecular weight of 300 to 1800. By setting the number average molecular weight within the above range, the compatibility can be greatly improved.

  As a method for controlling the number average molecular weight, the degree of dispersion, and the component content within the above preferred range, 2 to 5 mol of glycol is used per 1 mol of dibasic acid or ester-forming derivative thereof, and unreacted glycol is used. A method of distilling off under reduced pressure is preferred. The temperature at which the solvent is distilled off under reduced pressure is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and particularly preferably 130 to 170 ° C. The degree of reduced pressure when distilled off under reduced pressure is preferably 0.01 to 67 kPa (0.1 to 500 Torr), more preferably 0.06 to 27 kPa (0.5 to 200 Torr), and most preferably 0.13 to 13 kPa (1 to 100 Torr).

  The polyester polyol number average molecular weight (Mn) and dispersity can be measured using gel permeation chromatography (GPC).

  An example of measurement conditions is as follows, but is not limited to this, and an equivalent measurement method can be used.

Solvent: Tetrahydrofuran (THF)
Column: TSKgel G2000HXL (Tosoh Co., Ltd., two connected and used)
Column temperature: 40 ° C
Sample concentration: 0.1% by mass
Apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Flow rate: 1.0ml / min
Calibration curve: A calibration curve by PStQuick F (manufactured by Tosoh Corporation) is used.

  In obtaining the effects of the present invention, the polyester polyol is preferably contained in the film in an amount of 5 to 30% by mass. More preferably, it is 5-20 mass%.

  Specific examples of dibasic acids having 10 to 16 carbon atoms are shown below, but the present invention is not limited thereto.

(1) 2,6-naphthalenedicarboxylic acid (2) 2,3-naphthalenedicarboxylic acid (3) 2,6-anthracenedicarboxylic acid (4) 2,6-naphthalenedicarboxylic acid: succinic acid (75: 25-99: 1 molar ratio)
(5) 2,6-naphthalenedicarboxylic acid: terephthalic acid (50:50 to 99: 1 molar ratio)
(6) 2,3-naphthalenedicarboxylic acid: succinic acid (75:25 to 99: 1 molar ratio)
(7) 2,3-naphthalenedicarboxylic acid: terephthalic acid (50:50 to 99: 1 molar ratio)
(8) 2,6-anthracene dicarboxylic acid: succinic acid (50:50 to 99: 1 molar ratio)
(9) 2,6-anthracene dicarboxylic acid: terephthalic acid (25:75 to 99: 1 molar ratio)
(10) 2,6-naphthalenedicarboxylic acid: adipic acid (67:33 to 99: 1 molar ratio)
(11) 2,3-naphthalenedicarboxylic acid: adipic acid (67:33 to 99: 1 molar ratio)
(12) 2,6-anthracene dicarboxylic acid: adipic acid (40:60 to 99: 1 molar ratio)
(UV absorber)
The retardation film of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber that can be used include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. A benzotriazole-based compound with little coloring is preferable. Further, ultraviolet absorbers described in JP-A-10-182621, JP-A-8-337574, JP-A-2001-72782, JP-A-6-148430, JP-A-2002-31715, JP-A-2002-169020, 2002-2002. Polymer ultraviolet absorbers described in 47357, 2002-363420, and 2003-113317 are also preferably used. As an ultraviolet absorber, from the viewpoint of preventing the deterioration of polarizers and liquid crystals, it is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of liquid crystal display properties, the absorption of visible light having a wavelength of 400 nm or more is small. Is preferred.

  Specific examples of UV absorbers useful in the present invention include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis ( 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'- ert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5 -Chloro-2H-benzotriazol-2-yl) phenyl] propionate and the like can be mentioned, but not limited thereto. As commercially available products, TINUVIN 109, TINUVIN 171 and TINUVIN 326 (all manufactured by BASF Japan) can be preferably used. An example of the polymeric ultraviolet absorber is a reactive ultraviolet absorber RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

  Specific examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy- 5-benzoylphenylmethane) and the like, but is not limited thereto.

  The ultraviolet absorber described above preferably used in the present invention is preferably a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber, which has high transparency and is excellent in the effect of preventing the deterioration of the polarizing plate and the liquid crystal element, and unnecessary coloring. A benzotriazole-based ultraviolet absorber with a lower content is particularly preferably used.

  The ultraviolet absorber can be added to the dope without limitation as long as it dissolves the ultraviolet absorber in the dope. In the present invention, the ultraviolet absorber is cellulose such as methylene chloride, methyl acetate, dioxolane and the like. Dope by dissolving in a good solvent for the ester, or a mixed solvent of a good solvent and a poor solvent such as a lower aliphatic alcohol (methanol, ethanol, propanol, butanol, etc.) and adding it to the cellulose ester solution as an ultraviolet absorber solution Is preferred. In this case, it is preferable to make the dope solvent composition and the solvent composition of the ultraviolet absorber solution the same or close as possible. The content of the ultraviolet absorber is 0.01 to 5% by mass, particularly 0.5 to 3% by mass.

(Antioxidant)
As the antioxidant, hindered phenol compounds are preferably used. For example, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 , 5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanate Examples include nurate. In particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di-t A phosphorus-based processing stabilizer such as -butylphenyl) phosphite may be used in combination.

  The amount of these compounds added is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose ester.

  Moreover, it is also preferable to use the compound represented by the following general formula (L).

[Wherein, R _{2 to} R ₅ each independently represent a hydrogen atom or a substituent, R ₆ represents a hydrogen atom or a substituent, and n represents 1 or 2. When n is 1, R ₁ represents a substituent, and when n is 2, R ₁ represents a divalent linking group. ]
In the general formula (L), R _{2 to} R ₅ each independently represent a hydrogen atom or a substituent. The substituent represented by R _{2 to} R ₅ is not particularly limited, and examples thereof include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group). Group, dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino) Group), alkylthio group (for example, methylthio group, ethylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkenyl group (for example, vinyl group, 2-propenyl group, 3-butenyl group, 1- Methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl , Cyclohexenyl group etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group) , Imidazolyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl group (eg, methylsulfinyl group, etc.), An arylsulfinyl group (for example, phenylsulfinyl group), a phosphono group, an acyl group (for example, acetyl group, pivaloyl group, benzoyl group, etc.), a carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, Butyl Minocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group) , Cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc., sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, etc.) ), Cyano group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.) , Heterocyclic oxy group, siloxy group, acyloxy group (for example, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, Dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group) Group), imide group, ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc. ) Coxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.) ), Heterocyclic thio group, thioureido group, carboxyl group, carboxylic acid salt, hydroxyl group, mercapto group, nitro group and the like. These substituents may be further substituted with the same substituent.

In the general formula (L), R _{2 to} R ₅ are preferably a hydrogen atom or an alkyl group.

In the general formula (L), R ₆ represents a hydrogen atom or a substituent, and examples of the substituent represented by R ₆ include the same groups as the substituents represented by R _{2 to} R ₅ .

In the general formula (L), R ₆ is preferably a hydrogen atom.

  In the general formula (L), n represents 1 or 2.

In the general formula (L), when n is 1, R ₁ represents a substituent, and when n is 2, R ₁ represents a divalent linking group. When R ₁ represents a substituent, examples of the substituent include the same groups as the substituents represented by R _{2 to} R ₅ . When R ₁ represents a divalent linking group, examples of the divalent linking group include an alkylene group that may have a substituent, an arylene group that may have a substituent, an oxygen atom, a nitrogen atom, and a sulfur atom. Or a combination of these linking groups.

In the general formula (L), n is preferably 1, and R ₁ at that time is preferably a substituted or unsubstituted phenyl group, and more preferably a phenyl group substituted with an alkyl group.

  Next, although the specific example of a compound represented by the said general formula (L) in this invention is shown, this invention is not limited by the following specific examples.

  These compounds can be used singly or in combination of two or more, and the blending amount is appropriately selected within a range not impairing the object of the present invention, but is usually 0.001 per 100 parts by mass of the cellulose ester. -10.0 mass parts, Preferably it is 0.01-5.0 mass parts, More preferably, it is 0.1-3.0 mass parts.

(Retardation adjuster)
As the compound to be added for adjusting the retardation, an aromatic compound having two or more aromatic rings as described in EP 911,656A2 can be used.

  Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to the aromatic hydrocarbon ring. Particularly preferred is an aromatic heterocycle, and the aromatic heterocycle is generally an unsaturated heterocycle. Of these, a 1,3,5-triazine ring is particularly preferred.

  The number of aromatic rings contained in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, still more preferably 2 to 8, and most preferably 3 to 6. The bonding relationship between two aromatic rings can be classified into (a) when forming a condensed ring, (b) when directly connecting with a single bond, and (c) when connecting via a linking group (for aromatic rings). , Spiro bonds cannot be formed). The connection relationship may be any of (a) to (c).

  Examples of the condensed ring of (a) (condensed ring of two or more aromatic rings) include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a naphthacene ring, a pyrene ring, Indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline ring, quinolidine Ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, pteridine ring, carbazole ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring and thianthrene ring It is. Naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferred.

  The single bond (b) is preferably a bond between carbon atoms of two aromatic rings. Two aromatic rings may be bonded by two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.

  The linking group in (c) is also preferably bonded to carbon atoms of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, —CO—, —O—, —NH—, —S—, or a combination thereof. Examples of linking groups composed of combinations are shown below. In addition, the relationship between the left and right in the following examples of the linking group may be reversed.

  -CO-O-, -CO-NH-, -alkylene-O-, -NH-CO-NH-, -NH-CO-O-, -O-CO-O-, -O-alkylene-O-, -CO-alkenylene-, -CO-alkenylene-NH-, -CO-alkenylene-O-, -alkylene-CO-O-alkylene-O-CO-alkylene-, -O-alkylene-CO-O-alkylene-O -CO-alkylene-O-, -O-CO-alkylene-CO-O-, -NH-CO-alkenylene-, -O-CO-alkenylene-.

  The aromatic ring and the linking group may have a substituent. Examples of the substituent include halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, aliphatic acyl group , Aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic Substituted sulfamoyl groups, aliphatic substituted ureido groups and non-aromatic heterocyclic groups are included.

  It is preferable that the alkyl group has 1 to 8 carbon atoms. A chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable. The alkyl group may further have a substituent (eg, hydroxyl group, carboxyl group, alkoxy group, alkyl-substituted amino group). Examples of the alkyl group (including a substituted alkyl group) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethylaminoethyl. The alkenyl group preferably has 2 to 8 carbon atoms. A chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable. The alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl. The alkynyl group preferably has 2 to 8 carbon atoms. A chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable. The alkynyl group may further have a substituent. Examples of alkynyl groups include ethynyl, 1-butynyl and 1-hexynyl.

  The aliphatic acyl group preferably has 1 to 10 carbon atoms. Examples of the aliphatic acyl group include acetyl, propanoyl and butanoyl. The number of carbon atoms in the aliphatic acyloxy group is preferably 1-10. Examples of the aliphatic acyloxy group include acetoxy. The alkoxy group preferably has 1 to 8 carbon atoms. The alkoxy group may further have a substituent (eg, an alkoxy group). Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy and methoxyethoxy. The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl. The number of carbon atoms of the alkoxycarbonylamino group is preferably 2-10. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.

  The alkylthio group preferably has 1 to 12 carbon atoms. Examples of the alkylthio group include methylthio, ethylthio and octylthio. The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl. The number of carbon atoms in the aliphatic amide group is preferably 1-10. Examples of the aliphatic amide group include acetamide. The number of carbon atoms of the aliphatic sulfonamide group is preferably 1-8. Examples of the aliphatic sulfonamido group include methanesulfonamido, butanesulfonamido and n-octanesulfonamido. The number of carbon atoms of the aliphatic substituted amino group is preferably 1-10. Examples of the aliphatic substituted amino group include dimethylamino, diethylamino and 2-carboxyethylamino. The aliphatic substituted carbamoyl group preferably has 2 to 10 carbon atoms. Examples of the aliphatic substituted carbamoyl group include methylcarbamoyl and diethylcarbamoyl. The number of carbon atoms in the aliphatic substituted sulfamoyl group is preferably 1-8. Examples of the aliphatic substituted sulfamoyl group include methylsulfamoyl and diethylsulfamoyl. The number of carbon atoms in the aliphatic substituted ureido group is preferably 2-10. Examples of the aliphatic substituted ureido group include methylureido. Examples of non-aromatic heterocyclic groups include piperidino and morpholino.

  The molecular weight of the retardation adjusting agent is preferably 300 or more and 800 or less. This can arbitrarily select the polarity of the molecular structure from the viewpoint of suppressing the outflow at the time of use and processing of the polarizing plate.

  Among them, the compound having a 1,3,5-triazine ring is preferably a compound represented by the following general formula (R).

In the general formula (R), X ¹ is a single bond, —NR ₄ —, —O— or —S—; X ² is a single bond, —NR ₅ —, —O— or —S—; X ³ is a single bond, —NR ₆ —, —O— or —S—; R ¹ , R ² and R ³ are an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The compound represented by the general formula (R) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (R), X ¹ , X ² and X ³ are —NR ₄ —, —NR ₅ — and —NR ₆ —, respectively, or X ¹ , X ² and X 3 ³ is a single bond, and R ¹ , R ² and R ³ are heterocyclic groups having a free valence on the nitrogen atom. ^{-X 1 -R 1, -X 2 -R} 2 and ^-X 3 -R ³ are preferably the same substituents. R ¹ , R ² and R ³ are particularly preferably aryl groups. R ₄ , R ₅ and R ₆ are particularly preferably hydrogen atoms.

  The alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group. A linear alkyl group is preferred to a branched alkyl group.

  The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, still more preferably 1-8, 6 is most preferred. The alkyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy). The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. A linear alkenyl group is preferable to a branched chain alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, 6 is most preferred. The alkenyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) or an acyloxy group (for example, each group such as acryloyloxy and methacryloyloxy).

  The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

  Specific examples of the substituent include, for example, a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxy Carbonyl group, aryloxycarbonyl group, sulfamoyl, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamido group, carbamoyl, alkyl-substituted carbamoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio Groups, alkenylthio groups, arylthio groups and acyl groups are included. The said alkyl group is synonymous with the alkyl group mentioned above.

  The alkyl group of the alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl-substituted sulfamoyl group, sulfonamido group, alkyl-substituted carbamoyl group, amide group, alkylthio group and acyl group is also synonymous with the alkyl group described above.

  The said alkenyl group is synonymous with the alkenyl group mentioned above.

  The alkenyl part of the alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl-substituted sulfamoyl group, sulfonamido group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group is also synonymous with the alkenyl group described above.

  Specific examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl, and 4-dodecyloxyphenyl. Can be mentioned.

  Examples of the aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamido group, aryl-substituted carbamoyl group, amide group, arylthio group, and acyl group are the same as the above aryl group.

The heterocyclic group in the case where X ¹ , X ² or X ³ is —NR—, —O— or —S— preferably has aromaticity.

  The heterocyclic ring in the heterocyclic group having aromaticity is generally an unsaturated heterocyclic ring, preferably a heterocyclic ring having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring.

  The hetero atom in the heterocyclic ring is preferably an atom such as N, S or O, and particularly preferably an N atom.

  As the heterocyclic ring having aromaticity, a pyridine ring (as the heterocyclic group, for example, each group such as 2-pyridyl or 4-pyridyl) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.

When X ¹ , X ² or X ³ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms.

  Moreover, the hetero atom in a heterocyclic group may have hetero atoms other than a nitrogen atom (for example, O atom, S atom). The heterocyclic group may have a substituent. Specific examples of the substituent of the heterocyclic group are the same as the specific examples of the substituent of the aryl moiety.

  Specific examples of the heterocyclic group having a free valence on the nitrogen atom are shown below.

  Specific examples of the compound having a 1,3,5-triazine ring are shown below.

  In addition, several R shown below represents the same group.

(1) Butyl (2) 2-Methoxy-2-ethoxyethyl (3) 5-Undecenyl (4) Phenyl (5) 4-Ethoxycarbonylphenyl (6) 4-Butoxyphenyl (7) p-Biphenylyl (8) 4 -Pyridyl (9) 2-naphthyl (10) 2-methylphenyl (11) 3,4-dimethoxyphenyl (12) 2-furyl

(14) phenyl (15) 3-ethoxycarbonylphenyl (16) 3-butoxyphenyl (17) m-biphenylyl (18) 3-phenylthiophenyl (19) 3-chlorophenyl (20) 3-benzoylphenyl (21) 3 -Acetoxyphenyl (22) 3-benzoyloxyphenyl (23) 3-phenoxycarbonylphenyl (24) 3-methoxyphenyl (25) 3-anilinophenyl (26) 3-isobutyrylaminophenyl (27) 3-phenoxy Carbonylaminophenyl (28) 3- (3-ethylureido) phenyl (29) 3- (3,3-diethylureido) phenyl (30) 3-methylphenyl (31) 3-phenoxyphenyl (32) 3-hydroxyphenyl (33) 4-Ethoxycarbonylphenyl (34) 4-butoxyphenyl (35) p-biphenylyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl (38) 4-benzoylphenyl (39) 4-acetoxyphenyl (40) 4-benzoyloxyphenyl ( 41) 4-phenoxycarbonylphenyl (42) 4-methoxyphenyl (43) 4-anilinophenyl (44) 4-isobutyrylaminophenyl (45) 4-phenoxycarbonylaminophenyl (46) 4- (3-ethyl (Ureido) phenyl (47) 4- (3,3-diethylureido) phenyl (48) 4-methylphenyl (49) 4-phenoxyphenyl (50) 4-hydroxyphenyl (51) 3,4-diethoxycarbonylphenyl ( 52) 3,4-dibutoxyphenyl (53) 3 -Diphenylphenyl (54) 3,4-diphenylthiophenyl (55) 3,4-dichlorophenyl (56) 3,4-dibenzoylphenyl (57) 3,4-diacetoxyphenyl (58) 3,4-dibenzoyl Oxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxyphenyl (61) 3,4-dianilinophenyl (62) 3,4-dimethylphenyl (63) 3,4-diphenoxy Phenyl (64) 3,4-dihydroxyphenyl (65) 2-naphthyl (66) 3,4,5-triethoxycarbonylphenyl (67) 3,4,5-tributoxyphenyl (68) 3,4,5- Triphenylphenyl (69) 3,4,5-triphenylthiophenyl (70) 3,4,5-trichlorophenyl (71) 3,4,5-tribenzoylphenyl (72) 3,4,5-triacetoxyphenyl (73) 3,4,5-tribenzoyloxyphenyl (74) 3,4,5-triphenoxycarbonylphenyl (75) 3,4,5-trimethoxyphenyl (76) 3,4,5-trianilinophenyl (77) 3,4,5-trimethylphenyl (78) 3,4,5-triphenoxyphenyl (79 ) 3,4,5-trihydroxyphenyl

(80) phenyl (81) 3-ethoxycarbonylphenyl (82) 3-butoxyphenyl (83) m-biphenylyl (84) 3-phenylthiophenyl (85) 3-chlorophenyl (86) 3-benzoylphenyl (87) 3 -Acetoxyphenyl (88) 3-benzoyloxyphenyl (89) 3-phenoxycarbonylphenyl (90) 3-methoxyphenyl (91) 3-anilinophenyl (92) 3-isobutyrylaminophenyl (93) 3-phenoxy Carbonylaminophenyl (94) 3- (3-ethylureido) phenyl (95) 3- (3,3-diethylureido) phenyl (96) 3-methylphenyl (97) 3-phenoxyphenyl (98) 3-hydroxyphenyl (99) 4-Ethoxycarbonylphenyl (100) 4-butoxyphenyl (101) p-biphenylyl (102) 4-phenylthiophenyl (103) 4-chlorophenyl (104) 4-benzoylphenyl (105) 4-acetoxyphenyl (106) 4-benzoyloxyphenyl ( 107) 4-phenoxycarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-isobutyrylaminophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4- (3-ethyl (Ureido) phenyl (113) 4- (3,3-diethylureido) phenyl (114) 4-methylphenyl (115) 4-phenoxyphenyl (116) 4-hydroxyphenyl (117) 3,4-diethoxycarbonylphenyl ( 118) 3 , 4-dibutoxyphenyl (119) 3,4-diphenylphenyl (120) 3,4-diphenylthiophenyl (121) 3,4-dichlorophenyl (122) 3,4-dibenzoylphenyl (123) 3,4- Diacetoxyphenyl (124) 3,4-dibenzoyloxyphenyl (125) 3,4-diphenoxycarbonylphenyl (126) 3,4-dimethoxyphenyl (127) 3,4-dianilinophenyl (128) 3,4 -Dimethylphenyl (129) 3,4-diphenoxyphenyl (130) 3,4-dihydroxyphenyl (131) 2-naphthyl (132) 3,4,5-triethoxycarbonylphenyl (133) 3,4,5- Tributoxyphenyl (134) 3,4,5-triphenylphenyl (135) 3 4,5-triphenylthiophenyl (136) 3,4,5-trichlorophenyl (137) 3,4,5-tribenzoylphenyl (138) 3,4,5-triacetoxyphenyl (139) 3,4 5-tribenzoyloxyphenyl (140) 3,4,5-triphenoxycarbonylphenyl (141) 3,4,5-trimethoxyphenyl (142) 3,4,5-trianilinophenyl (143) 3,4 , 5-trimethylphenyl (144) 3,4,5-triphenoxyphenyl (145) 3,4,5-trihydroxyphenyl

(146) phenyl (147) 4-ethoxycarbonylphenyl (148) 4-butoxyphenyl (149) p-biphenylyl (150) 4-phenylthiophenyl (151) 4-chlorophenyl (152) 4-benzoylphenyl (153) 4 -Acetoxyphenyl (154) 4-benzoyloxyphenyl (155) 4-phenoxycarbonylphenyl (156) 4-methoxyphenyl (157) 4-anilinophenyl (158) 4-isobutyrylaminophenyl (159) 4-phenoxy Carbonylaminophenyl (160) 4- (3-ethylureido) phenyl (161) 4- (3,3-diethylureido) phenyl (162) 4-methylphenyl (163) 4-phenoxyphenyl (164) 4-hydroxyphenyl

(165) phenyl (166) 4-ethoxycarbonylphenyl (167) 4-butoxyphenyl (168) p-biphenylyl (169) 4-phenylthiophenyl (170) 4-chlorophenyl (171) 4-benzoylphenyl (172) 4 -Acetoxyphenyl (173) 4-benzoyloxyphenyl (174) 4-phenoxycarbonylphenyl (175) 4-methoxyphenyl (176) 4-anilinophenyl (177) 4-isobutyrylaminophenyl (178) 4-phenoxy Carbonylaminophenyl (179) 4- (3-ethylureido) phenyl (180) 4- (3,3-diethylureido) phenyl (181) 4-methylphenyl (182) 4-phenoxyphenyl (183) 4-hydroxyphenyl

(184) phenyl (185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenylyl (188) 4-phenylthiophenyl (189) 4-chlorophenyl (190) 4-benzoylphenyl (191) 4 -Acetoxyphenyl (192) 4-benzoyloxyphenyl (193) 4-phenoxycarbonylphenyl (194) 4-methoxyphenyl (195) 4-anilinophenyl (196) 4-isobutyrylaminophenyl (197) 4-phenoxy Carbonylaminophenyl (198) 4- (3-ethylureido) phenyl (199) 4- (3,3-diethylureido) phenyl (200) 4-methylphenyl (201) 4-phenoxyphenyl (202) 4-hydroxyphenyl

(203) phenyl (204) 4-ethoxycarbonylphenyl (205) 4-butoxyphenyl (206) p-biphenylyl (207) 4-phenylthiophenyl (208) 4-chlorophenyl (209) 4-benzoylphenyl (210) 4 -Acetoxyphenyl (211) 4-benzoyloxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutyrylaminophenyl (216) 4-phenoxy Carbonylaminophenyl (217) 4- (3-ethylureido) phenyl (218) 4- (3,3-diethylureido) phenyl (219) 4-methylphenyl (220) 4-phenoxyphenyl (221) 4-hydroxyphenyl

(222) phenyl (223) 4-butylphenyl (224) 4- (2-methoxy-2-ethoxyethyl) phenyl (225) 4- (5-nonenyl) phenyl (226) p-biphenylyl (227) 4-ethoxy Carbonylphenyl (228) 4-butoxyphenyl (229) 4-methylphenyl (230) 4-chlorophenyl (231) 4-phenylthiophenyl (232) 4-benzoylphenyl (233) 4-acetoxyphenyl (234) 4-benzoyl Oxyphenyl (235) 4-phenoxycarbonylphenyl (236) 4-methoxyphenyl (237) 4-anilinophenyl (238) 4-isobutyrylaminophenyl (239) 4-phenoxycarbonylaminophenyl (240) 4- ( 3-ethylureido Phenyl (241) 4- (3,3-diethylureido) phenyl (242) 4-phenoxyphenyl (243) 4-hydroxyphenyl (244) 3-butylphenyl (245) 3- (2-methoxy-2-ethoxyethyl) ) Phenyl (246) 3- (5-nonenyl) phenyl (247) m-biphenylyl (248) 3-ethoxycarbonylphenyl (249) 3-butoxyphenyl (250) 3-methylphenyl (251) 3-chlorophenyl (252) 3-phenylthiophenyl (253) 3-benzoylphenyl (254) 3-acetoxyphenyl (255) 3-benzoyloxyphenyl (256) 3-phenoxycarbonylphenyl (257) 3-methoxyphenyl (258) 3-anilinophenyl (259) 3-I Butyrylaminophenyl (260) 3-phenoxycarbonylaminophenyl (261) 3- (3-ethylureido) phenyl (262) 3- (3,3-diethylureido) phenyl (263) 3-phenoxyphenyl (264) 3 -Hydroxyphenyl (265) 2-butylphenyl (266) 2- (2-methoxy-2-ethoxyethyl) phenyl (267) 2- (5-nonenyl) phenyl (268) o-biphenylyl (269) 2-ethoxycarbonyl Phenyl (270) 2-Butoxyphenyl (271) 2-Methylphenyl (272) 2-Chlorophenyl (273) 2-Phenylthiophenyl (274) 2-Benzoylphenyl (275) 2-Acetoxyphenyl (276) 2-Benzoyloxy Phenyl (277) 2 Phenoxycarbonylphenyl (278) 2-methoxyphenyl (279) 2-anilinophenyl (280) 2-isobutyrylaminophenyl (281) 2-phenoxycarbonylaminophenyl (282) 2- (3-ethylureido) phenyl ( 283) 2- (3,3-diethylureido) phenyl (284) 2-phenoxyphenyl (285) 2-hydroxyphenyl (286) 3,4-dibutylphenyl (287) 3,4-di (2-methoxy-2) -Ethoxyethyl) phenyl (288) 3,4-diphenylphenyl (289) 3,4-diethoxycarbonylphenyl (290) 3,4-didodecyloxyphenyl (291) 3,4-dimethylphenyl (292) 3, 4-dichlorophenyl (293) 3,4-dibenzoyl Enyl (294) 3,4-diacetoxyphenyl (295) 3,4-dimethoxyphenyl (296) 3,4-di-N-methylaminophenyl (297) 3,4-diisobutyrylaminophenyl (298) 3 , 4-diphenoxyphenyl (299) 3,4-dihydroxyphenyl (300) 3,5-dibutylphenyl (301) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl (302) 3,5- Diphenylphenyl (303) 3,5-diethoxycarbonylphenyl (304) 3,5-didodecyloxyphenyl (305) 3,5-dimethylphenyl (306) 3,5-dichlorophenyl (307) 3,5-dibenzoyl Phenyl (308) 3,5-diacetoxyphenyl (309) 3,5-dimethoxyphenyl (3 0) 3,5-di-N-methylaminophenyl (311) 3,5-diisobutyrylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3,5-dihydroxyphenyl (314) 2,4 -Dibutylphenyl (315) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl (316) 2,4-diphenylphenyl (317) 2,4-diethoxycarbonylphenyl (318) 2,4-di Dodecyloxyphenyl (319) 2,4-dimethylphenyl (320) 2,4-dichlorophenyl (321) 2,4-dibenzoylphenyl (322) 2,4-diacetoxyphenyl (323) 2,4-dimethoxyphenyl ( 324) 2,4-di-N-methylaminophenyl (325) 2,4-diisobutyrylaminopheny (326) 2,4-diphenoxyphenyl (327) 2,4-dihydroxyphenyl (328) 2,3-dibutylphenyl (329) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl (330) 2,3-diphenylphenyl (331) 2,3-diethoxycarbonylphenyl (332) 2,3-didodecyloxyphenyl (333) 2,3-dimethylphenyl (334) 2,3-dichlorophenyl (335) 2, 3-dibenzoylphenyl (336) 2,3-diacetoxyphenyl (337) 2,3-dimethoxyphenyl (338) 2,3-di-N-methylaminophenyl (339) 2,3-diisobutyrylaminophenyl (340) 2,3-diphenoxyphenyl (341) 2,3-dihydroxyphenyl (342 2,6-dibutylphenyl (343) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl (344) 2,6-diphenylphenyl (345) 2,6-diethoxycarbonylphenyl (346) 2, 6-didodecyloxyphenyl (347) 2,6-dimethylphenyl (348) 2,6-dichlorophenyl (349) 2,6-dibenzoylphenyl (350) 2,6-diacetoxyphenyl (351) 2,6- Dimethoxyphenyl (352) 2,6-di-N-methylaminophenyl (353) 2,6-diisobutyrylaminophenyl (354) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl (356) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2-ethoxy) Til) phenyl (358) 3,4,5-triphenylphenyl (359) 3,4,5-triethoxycarbonylphenyl (360) 3,4,5-tridodecyloxyphenyl (361) 3,4,5- Trimethylphenyl (362) 3,4,5-trichlorophenyl (363) 3,4,5-tribenzoylphenyl (364) 3,4,5-triacetoxyphenyl (365) 3,4,5-trimethoxyphenyl ( 366) 3,4,5-tri-N-methylaminophenyl (367) 3,4,5-triisobutyrylaminophenyl (368) 3,4,5-triphenoxyphenyl (369) 3,4,5 -Trihydroxyphenyl (370) 2,4,6-tributylphenyl (371) 2,4,6-tri (2-methoxy-2-ethoxyethyl) ) Phenyl (372) 2,4,6-triphenylphenyl (373) 2,4,6-triethoxycarbonylphenyl (374) 2,4,6-tridodecyloxyphenyl (375) 2,4,6-trimethyl Phenyl (376) 2,4,6-trichlorophenyl (377) 2,4,6-tribenzoylphenyl (378) 2,4,6-triacetoxyphenyl (379) 2,4,6-trimethoxyphenyl (380 ) 2,4,6-tri-N-methylaminophenyl (381) 2,4,6-triisobutyrylaminophenyl (382) 2,4,6-triphenoxyphenyl (383) 2,4,6- Trihydroxyphenyl (384) Pentafluorophenyl (385) Pentachlorophenyl (386) Pentamethoxyphenyl (38 ) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl (388) 5-N-methylsulfamoyl-2-naphthyl (389) 6-N-phenylsulfamoyl-2-naphthyl (390) 5-Ethoxy-7-N-methylsulfamoyl-2-naphthyl (391) 3-methoxy-2-naphthyl (392) 1-ethoxy-2-naphthyl (393) 6-N-phenylsulfamoyl-8- Methoxy-2-naphthyl (394) 5-methoxy-7-N-phenylsulfamoyl-2-naphthyl (395) 1- (4-methylphenyl) -2-naphthyl (396) 6,8-di-N- Methylsulfamoyl-2-naphthyl (397) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2-naphthyl (398) 5-acetoxy-7- N-phenylsulfamoyl-2-naphthyl (399) 3-benzoyloxy-2-naphthyl (400) 5-acetylamino-1-naphthyl (401) 2-methoxy-1-naphthyl (402) 4-phenoxy-1 -Naphtyl (403) 5-N-methylsulfamoyl-1-naphthyl (404) 3-N-methylcarbamoyl-4-hydroxy-1-naphthyl (405) 5-methoxy-6-N-ethylsulfamoyl- 1-naphthyl (406) 7-tetradecyloxy-1-naphthyl (407) 4- (4-methylphenoxy) -1-naphthyl (408) 6-N-methylsulfamoyl-1-naphthyl (409) 3- N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl (410) 5-methoxy-6-N-benzylsulfamoyl 1-naphthyl (411) 3,6-di-N-phenylsulfamoyl-1-naphthyl (412) methyl (413) ethyl (414) butyl (415) octyl (416) dodecyl (417) 2-butoxy-2 -Ethoxyethyl (418) benzyl (419) 4-methoxybenzyl

(424) Methyl (425) Phenyl (426) Butyl

(430) methyl (431) ethyl (432) butyl (433) octyl (434) dodecyl (435) 2-butoxy-2-ethoxyethyl (436) benzyl (437) 4-methoxybenzyl

  In the present invention, a melamine polymer may be used as the compound having a 1,3,5-triazine ring. The melamine polymer is preferably synthesized by a polymerization reaction between a melamine compound represented by the following general formula (M) and a carbonyl compound.

In the above synthetic reaction scheme, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

  The alkyl group, alkenyl group, aryl group, heterocyclic group, and substituents thereof have the same meanings as the groups and substituents described in the general formula (R).

  The polymerization reaction between the melamine compound and the carbonyl compound is the same as the method for synthesizing a normal melamine resin (for example, melamine formaldehyde resin). Moreover, you may use a commercially available melamine polymer (melamine resin).

  The molecular weight of the melamine polymer is preferably 2,000 to 400,000. Specific examples of the repeating unit of the melamine polymer are shown below.

MP-1: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
MP-2: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
^{MP-3: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-4: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-5: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-6: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-7: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
_{^{MP-8: R 13, R}} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
_{^{MP-9: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
_{^{MP-10: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
_{^{MP-11: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
_{^{MP-12: R 13, R}} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
MP-13: R ¹³ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁴ , R ¹⁵ : CH ₂ OH
_{^{MP-14: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
_{^{MP-15: R 13, R}} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
_{^{MP-16: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
_{^{MP-17: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
_{^{MP-18: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{^{MP-19: R 13, R}} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
_{^{MP-20: R 13, R}} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
_{^{MP-21: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-22: R 13, R}} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{^{MP-23: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-24: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
_{^{MP-25: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-26: R 13, R}} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
_{^{MP-27: R 13, R}} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
_{^{MP-28: R 13, R}} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{^{MP-29: R 13, R}} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{^{MP-30: R 13, R}} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{^{MP-31: R 13: CH}} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{^{MP-32: R 13: CH}} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{^{MP-33: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-34: R 13: CH}} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{^{MP-35: R 13, R}} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-36: R 13, R}} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{^{MP-37: R 13: CH}} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-38: R 13, R}} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
_{^{MP-39: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-
C ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH═CH _{2
^{MP-40: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{^{MP-41: R 13: CH}} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{^{MP-42: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{^{MP-43: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{^{MP-44: R 13: CH}} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
_{^{MP-45: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{^{MP-46: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-47: R 13: CH}} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{^{MP-48: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{^{MP-49: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-50: R 13: CH}} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-51: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-52: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-53: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-54: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-55: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-56: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-57: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
MP-58: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OCH _{3
^{MP-59: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
_{^{MP-60: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
_{^{MP-61: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
_{^{MP-62: R 13, R}} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
_{^{MP-63: R 13, R}} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
_{^{MP-64: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
_{^{MP-65: R 13, R}} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
_{^{MP-66: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
_{^{MP-67: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
_{^{MP-68: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{^{MP-69: R 13, R}} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
_{^{MP-70: R 13, R}} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
_{^{MP-71: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-72: R 13, R}} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{^{MP-73: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-74: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
_{^{MP-75: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-76: R 13, R}} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
_{^{MP-77: R 13, R}} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
_{^{MP-78: R 13, R}} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{^{MP-79: R 13, R}} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{^{MP-80: R 13, R}} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{^{MP-81: R 13: CH}} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{^{MP-82: R 13: CH}} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{^{MP-83: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-84: R 13: CH}} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{^{MP-85: R 13, R}} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-86: R 13, R}} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{^{MP-87: R 13: CH}} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-88: R 13, R}} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
_{^{MP-89: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{^{MP-90: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{^{MP-91: R 13: CH}} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{^{MP-92: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{^{MP-93: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{^{MP-94: R 13: CH}} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
_{^{MP-95: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{^{MP-96: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-97: R 13: CH}} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{^{MP-98: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{^{MP-99: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-100: R 13: CH}} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

MP-101: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
^{MP-102: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-103: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-104: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-105: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-106: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-107: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
_{^{MP-108: R 13, R}} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
_{^{MP-109: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
_{^{MP-110: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
_{^{MP-111: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
_{^{MP-112: R 13, R}} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
_{^{MP-113: R 13, R}} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
_{^{MP-114: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
_{^{MP-115: R 13, R}} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
_{^{MP-116: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
_{^{MP-117: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
_{^{MP-118: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{^{MP-119: R 13, R}} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
_{^{MP-120: R 13, R}} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
MP-121: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH _{2 On} -C ₄ H ₉
MP-122: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH _{2 On} -C ₄ H _{9
^{MP-123: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-124: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
_{^{MP-125: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-126: R 13, R}} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
_{^{MP-127: R 13, R}} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
_{^{MP-128: R 13, R}} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{^{MP-129: R 13, R}} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{^{MP-130: R 13, R}} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{^{MP-131: R 13: CH}} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{^{MP-132: R 13: CH}} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{^{MP-133: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-134: R 13: CH}} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{^{MP-135: R 13, R}} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-136: R 13, R}} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{^{MP-137: R 13: CH}} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-138: R 13, R}} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
_{^{MP-139: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{^{MP-140: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{^{MP-141: R 13: CH}} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{^{MP-142: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{^{MP-143: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{^{MP-144: R 13: CH}} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
_{^{MP-145: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{^{MP-146: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-147: R 13: CH}} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{^{MP-148: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{^{MP-149: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-150: R 13: CH}} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

MP-151: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
^{MP-152: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-153: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-154: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
MP-155: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ NHCOCH═CH ₂
^{MP-156: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
MP-157: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OCH ₃
MP-158: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OCH ₃
MP-159: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OCH _{3
^{MP-160: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
MP-161: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH _{3
^{MP-162: R 13, R}} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
_{^{MP-163: R 13, R}} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
_{^{MP-164: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
_{^{MP-165: R 13, R}} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
_{^{MP-166: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
_{^{MP-167: R 13, R}} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
_{^{MP-168: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
_{^{MP-169: R 13, R}} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
_{^{MP-170: R 13, R}} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
_{^{MP-171: R 13, R}} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
MP-172: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH _{2 On} -C ₄ H _{9
^{MP-173: R 13, R}} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
MP-174: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH _{2 On} -C ₄ H _{9
^{MP-175: R 13: CH}} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
MP-176: R ¹³ , R ¹⁴ , R ¹⁶ : CH _{2 On} -C ₄ H ₉ ; R ¹⁵ : CH ₂ OH
_{^{MP-177: R 13, R}} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
_{^{MP-178: R 13, R}} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{^{MP-179: R 13, R}} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{^{MP-180: R 13, R}} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{^{MP-181: R 13: CH}} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
_{^{MP-182: R 13: CH}} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
_{^{MP-183: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
_{^{MP-184: R 13: CH}} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
_{^{MP-185: R 13, R}} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-186: R 13, R}} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
_{^{MP-187: R 13: CH}} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
_{^{MP-188: R 13, R}} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
_{^{MP-189: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{^{MP-190: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{^{MP-191: R 13: CH}} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{^{MP-192: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
_{^{MP-193: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
_{^{MP-194: R 13: CH}} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
_{^{MP-195: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{^{MP-196: R 13: CH}} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-197: R 13: CH}} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
_{^{MP-198: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
_{^{MP-199: R 13: CH}} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
_{^{MP-200: R 13: CH}} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
In the present invention, a copolymer obtained by combining two or more of the above repeating units may be used. Two or more homopolymers or copolymers may be used in combination.

  Moreover, you may use together the compound which has a 2 or more types of 1,3,5- triazine ring. Two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton) may be used in combination.

  In this invention, it is preferable to use at least 1 type of a benzoic acid phenylester compound as a retardation regulator, and it is preferable to add the benzoic acid phenylester compound shown by following General formula (6) to a cellulose ester especially.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent, and R ¹ , R ² , At least one of R ³ , R ⁴ and R ⁵ represents an electron donating group, R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 2 to 2 carbon atoms. 6 alkynyl groups, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 6 to 12 carbon atoms, alkoxycarbonyl groups having 2 to 12 carbon atoms, acylamino having 2 to 12 carbon atoms Represents a group, a cyano group or a halogen atom.)
In the general formula (6), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, Substituent T described later can be applied as the substituent.

At least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents an electron donating group. Preferably, one of R ¹ , R ³ or R ⁵ is an electron donating group, and R ³ is more preferably an electron donating group.

  The electron donating group is one having Hammet's σp value of 0 or less. Rev. , 91, 165 (1991), and those having Hammet's σp value of 0 or less are preferably applicable, and those having −0.85 to 0 are more preferably used. Examples thereof include an alkyl group, an alkoxy group, an amino group, and a hydroxyl group (hydroxyl group).

  The electron donating group is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 6 carbon atoms). Having 1 to 4 carbon atoms).

R ¹ is preferably a hydrogen atom or an electron donating group, more preferably an alkyl group, an alkoxy group, an amino group, or a hydroxyl group (hydroxyl group), still more preferably an alkyl group having 1 to 4 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, particularly preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to carbon atoms). 4), and most preferably a methoxy group.

R ² is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group (hydroxyl group), more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group. (Preferably 1 to 4 carbon atoms, more preferably a methyl group), an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably Is carbon number 1-4. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

R ³ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group (hydroxyl group), still more preferably an alkyl group or an alkoxy group. And particularly preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred are n-propoxy group, ethoxy group and methoxy group.

R ⁴ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group (hydroxyl group), still more preferably a hydrogen atom or a carbon number of 1 Alkyl group having 1 to 4 carbon atoms and alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Particularly preferred are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and most preferred are a hydrogen atom, a methyl group and a methoxy group.

R ⁵ is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group (hydroxyl group), more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group. (Preferably 1 to 4 carbon atoms, more preferably methyl group), alkoxy groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom). ~ 4). Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, and more preferably a hydrogen atom or a halogen atom. And more preferably a hydrogen atom.

R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl having 6 to 12 carbon atoms. Represents an oxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group or a halogen atom, and if possible, may have a substituent. Substituent T can be applied. Further, the substituent may be further substituted.

R ⁸ is preferably an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkoxycarbonyl having 2 to 12 carbon atoms. A cyano group, more preferably an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, and a cyano group, and more preferably 1 carbon atom. An alkoxy group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and a cyano group, particularly preferably an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and p-cyanophenyl. Group, a p-methoxyphenyl group, an alkoxycarbonyl group having 2 to 4 carbon atoms, and a cyano group.

  Among the compounds represented by the general formula (6), a more preferable compound is a compound represented by the following general formula (6-A).

In general formula (6-A), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as those in general formula (6), The preferred range is also the same.

R ¹¹ represents an alkyl group having 1 to 12 carbon atoms. The alkyl group represented by R ¹¹ may be linear or branched, and may further have a substituent, but is preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. An alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso group). -Butyl group, tert-butyl group and the like).

  Among the compounds represented by the general formula (6), a more preferable compound is a compound represented by the following general formula (6-B).

In general formula (6-B), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ have the same meanings as those in general formula (6), and the preferred ranges are also the same. It is.

R ¹¹ has the same meaning as that in formula (6-A), and the preferred range is also the same.

  X is an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, carbon An alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom is represented.

When R ¹ , R ² , R ⁴ and R ⁵ are all hydrogen atoms, X is preferably an alkyl group, alkynyl group, aryl group, alkoxy group or aryloxy group, more preferably an aryl group or alkoxy group. Group, aryloxy group, more preferably alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms). And particularly preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group or an n-butoxy group.

When at least one of R ¹ , R ² , R ⁴ , and R ⁵ is a substituent, X is preferably an alkynyl group, an aryl group, an alkoxycarbonyl group, or a cyano group, more preferably an aryl group (preferably Is a cyano group or an alkoxycarbonyl group (preferably a carbon number of 2 to 12), more preferably an aryl group (preferably an aryl group of 6 to 12 carbon atoms, more preferably a phenyl group). , P-cyanophenyl group and p-methoxyphenyl), an alkoxycarbonyl group (preferably having 2 to 12, more preferably 2 to 6, more preferably 2 to 4 carbon atoms, particularly preferably methoxycarbonyl, Ethoxycarbonyl, n-propoxycarbonyl), cyano group, particularly preferably phenyl group, methoxy group A carbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and a cyano group.

  Among the compounds represented by the general formula (6), a more preferable compound is a compound represented by the following general formula (6-C).

In general formula (6-C), R ¹ , R ² , R ⁴ , R ⁵ , R ¹¹ and X are synonymous with those in general formula (6-B), and preferred ranges are also the same.

  Among the compounds represented by the general formula (6), a particularly preferable compound is a compound represented by the following general formula (6-D).

In general formula (6-D), R ² , R ⁴ and R ⁵ have the same meanings as those in general formula (6-C), and the preferred ranges are also the same. R ²¹ and R ²² each independently represents an alkyl group having 1 to 4 carbon atoms. X1 represents an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group.

R ²¹ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an ethyl group or a methyl group.

R ²² represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

X ¹ is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group, preferably an aryl group having 6 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a cyano group. More preferably a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl group, a methoxycarbonyl, an ethoxycarbonyl, an n-propoxycarbonyl, a cyano group, and still more preferably a phenyl group, a methoxycarbonyl group, an ethoxycarbonyl group. , N-propoxycarbonyl group and cyano group.

  Among the compounds represented by the general formula (6), the most preferable compound is a compound represented by the following general formula (6-E).

In general formula (6-E), R ² , R ⁴ and R ⁵ have the same meanings as those in general formula (6-D), and the preferred ranges are also the same. However, any one is a group represented by —OR ¹³ . Here, R ¹³ is an alkyl group having 1 to 4 carbon atoms. R ²¹ , R ²² and X ¹ have the same meanings as those in formula (6-D), and preferred ranges are also the same.

Preferably, at least one of R ⁴ and R ⁵ is a group represented by —OR ¹³ , and more preferably, R ⁴ is a group represented by —OR ¹³ .

R ¹³ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

  Hereinafter, the aforementioned substituent T will be described.

  Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert- Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably C2-8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably C2-20, more preferably C2-12, particularly preferably Has 2 to 8 carbon atoms, for example, propargyl, 3-pentynyl, etc.), aryl group (preferably 6 carbon atoms) 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc.), a substituted or unsubstituted amino group (preferably having a carbon number) 0 to 20, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), alkoxy groups (preferably C1-C20, More preferably, it is C1-C12, Most preferably, it is C1-C8, for example, a methoxy, an ethoxy, butoxy etc. are mentioned, and an aryloxy group (preferably C6-C20). More preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 2-naphthyloxy, etc. And an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl A group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms such as phenyloxycarbonyl), an acyloxy group (preferably having 2 to 2 carbon atoms). 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms. And benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), alkoxycarbonylamino group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group (preferably having carbon number) 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and the like, and sulfonylamino groups (preferably 1 to 20 carbon atoms, more preferably Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. And sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl and methylsulfamoyl). , Dimethylsulfamoyl, phenylsulfamoyl, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl). , Methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, Ethylthio etc.), arylthio group (preferably Has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably Has 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms) More preferably, it is C1-C16, Most preferably, it is C1-C12, for example, diethyl phosphoric acid amide, phenylphosphoric acid amide etc. are mentioned. ), Hydroxyl group, mercapto group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl , Morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms). For example, trimethylsilyl, triphenylsilyl, etc.) That. These substituents may be further substituted.

  Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

  Hereinafter, the compound represented by the general formula (6) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

  The compound represented by the general formula (6) used in the present invention can be synthesized by a general ester reaction of a substituted benzoic acid and a phenol derivative, and any reaction may be used as long as it is an ester bond forming reaction. Examples thereof include a method of converting a substituted benzoic acid into an acid halide and then condensing with phenol, a method of dehydrating condensation of a substituted benzoic acid and a phenol derivative using a condensing agent or a catalyst, and the like.

  In view of the production process and the like, a method in which the substituted benzoic acid is functionally converted to an acid halide and then condensed with phenol is preferable.

  Examples of the reaction solvent include hydrocarbon solvents (preferably toluene and xylene), ether solvents (preferably dimethyl ether, tetrahydrofuran, dioxane and the like), ketone solvents, ester solvents, acetonitrile and dimethyl. Formamide, dimethylacetamide and the like can be used. These solvents may be used alone or in admixture of several kinds, and preferred reaction solvents are toluene, acetonitrile, dimethylformamide and dimethylacetamide.

  The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.

  In this reaction, it is preferable not to use a base. When a base is used, either an organic base or an inorganic base may be used, preferably an organic base such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiisopropyl). Pyramine and the like).

  Furthermore, the retardation film of the present invention preferably contains a rod-like compound having a maximum absorption wavelength (λmax) of the ultraviolet absorption spectrum of the solution shorter than 250 nm as a retardation adjusting agent.

  From the viewpoint of the function of the retardation adjusting agent, the rod-like compound preferably has at least one aromatic ring, and more preferably has at least two aromatic rings. The rod-like compound preferably has a linear molecular structure. The linear molecular structure means that the molecular structure of the rod-like compound is linear in the most thermodynamically stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculation can be performed using molecular orbital calculation software (eg, WinMOPAC2000, manufactured by Fujitsu Limited) to obtain a molecular structure that minimizes the heat of formation of a compound. The molecular structure being linear means that the angle of the molecular structure is 140 degrees or more in the thermodynamically most stable structure obtained by calculation as described above. The rod-shaped compound preferably exhibits liquid crystallinity. More preferably, the rod-like compound exhibits liquid crystallinity upon heating (has thermotropic liquid crystallinity). The liquid crystal phase is preferably a nematic phase or a smectic phase.

  The rod-like compound is preferably a trans-1,4-cyclohexanedicarboxylic acid ester compound represented by the following general formula (7).

Formula ^{(7): Ar 1 -L 1} -Ar 2
In the general formula (7), Ar ¹ and Ar ² are each independently an aromatic group. In the present specification, the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group. An aryl group and a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The heterocyclic ring of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As a hetero atom, a nitrogen atom, an oxygen atom or a sulfur atom is preferable, and a nitrogen atom or a sulfur atom is more preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , A pyridazine ring, a pyrimidine ring, a pyrazine ring, and a 1,3,5-triazine ring. As the aromatic ring of the aromatic group, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring and a pyrazine ring are preferable, and a benzene ring is particularly preferable. .

  Examples of substituents for substituted aryl groups and substituted aromatic heterocyclic groups include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, alkylamino groups (eg, methylamino, ethylamino) , Butylamino, dimethylamino), nitro, sulfo, carbamoyl, alkylcarbamoyl groups (eg, N-methylcarbamoyl, N-ethylcarbamoyl, N, N-dimethylcarbamoyl), sulfamoyl, alkylsulfamoyl groups (eg, N- Methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), ureido, alkylureido groups (eg, N-methylureido, N, N-dimethylureido, N, N, N′-trimethyl) Ureido), alkyl groups (eg, methyl, ethyl, propyl, butyl, pentyl, Butyl, octyl, isopropyl, s-butyl, t-amyl, cyclohexyl, cyclopentyl), alkenyl groups (eg, vinyl, allyl, hexenyl), alkynyl groups (eg, ethynyl, butynyl), acyl groups (eg, formyl, acetyl, Butyryl, hexanoyl, lauryl), acyloxy groups (eg, acetoxy, butyryloxy, hexanoyloxy, lauryloxy), alkoxy groups (eg, methoxy, ethoxy, propoxy, butoxy, pentyloxy, heptyloxy, octyloxy), aryloxy groups (Eg, phenoxy), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, heptyloxycarbonyl), aryloxycarbo Group (eg, phenoxycarbonyl), alkoxycarbonylamino group (eg, butoxycarbonylamino, hexyloxycarbonylamino), alkylthio group (eg, methylthio, ethylthio, propylthio, butylthio, pentylthio, heptylthio, octylthio), arylthio group (eg, , Phenylthio), alkylsulfonyl groups (eg, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, heptylsulfonyl, octylsulfonyl), amide groups (eg, acetamide, butylamide group, hexylamide, laurylamide) and non- Aromatic heterocyclic groups (eg, morpholyl, pyrazinyl) are included.

  Substituents for substituted aryl groups and substituted aromatic heterocyclic groups include halogen atoms, cyano, carboxyl, hydroxyl, amino, alkyl-substituted amino groups, acyl groups, acyloxy groups, amide groups, alkoxycarbonyl groups, alkoxy groups, alkylthios. And groups and alkyl groups are preferred. The alkyl moiety of the alkylamino group, alkoxycarbonyl group, alkoxy group, and alkylthio group and the alkyl group may further have a substituent. Examples of alkyl moieties and substituents of alkyl groups include halogen atoms, hydroxyl, carboxyl, cyano, amino, alkylamino groups, nitro, sulfo, carbamoyl, alkylcarbamoyl groups, sulfamoyl, alkylsulfamoyl groups, ureido, alkylureido Group, alkenyl group, alkynyl group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkylsulfonyl group, amide group and non-aromatic An aromatic heterocyclic group is included. As the substituent for the alkyl moiety and the alkyl group, a halogen atom, hydroxyl, amino, alkylamino group, acyl group, acyloxy group, acylamino group, alkoxycarbonyl group and alkoxy group are preferable.

In General Formula (7), L ¹ is a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, a divalent saturated heterocyclic group, —O—, —CO—, and combinations thereof. It is. The alkylene group may have a cyclic structure. As the cyclic alkylene group, cyclohexylene is preferable, and 1,4-cyclohexylene is particularly preferable. As the chain alkylene group, a linear alkylene group is more preferable than a branched alkylene group. The number of carbon atoms of the alkylene group is preferably 1-20, more preferably 1-15, still more preferably 1-10, still more preferably 1-8, 6 is most preferred.

  The alkenylene group and the alkynylene group preferably have a chain structure rather than a cyclic structure, and more preferably have a linear structure rather than a branched chain structure. The number of carbon atoms in the alkenylene group and the alkynylene group is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, and still more preferably 2 to 4. 2 (vinylene or ethynylene) is most preferred. The divalent saturated heterocyclic group preferably has a 3- to 9-membered heterocyclic ring. The hetero atom of the hetero ring is preferably an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a silicon atom, a phosphorus atom or a germanium atom. Examples of saturated heterocycles include piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, imidazolidine ring, tetrahydrofuran ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, tetrahydrothiophene ring, 1 , 3-thiazolidine ring, 1,3-oxazolidine ring, 1,3-dioxolane ring, 1,3-dithiolane ring and 1,3,2-dioxaborolane. Particularly preferred divalent saturated heterocyclic groups are piperazine-1,4-diylene, 1,3-dioxane-2,5-diylene and 1,3,2-dioxaborolane-2,5-diylene.

  The example of the bivalent coupling group which consists of a combination is shown.

L-1: —O—CO-alkylene group —CO—O—
L-2: -CO-O-alkylene group -O-CO-
L-3: —O—CO—alkenylene group —CO—O—
L-4: -CO-O-alkenylene group -O-CO-
L-5: -O-CO-alkynylene group -CO-O-
L-6: -CO-O-alkynylene group -O-CO-
L-7: -O-CO-divalent saturated heterocyclic group -CO-O-
L-8: -CO-O-divalent saturated heterocyclic group -O-CO-
In the molecular structure of the general formula (7), the angle formed by Ar ¹ and Ar ² across L ¹ is preferably 140 degrees or more. As the rod-like compound, a compound represented by the following general formula (8) is more preferable.

Formula ^{(8): Ar 1 -L 2} -X-L 3 -Ar 2
In the general formula (8), Ar ¹ and Ar ² are each independently an aromatic group. The definition and examples of the aromatic group are the same as those of Ar ¹ and Ar ^{2 in} the general formula (7).

In General Formula (8), L ² and L ³ are each independently a divalent linking group selected from the group consisting of an alkylene group, —O—, —CO—, and combinations thereof. The alkylene group preferably has a chain structure rather than a cyclic structure, and more preferably has a linear structure rather than a branched chain structure. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, still more preferably 1 to 4, and 1 or Most preferred is 2 (methylene or ethylene). L ² and L ³ are particularly preferably —O—CO— or —CO—O—.

  In General formula (8), X is 1, 4- cyclohexylene, vinylene, or ethynylene. The specific example of a compound represented by General formula (7) below is shown.

  Specific examples (1) to (34), (41), (42), (46), (47), (52), (53) are two asymmetric carbons at the 1st and 4th positions of the cyclohexane ring. Has atoms. However, the specific examples (1), (4) to (34), (41), (42), (46), (47), (52), (53) have a symmetric meso type molecular structure. Therefore, there is no optical isomer (optical activity) and only geometric isomers (trans and cis forms) exist. The trans type (1-trans) and cis type (1-cis) of specific example (1) are shown below.

  As described above, the rod-like compound preferably has a linear molecular structure. Therefore, the trans type is preferable to the cis type. Specific examples (2) and (3) have optical isomers (a total of four isomers) in addition to geometric isomers. As for geometric isomers, the trans type is similarly preferable to the cis type. The optical isomer is not particularly superior or inferior, and may be D, L, or a racemate. In specific examples (43) to (45), the central vinylene bond includes a trans type and a cis type. For the same reason as above, the trans type is preferable to the cis type.

  Two or more rod-shaped compounds having a maximum absorption wavelength (λmax) shorter than 250 nm in the ultraviolet absorption spectrum of the solution may be used in combination. The rod-like compound can be synthesized with reference to methods described in literature. As literature, Mol. Cryst. Liq. Cryst. 53, 229 (1979), 89, 93 (1982), 145, 111 (1987), 170, 43 (1989); Am. Chem. Soc. 113, p. 1349 (1991), p. 118, p. 5346 (1996), p. 92, p. 1582 (1970). Org. Chem. 40, 420 (1975), Tetrahedron, 48, 16, 3437 (1992).

<Polymer or oligomer>
The retardation film of the present invention has a cellulose ester and a substituent selected from a carboxyl group, a hydroxyl group, an amino group, an amide group, and a sulfonic acid group and has a weight average molecular weight in the range of 500 to 200,000. It preferably contains a polymer or oligomer of a certain vinyl compound. The mass ratio of the content of the cellulose ester and the polymer or oligomer is preferably in the range of 95: 5 to 50:50.

  Hereinafter, the polymer or oligomer used in the present invention will be described.

The carboxyl group is a group having a structure of —COO—. The amino group is a group having a structure of —NR ₁ , R ₂ , R ₃ , and R ₁ , R ₂ , R ₃ each represents a substituent such as a hydrogen atom, an alkyl group, or a phenyl group. The amide group is a group having a structure of —NHCO—, and a substituent such as an alkyl group or a phenyl group may be linked thereto.

  Examples of the polymer and oligomer used in the present invention include the following acrylic polymers and oligomers.

  These compounds are preferably used in the range of 5 to 50% by mass with respect to the cellulose ester, and are preferably excellent in compatibility. The transmittance is 80% over the entire visible range (400 nm to 800 nm) when formed into a film. Thus, 90% or more, more preferably 92% or more is obtained.

<Acrylic polymer and oligomer>
The acrylic polymer and oligomer used in the present invention are not particularly limited in structure, but a polymer having a weight average molecular weight of 500 or more and 200,000 or less obtained by polymerizing an ethylenically unsaturated monomer. It is preferable that

  The acrylic polymer and oligomer used in the present invention may be composed of a single monomer or a plurality of types of monomers. The monomer is preferably selected from acrylic acid ester or methacrylic acid ester, but appropriately contains other monomers such as maleic anhydride, styrene, etc. depending on the retardation characteristics, wavelength dispersion characteristics, and heat resistance of the film to be produced. It does not matter.

  Hereinafter, the acrylic polymer and oligomer used in the present invention will be described as polymer X.

<Polymer X>
The polymer X used in the present invention comprises an ethylenically unsaturated monomer Xa having no aromatic ring and a polar group in the molecule and an ethylenically unsaturated monomer Xb having no aromatic ring and a polar group in the molecule. A polymer represented by the following general formula (1) having a weight average molecular weight of 500 or more and 200,000 or less obtained by polymerization is preferred. Further, it is preferably solid at 30 ° C. or glass transition temperature of 35 ° C. or higher.

  When the weight average molecular weight is 500 or more and 200,000 or less, the compatibility with the cellulose ester and the transparency are excellent.

General formula (1):-[Xa] m- [Xb] n-
(M and n represent molar composition ratios, and m + n = 100.)
Although the monomer as a monomer unit which comprises the polymer X used for this invention is mentioned below, it is not limited to this.

  Examples of the ethylenically unsaturated monomer Xa having no aromatic ring and no polar group in the molecule include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), and butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl) , Acrylic acid (2-ethoxyethyl), or the like, or those obtained by replacing the acrylic ester with a methacrylic ester. Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate (i-, n-) are preferable.

  The ethylenically unsaturated monomer Xb having no polar ring in the molecule and having a polar group is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxyl group (hydroxyl group). For example, (meth) acrylic acid 2 -Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, (meth) acrylic acid 10 Hydroxyl group-containing monomers such as hydroxydecyl, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate; (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate , Itacon Carboxyl group-containing monomers such as maleic acid, fumaric acid and crotonic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; styrene sulfonic acid and allyl sulfonic acid, 2- ( Sulfonic acid group-containing monomers such as (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid; 2-hydroxyethylacryloyl phosphate, etc. And phosphoric acid group-containing monomers.

  In addition, (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc. Monomer; (Meth) acrylic acid aminoethyl, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid t-butylaminoethyl (meth) acrylic acid alkylaminoalkyl monomer; (Meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl acid and ethoxyethyl (meth) acrylate; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- ( (Meta) acryloyl- - oxy octamethylene succinimide, also including succinimide-based monomers such as N- acryloyl morpholine and the like as a monomer Examples of the reforming purposes.

  Further, vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N-vinyl carboxylic acid amide , Vinyl monomers such as styrene, α-methylstyrene, N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; (meth) acrylic Polyethylene glycol acid, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolypropylene (meth) acrylate Glycol acrylic ester monomers such as recall; (meth) acrylic acid tetrahydrofurfuryl, fluorine (meth) acrylate, silicone (meth) acrylate and acrylic acid ester monomers such as 2-methoxyethyl acrylate, etc. may also be used.

  In the present invention, the polymer X is synthesized by copolymerization using the hydrophobic monomer Xa and the polar monomer Xb. Further, the above-described hydrophobic monomer or polar monomer can be used as the monomer Xc to form a terpolymer.

  The use ratio in the synthesis of the hydrophobic monomer Xa and the polar monomer Xb is preferably in the range of 99: 1 to 50:50, more preferably in the range of 95: 5 to 60:40. When the use ratio of the hydrophobic monomer Xa is large, the compatibility with the cellulose ester is lowered, but the effect of reducing the fluctuation of the retardation value with respect to the environmental humidity is high. When the use ratio of the polar monomer Xb is large, the compatibility with the cellulose ester is improved, but the fluctuation of the retardation value with respect to the environmental humidity is increased. Moreover, since the haze comes out at the time of film forming when the usage-amount of polar monomer Xb exceeds the said range, it is unpreferable.

  In order to synthesize such a polymer, it is difficult to control the molecular weight in normal polymerization, and it is desirable to use a method that can align the molecular weight as much as possible without increasing the molecular weight. Such polymerization methods include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than normal polymerization, and a mercapto compound in addition to the polymerization initiator. And a method using a chain transfer agent such as carbon tetrachloride, a method using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further disclosed in JP-A No. 2000-128911 or 2000-344823. Examples thereof include a compound having one thiol group and a secondary hydroxyl group (hydroxyl group), or a bulk polymerization method using a polymerization catalyst in which the compound and an organometallic compound are used in combination. It is preferably used in the present invention.

  The weight average molecular weight of the polymer X used in the present invention can be adjusted by a known molecular weight adjusting method. Examples of such a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like. The polymerization temperature is usually from room temperature to 130 ° C., preferably from 50 ° C. to 100 ° C., but this temperature or the polymerization reaction time can be adjusted.

  The measuring method of a weight average molecular weight can be based on the said molecular weight measuring method.

  The amount of the polymer X added is appropriately adjusted so that the film has a desired performance. Addition to reduce fluctuation of photoelastic coefficient and retardation value with respect to environmental humidity. Addition of small amount to increase retardation performance. , Corner irregularities that change the color of the corners of the screen, and even if the phase difference value changes from the initially set value, the viewing angle fluctuates and the color changes. Since phase difference performance cannot be obtained, 5 mass% or more and 50 mass% or less are preferable.

<Acrylic polymer having a lactone ring structure>
The acrylic polymer is not particularly limited as long as it is a resin obtained by polymerizing a monomer composition containing (meth) acrylic acid ester as a main component. Moreover, what has two or more types of acrylic polymers as a main component may be used.

  Examples of the (meth) acrylic acid ester include the following general formula (I):

(In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
A compound (monomer) having a structure represented by the formula: Acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc. Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate; May be used alone, or two or more of them may be used in combination. Among these, a compound having a structure represented by the above general formula (I) and methyl methacrylate are more preferable because of excellent heat resistance and transparency. In addition, benzyl (meth) acrylate is preferred in terms of increasing positive birefringence (positive phase difference).

  In addition, when introduce | transducing a methacrylic acid benzyl monomer structural unit, the preferable content of the (meth) acrylic acid benzyl monomer structural unit in an acrylic polymer is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 15-30 mass%.

  Examples of the compound having a structure represented by the general formula (I) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, 2- (Hydroxymethyl) normal butyl acrylate, 2- (hydroxymethyl) tert-butyl acrylate, and the like. Among these, methyl 2- (hydroxymethyl) acrylate and 2- (hydroxymethyl) ethyl acrylate are preferable, and methyl 2- (hydroxymethyl) acrylate is particularly preferable in that the effect of improving heat resistance is high. As for the compound represented by general formula (I), only 1 type may be used and 2 or more types may be used together.

  The acrylic polymer may have a structure other than the structure obtained by polymerizing the (meth) acrylic acid ester described above. The structure other than the structure obtained by polymerizing (meth) acrylic acid ester is not particularly limited, but includes a hydroxyl group (hydroxyl group) -containing monomer, an unsaturated carboxylic acid, the following general formula (II)

(Wherein R ⁶ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁷ group, or —C It represents ^{-O-R 8} group, Ac group represents an acetyl group, ^{R 7} and ^{R 8} represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
The polymer structural unit (repeating structural unit) constructed by polymerizing at least one selected from the monomers represented by

  The hydroxyl group (hydroxyl group) -containing monomer is not particularly limited as long as it is a hydroxyl group (hydroxyl group) -containing monomer other than the monomer represented by formula (I). For example, methallyl alcohol, allyl 2- (hydroxyalkyl) acrylic acid esters such as alcohol, allyl alcohol such as 2-hydroxymethyl-1-butene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, methyl 2- (hydroxyethyl) acrylate; 2- (Hydroxyalkyl) acrylic acid such as (hydroxyethyl) acrylic acid; and the like. These may be used alone or in combination of two or more.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, α-substituted methacrylic acid and the like. These may be used alone or in combination of two or more. May be. Among these, acrylic acid and methacrylic acid are preferable in that the effects of the present invention are sufficiently exhibited.

  Examples of the compound represented by the general formula (II) include styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. These may be used alone. Two or more kinds may be used in combination. Among these, styrene and α-methylstyrene are particularly preferable in that the effects of the present invention are sufficiently exhibited.

  The polymerization method is not particularly limited, and a known polymerization method can be used. A suitable method may be employed depending on the type of monomer (monomer composition) to be used, the use ratio, and the like.

  The acrylic polymer used in the present invention has a glass transition temperature (Tg) of preferably 110 ° C to 200 ° C, more preferably 115 ° C to 200 ° C, still more preferably 120 ° C to 200 ° C, and particularly preferably 125 ° C. It is -190 degreeC, Most preferably, it is 130 to 180 degreeC.

  In terms of heat resistance, N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide, and methylmaleimide may be copolymerized in the molecular chain (also referred to as the main skeleton of the polymer or the main chain). A lactone ring structure, a glutaric anhydride structure, a glutarimide structure, or the like may be introduced. Among them, a monomer that does not contain a nitrogen atom is preferable from the viewpoint of difficulty in coloring (yellowing) the film, and positive birefringence (positive phase difference) is easily expressed in the main chain. Those having a lactone ring structure are preferred. Regarding the lactone ring structure in the main chain, a 4- to 8-membered ring may be used, but a 5- to 6-membered ring is more preferable, and a 6-membered ring is more preferable in view of the stability of the structure. Further, when the lactone ring structure in the main chain is a 6-membered ring, examples include the structure represented by the general formula (III) and Japanese Patent Application Laid-Open No. 2004-168882, and the lactone ring structure is introduced into the main chain. The point of high polymerization yield in the synthesis of the previous polymer, the point that a polymer with a high content of lactone ring structure is easily obtained with high polymerization yield, and (meth) acrylic acid esters such as methyl methacrylate From the viewpoint of good copolymerizability, a structure represented by the general formula (III) is preferable.

  When the acrylic polymer is a resin obtained by polymerizing a monomer containing a compound having a structure represented by the general formula (I), the acrylic polymer has a lactone ring structure. Is more preferable (hereinafter, an acrylic polymer having a lactone ring structure is referred to as a “lactone ring-containing polymer”). Hereinafter, the lactone ring-containing polymer will be described.

  In the retardation film of the present invention, it is also preferable to use a compound having a lactone ring structure.

  Examples of the lactone ring structure include the following general formula (III)

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.)
The structure represented by is mentioned.

  The organic residue in the general formula (III) is not particularly limited as long as it has a carbon number in the range of 1 to 20, but for example, a linear or branched alkyl group, a linear or branched alkyl group, and the like. An alkylene group, an aryl group, -OAc group, -CN group, etc. are mentioned.

  The content of the lactone ring structure in the acrylic polymer is preferably in the range of 5 to 90% by mass, more preferably in the range of 20 to 90% by mass, and still more preferably in the range of 30 to 90% by mass. More preferably, it is in the range of 35 to 90% by mass, particularly preferably in the range of 40 to 80% by mass, and most preferably in the range of 45 to 75% by mass. If the content of the lactone ring structure is more than 90% by mass, the moldability becomes poor. Moreover, there exists a tendency for the flexibility of the obtained film to fall, and it is not preferable. When the content of the lactone ring structure is less than 5% by mass, it is difficult to obtain a necessary retardation when formed into a film, and heat resistance, solvent resistance, and surface hardness may be insufficient. It is not preferable.

  In the lactone ring-containing polymer, the content ratio of the structure other than the lactone ring structure represented by the general formula (III) is that of a polymer structural unit (repeating structural unit) constructed by polymerizing (meth) acrylic acid ester. In the range of 10 to 95% by mass, more preferably in the range of 10 to 80% by mass, further preferably in the range of 10 to 65% by mass, particularly preferably in the range of 20 to 60% by mass, Preferably it exists in the range of 25-55 mass%. In the case of a polymer structural unit (repeating structural unit) constructed by polymerizing a hydroxyl group (hydroxyl group) -containing monomer, it is preferably in the range of 0 to 30% by mass, more preferably in the range of 0 to 20% by mass. More preferably, it is in the range of 0 to 15% by mass, particularly preferably in the range of 0 to 10% by mass. In the case of a polymer structural unit (repeating structural unit) constructed by polymerizing an unsaturated carboxylic acid, it is preferably in the range of 0 to 30% by mass, more preferably in the range of 0 to 20% by mass, and still more preferably 0. It is in the range of ˜15% by mass, particularly preferably in the range of 0 to 10% by mass.

  In the case of a polymer structural unit (repeating structural unit) constructed by polymerizing the monomer represented by formula (III), it is preferably in the range of 0 to 30% by mass, more preferably 0 to 20% by mass. Is more preferably in the range of 0 to 15% by mass, particularly preferably in the range of 0 to 10% by mass.

  The method for producing the lactone ring-containing polymer is not particularly limited, but preferably the polymer obtained after obtaining a polymer having a hydroxyl group (hydroxyl group) and an ester group in the molecular chain by a polymerization step. A lactone ring-containing polymer can be obtained by performing a lactone cyclization condensation step of introducing a lactone ring structure into the polymer by heat treatment.

(Matting agent)
In this invention, microparticles | fine-particles can be contained in a phase difference film as a mat agent, and when this phase difference film is a elongate film, conveyance and winding can be made easy.

  The particle size of the matting agent is preferably 10 nm to 0.1 μm of primary particles or secondary particles. A substantially spherical matting agent having a primary particle acicular ratio of 1.1 or less is preferably used.

  As the fine particles, those containing silicon are preferable, and silicon dioxide is particularly preferable. Preferred fine particles of silicon dioxide for the present invention include, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (Nippon Aerosil Co., Ltd.) manufactured by Nippon Aerosil Co., Ltd. What is marketed by a brand name can be mentioned, Aerosil 200V, R972, R972V, R974, R202, R812 can be used preferably. Examples of polymer fine particles include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. Examples include Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.). Can do.

  The fine particles of silicon dioxide preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / L or more. The average diameter of the primary particles is more preferably 5 to 16 nm, further preferably 5 to 12 nm. A smaller primary particle average diameter is preferred because haze is low. The apparent specific gravity is preferably 90 to 200 g / L or more, and more preferably 100 to 200 g / L or more. Higher apparent specific gravity makes it possible to produce a high-concentration fine particle dispersion, which is preferable because no haze or aggregates are generated.

The addition amount of the matting agent in the present invention is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and still more preferably 0.08 to 0.16 g per 1 m ^{2 of the} retardation film.

(Other additives)
In addition, thermal stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and alumina, and alkaline earth metal salts such as calcium and magnesium may be added. Further, a surfactant, a peeling accelerator, an antistatic agent, a flame retardant, a lubricant, an oil agent and the like may be added.

<Manufacture of raw film>
In the present application, the film before oblique stretching is referred to as “raw film”. A long film stretched in an oblique direction so as to have an in-plane slow axis in an oblique direction with respect to the conveying direction of the long film is referred to as a “retardation film”.

  The raw film according to the present invention may be produced by either a solution casting method or a melt casting method. Hereinafter, the solution casting method will be described. As the film raw material, the above-described thermoplastic resin can be used. In the following, a method for producing a retardation film containing cellulose ester as a main component will be described as a representative example.

  The production of the raw film according to the present invention is a step of preparing a dope by dissolving an additive such as cellulose ester and the plasticizer in a solvent, and a step of casting the dope on a belt-shaped or drum-shaped metal support. , A process of drying the cast dope as a web, a process of peeling from the metal support, a process of stretching, a process of further drying, a process of further heat treating the obtained film if necessary, and a process of winding after cooling. Is called. The raw film according to the present invention preferably contains 60 to 95% by mass of cellulose ester in the solid content.

  The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  Organic solvents that dissolve cellulose esters and are useful for forming cellulose ester solutions or dopes include chlorinated organic solvents and non-chlorinated organic solvents. Methylene chloride (methylene chloride) can be mentioned as a chlorinated organic solvent, and it is suitable for dissolving cellulose esters, particularly cellulose triacetate. Due to recent environmental problems, the use of non-chlorine organic solvents has been studied. Examples of the non-chlorine organic solvent include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1, Examples include 1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, and the like. When these organic solvents are used for cellulose triacetate, a dissolution method at room temperature can be used, but an insoluble material can be obtained by using a dissolution method such as a high-temperature dissolution method, a cooling dissolution method, or a high-pressure dissolution method. Can be reduced, which is preferable. Methylene chloride can be used for cellulose esters other than cellulose triacetate, but methyl acetate, ethyl acetate, and acetone are preferably used. Particularly preferred is methyl acetate. In the present invention, an organic solvent having good solubility with respect to the cellulose ester is referred to as a good solvent, and has a main effect on dissolution, and an organic solvent used in a large amount among them is a main (organic) solvent or a main ( Organic) solvent.

  The dope used in the present invention preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. These are gelling solvents that make dope film (web) gel when the dope is cast on a metal support and the solvent starts to evaporate and the ratio of alcohol increases, making the web strong and easy to peel off from the metal support. When these ratios are small, there is also a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Of these, ethanol is preferred because it has excellent dope stability, has a relatively low boiling point, and has good drying properties. These organic solvents are called poor solvents because they are not soluble in cellulose esters alone.

  It is preferable that the concentration of the cellulose ester in the dope is adjusted to 15 to 30% by mass and the dope viscosity is adjusted to a range of 100 to 500 Pa · s in order to obtain good film surface quality.

  A general method can be used as a dissolution method of the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamaco. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature with the addition of a solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

A bright spot foreign material is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate. The preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%. The temperature at the peeling position on the metal support is preferably −50 to 40 ° C., more preferably 10 to 40 ° C., and most preferably 15 to 30 ° C.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Moreover, in the drying process of the cellulose ester film, the web is peeled off from the metal support, further dried, and dried until the residual solvent amount is 0.5% by mass or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  When peeling from the metal support, the web is stretched in the longitudinal direction due to the peeling tension and the subsequent conveying tension. Therefore, in the present invention, when peeling the web from the casting support, the peeling and conveying tensions are reduced as much as possible. It is preferable to carry out in the state. Specifically, for example, it is effective to set it to 50 to 170 N / m or less. At that time, it is preferable to apply a cold air of 20 ° C. or less to fix the web rapidly.

  Next, the dried film can be used as a raw film (raw film) according to the present invention, and stretched at a desired angle by the above-described oblique stretching tenter according to the present invention to obtain a retardation film.

<Method for producing retardation film>
As a method for producing the retardation film of the present invention, various methods can be adopted, so as to have an in-plane slow axis at an angle within a range of 10 to 45 ° with respect to the conveying direction of the long film. After stretching in the oblique direction, the grip means causes the both ends of the long film to be at an angle in the range of −90 to −70 ° with respect to the transport direction and at a stretch ratio in the range of 0 to 20%. It is preferable that it is the manufacturing method of the aspect extended | stretched.

  Moreover, it is preferable that it is a manufacturing method controlled so that it may become the elongate phase difference film in which an in-plane slow axis has an angle variation in the range of +/- 0.5 degree with respect to the film width direction.

  In the present application, the film before oblique stretching is referred to as “raw film”. A long film stretched in an oblique direction so as to have an in-plane slow axis in an oblique direction with respect to the conveying direction of the long film is referred to as “film F”.

  In addition, the conveyance direction when “stretching both ends of the film at an angle within a range of −90 to −70 ° with respect to the conveyance direction and a stretching ratio within a range of 0 to 20% by the gripping means” Is a transport direction after giving an in-plane slow axis in a range of 10 to 45 ° with respect to the transport direction of the film by obliquely stretching a long film, and means the direction of DR2 in FIG. To do.

  Furthermore, a positive or negative sign is attached to an angle formed clockwise or counterclockwise on the film surface with respect to the transport direction, but the positive sign is not limited to either clockwise or counterclockwise.

  “Stretching both ends of the film at an angle in the range of −90 to −70 ° with respect to the conveyance direction” means, for example, when the clockwise direction is the positive direction with respect to the conveyance direction, When an in-plane slow axis is given to the film in the range of 10 to 45 ° clockwise on the film surface with respect to the transport direction, the film is stretched in a direction of 70 to 90 ° counterclockwise with respect to the transport direction. Means. On the other hand, when the clockwise direction is negative with respect to the transport direction, an in-plane slow axis is imparted to the film in the range of 10 to 45 ° counterclockwise on the film surface with respect to the transport direction by oblique stretching. In this case, after oblique stretching, the film is stretched in the direction of 70 to 90 ° clockwise with respect to the transport direction.

  In the present application, the “long shape” means a film having a length of at least about 5 times the width of the film, preferably a length of 10 times or more, specifically a roll. It can be a film roll having a length that can be stored or transported by being wound into a shape.

  In the manufacturing method of a long film, a film can be manufactured to desired arbitrary length by manufacturing a film continuously. The method for producing a retardation film may be wound around a core once after film formation and supplied to an oblique stretching process after forming a wound body, or without being wound up after film formation. You may supply to the diagonal stretch process continuously from a film | membrane process. It is preferable to perform the film forming step and the oblique stretching step continuously because the film thickness after the stretching and the result of the optical value are fed back to change the film forming conditions to obtain a desired retardation film.

  The film F according to the present invention is stretched in an oblique direction so as to have an in-plane slow axis in a direction that is neither the orthogonal direction nor the orthogonal direction of the long film. It is obtained by stretching at an angle exceeding 0 ° and less than 90 °. Here, the angle with respect to the film conveyance direction is an angle in the slow axis direction in the film plane.

  Since the slow axis is usually expressed in the stretching direction or a direction perpendicular to the stretching direction, in the production method of the present invention, by stretching at an angle of more than 0 ° and less than 90 ° with respect to the film extension direction, A film F having such an in-plane slow axis can be produced.

  The angle (θ) formed between the transport direction of the film F and the in-plane slow axis can be arbitrarily set within a range of 10 to 45 °, more preferably 20 to 40 °, and more preferably Preferably it is 25 degrees-35 degrees.

  The retardation film of the present invention is long and rolled up, and the in-plane slow axis of the film faces 15 to 75 ° with respect to the long direction, preferably 30 to 60 °. Further, it is preferable that the surface is oriented in the direction of 45 ° ± 5 °.

  The raw film can be obtained by a known method, for example, a solution cast molding method, an extrusion molding method, an inflation molding method, or the like. Among these, the solution cast molding method is excellent in the flatness and transparency of the film, and the extrusion molding method makes it easy to reduce the retardation Rt in the thickness direction after oblique stretching, and the amount of residual volatile components is small and the film dimensions are small. It is preferable because it is excellent in stability. This raw film may be a single layer or a laminated film of two or more layers. The laminated film can be obtained by a known method such as a coextrusion molding method, a co-casting molding method, a film lamination method, or a coating method. Of these, the coextrusion molding method and the co-casting molding method are preferable.

  The thickness unevenness σm in the flow direction of the elongated raw film subjected to stretching maintains the film take-up tension at the entrance of the oblique stretching tenter, and has optical characteristics such as in-plane slow axis direction and retardation. From the viewpoint of stabilization, it is necessary to be less than 0.30 μm, preferably less than 0.25 μm, more preferably less than 0.20 μm. When σm is 0.30 μm or more, variations in optical properties such as retardation of the retardation film and in-plane slow axis direction are remarkably deteriorated.

  Moreover, the film which has the thickness gradient of the width direction may be supplied as a raw film. The thickness gradient of the raw film so that the film thickness can be made the most uniform at the position where stretching has been completed is empirically determined by stretching films with various thickness gradients experimentally. Can be sought. The gradient of the thickness of the raw film can be adjusted, for example, so that the thickness of the end portion on the thick side is about 0.5 to 3% thicker than the end portion on the thin side. it can.

  Although the width | variety of a raw film is not specifically limited, 500-4000 mm, Preferably it can be 1000-2000 mm. The total thickness of the film is not particularly limited, but is preferably in the range of 20 to 400 μm, preferably 20 to 200 μm.

  A preferable elastic modulus at a stretching temperature at the time of oblique stretching of the raw film is 0.01 Mpa or more and 5000 Mpa or less, more preferably 0.1 Mpa or more and 500 Mpa or less, expressed as Young's modulus. If the elastic modulus is too low, the shrinkage rate during stretching and after stretching will be low and wrinkles will be difficult to disappear, and if it is too high, the tension applied during stretching will increase, increasing the strength of the part holding both side edges of the film. This necessitates an increase in the load on the tenter.

<Stretching with an oblique stretching tenter>
An oblique stretching apparatus (obliquely stretched tenter) is used in order to impart orientation to the long original film subjected to stretching of the present invention. The obliquely stretched tenter of the present invention can freely set the in-plane slow axis direction of the film by changing the rail pattern in various ways. A film stretching apparatus that can be oriented and can control the film thickness and retardation with high accuracy is preferable.

  FIG. 1 is a schematic diagram of a tenter capable of oblique stretching used in the method for producing a retardation film of the present invention. However, this is an example, and the present invention is not limited to this.

  The original film 1 whose direction is controlled by the guide roll 8-1 on the tenter entrance side is held at the position of the film holding start point 2-1 on the right side and the film holding start point 2-2 on the left side. The film is conveyed and stretched by the tenter 4 in the oblique direction indicated by the locus 3-1 of the right film holding means and the locus 3-2 of the left film holding means, and the right film holding end point 5- 1. Grasping is released by the film holding end point 5-2 on the left side, and conveyance is controlled by the guide roll 8-2 on the tenter outlet side, so that the obliquely stretched film 6 is formed. In the figure, the original film is stretched obliquely at an angle of the film stretching direction 9 with respect to the film feeding direction 7-1.

In the present invention, the distances X ₁ and X ₂ between the main shaft position of the guide roll 8-1 closest to the entrance of the obliquely stretched tenter and the gripping tool at the entrance of the obliquely stretched tenter need to be 20 to 100 cm. Yes, by maintaining the distance, the plane of the film can be maintained when the film is gripped, and the optical characteristics such as the in-plane slow axis direction θs and retardation of the stretched film in the longitudinal direction can be stabilized. Preferably it is 20-60 cm, More preferably, it is 20-40 cm. Wherein, X ₁ is the distance of the main shaft position of the guide roll 8-1 and the right film holding start point 2-1 gripper in (clip gripping portion), X ₂ is a guide roll 8-1 spindle It is the distance between the position and the gripping tool (clip gripping portion) at the film holding start point 2-2 on the left side.

X ₁ and X ₂ may be either X ₁ = X ₂ or X ₁ ≠ X ₂ , but preferably X ₁ = X ₂ . In the present invention, both X ₁ and X ₂ need to be in the range of 20 to 100 cm.

  When the distance between the main shaft position of the guide roll 8-1 closest to the entrance portion of the obliquely stretched tenter and the gripping tool at the entrance portion of the obliquely stretched tenter becomes longer than 100 cm, the in-plane slow axis direction θs in the longitudinal direction of the retardation film Variation in optical properties such as retardation and retardation is significantly deteriorated.

  In order to set the distance between the main shaft position of the guide roll 8-1 closest to the entrance of the obliquely stretched tenter and the gripping tool of the obliquely stretched tenter to the above range, a mechanism capable of adjusting the position of the guide roll and the clip gripping part; The length of the gripping tool in the conveying direction is 1 to 5 inches (1 inch is 2.54 cm), and the diameter of the guide roll 8-1 closest to the entrance portion of the obliquely stretched tenter is 1 to 20 cm. And a mechanism that can further install a roll in the vicinity of the entrance of the obliquely stretched tenter.

  The retardation film of the present invention is produced using the above-mentioned tenter that can be stretched obliquely. This tenter is prepared by subjecting a long film to an advancing direction (the middle point in the film width direction) in an oven heating environment. It is a device that widens in an oblique direction with respect to (moving direction). This tenter includes an oven, a pair of rails on the left and right on which a gripping tool for transporting the film travels, and a number of gripping tools that travel on the rails. Both ends of the film fed out from the film roll and sequentially supplied to the entrance portion of the tenter are gripped by a gripping tool, the film is guided into the oven, and the film is released from the gripping tool at the exit portion of the tenter. The film released from the gripping tool is wound around the core. Each of the pair of rails has an endless continuous track, and the gripping tool which has released the grip of the film at the exit portion of the tenter travels outside and is sequentially returned to the entrance portion.

  The rail shape of the tenter has an asymmetric shape on the left and right depending on the in-plane slow axis direction θs, the draw ratio, etc. given to the retardation film to be manufactured, and can be finely adjusted manually or automatically. It has become. In the present invention, a long thermoplastic resin film is stretched, and the in-plane slow axis direction θs can be set at an arbitrary angle with respect to the winding direction after stretching. In the present invention, the gripping tool of the tenter is configured to travel at a constant speed with a certain distance from the front and rear gripping tools.

  The traveling speed of the gripping tool can be selected as appropriate, but is usually 10 to 100 m / min. The difference in travel speed between the pair of left and right grippers is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less of the travel speed. This is because if there is a difference in the traveling speed between the left and right sides of the film at the exit of the stretching process, wrinkles and shifts will occur at the exit of the stretching process, so the speed difference between the right and left gripping tools is required to be substantially the same speed. Because. In general tenter devices, etc., there are speed irregularities that occur on the order of seconds or less depending on the period of the sprocket teeth that drive the chain, the frequency of the drive motor, etc. This does not correspond to the speed difference described in the invention.

Moreover, in the diagonally stretched tenter used in the present invention, it is preferable that the positions of the rail portions and the rail connecting portions can be freely set. Therefore, when an arbitrary entrance width and exit width are set, the stretch ratio corresponding to this is set. be able to. (The circled portion in FIG. 2 below is an example of a connecting portion.)
In the obliquely stretched tenter used in the present invention, a large bending rate is often required for the rail that regulates the trajectory of the gripping tool. In order to avoid interference between gripping tools due to sudden bending or local stress concentration, it is desirable that the trajectory of the gripping tool draws an arc at the bent portion.

  FIG. 2 shows a rail track (rail pattern) of a tenter used in the manufacturing method of the present invention. The travel direction DR1 at the tenter inlet of the original film is different from the travel direction DR2 at the tenter exit side of the stretched film, which makes it possible to obtain a wide and uniform optical characteristic. The feeding angle θi is an angle formed by the traveling direction D1 at the tenter entrance and the traveling direction DR2 on the tenter exit side of the stretched film. In the present invention, as described above, in order to produce a retardation film having an in-plane slow axis direction θs in which the angle between the extension direction and the slow axis exceeds 0 and less than 90 °, the feeding angle θi is 10 ° <θi <60 °, preferably 15 ° <θi <50 °. By setting the feeding angle θi in the above range, the variation in the optical characteristics in the width direction of the obtained film becomes good (smaller).

  The long film is sequentially gripped at both ends (both sides) by the left and right grippers at the tenter entrance (position a), and travels as the grippers travel. The left and right grips CL, CR facing the direction of the film travel (DR1) at the tenter entrance (position a) run on the left-right asymmetric rail, preheating zone, stretching Pass through an oven with zones and cooling zones. Here, “substantially perpendicular” indicates that the angle formed by the straight line connecting the aforementioned gripping tools CL and CR and the film feeding direction DR1 is within 90 ± 1 °.

  The preheating zone refers to a section in which the vehicle travels while maintaining a constant interval between the gripping tools gripping both ends at the oven entrance. The stretching zone refers to an interval until the gap between the gripping tools gripping both ends starts to become constant again. In addition, the cooling zone refers to a section in which the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg ° C. of the thermoplastic resin constituting the film during a period in which the interval between the gripping tools after the stretching zone becomes constant again. .

  The temperature of each zone is set to Tg to Tg + 30 ° C., the temperature of the stretching zone is set to Tg to Tg + 30 ° C., and the temperature of the cooling zone is set to Tg−30 to Tg ° C. with respect to the glass transition temperature Tg of the thermoplastic resin. It is preferable to do.

  In order to control the thickness unevenness in the width direction, a temperature difference may be given in the width direction in the stretching zone. In order to create a temperature difference in the width direction in the stretching zone, a method of adjusting the opening degree of the nozzle for sending warm air into the temperature-controlled room so as to make a difference in the width direction, or controlling the heating by arranging the heaters in the width direction is known. Can be used. The length of the preheating zone, the stretching zone and the cooling zone can be appropriately selected. The length of the preheating zone is usually 100 to 150% and the length of the fixed zone is usually 50 to 100% with respect to the length of the stretching zone. .

  Further, in order to solve the occurrence of wrinkles and shifts in the retardation film, the support of the film is maintained at the time of stretching, and the film is stretched in the state where the volatile content is 5% by volume or more, and then the volatile content is reduced while shrinking. It is also preferable to reduce the rate. To maintain the support of the film means to grip both side edges without impairing the film property of the film. As for the volatile content, the state of 5% by volume or more may always be maintained in the stretching operation process, and the state of the volatile content is maintained at 5% by volume or more only in a part of the stretching operation process. May be. In the latter case, it is preferable that the entrance position is a starting point, and that the section of 50% or more of the entire stretching section and the volatile content rate are 12% by volume or more. In any case, it is preferable to have a volatile content of 12% by volume or more before stretching. Here, the volatile fraction (unit: volume%) represents the volume of the volatile component contained per unit volume of the film, and is a value obtained by dividing the volatile component volume by the film volume.

  The draw ratio R (W / W0) in the drawing step is preferably 1.3 to 3.0, more preferably 1.5 to 2.5. If the draw ratio is within this range, the thickness unevenness in the width direction is preferably reduced. In the stretching zone of the oblique stretching tenter, if the stretching temperature is differentiated in the width direction, the thickness unevenness in the width direction can be further improved. W0 represents the width of the film before stretching, and W represents the width of the film after stretching.

  The guide roll closest to the entrance of the tenter is a follower roll that guides the travel of the film, and is rotatably supported by bearings (not shown). A known material can be used for the roll, but it is preferable to reduce the weight by applying a ceramic coat to prevent the film from being damaged or by applying chrome plating to a light metal such as aluminum. . This roll is provided in order to stabilize the track when the film travels.

  Moreover, it is preferable that one of the rolls on the upstream side of the roll is nipped by pressing the rubber roll. This is because such a nip roll can suppress fluctuations in the drawing tension in the film flow direction.

  A pair of bearing portions at both ends (left and right) of the guide roll closest to the entrance of the tenter are provided with a first tension detecting device and a second film tension detecting device for detecting the tension generated in the film in the roll. It has been. For example, a load cell can be used as the film tension detection device. As the load cell, a known tensile or compression type can be used. A load cell is a device that detects a load acting on an applied point by converting it into an electrical signal using a strain gauge attached to the strain generating body.

  The load cell is installed on the left and right bearings of the guide roll closest to the entrance of the diagonally stretched tenter, so that the force exerted on the roll by the running film, i.e., the tension in the film traveling direction that is generated near both side edges of the film, is measured. It is detected independently on the left and right. In addition, a strain gauge may be directly attached to the support that constitutes the bearing portion of the roll, and the load, that is, the film tension may be detected based on the strain generated in the support. The relationship between the generated strain and the film tension is measured in advance and is known.

  The film tension detection device as described above is provided so that the tension in the vicinity of both side edges of the film in the guide roll closest to the entrance of the oblique stretching tenter is detected because the position and direction of the film is the same as that of the film stretching device. If there is a deviation with respect to the position and direction of the entrance, depending on the amount of deviation, there will be a difference in the tension in the vicinity of both side edges of the film in the guide roll closest to the entrance of the obliquely stretched tenter. This is because the degree of deviation is determined by detecting this tension difference. If the position and direction of the film are appropriate in relation to the position and direction of the inlet portion of the film stretching apparatus, the load acting on the roll will be roughly equal on the left and right, and if the positions are misaligned, the left and right films There is a difference in tension.

  Therefore, if the film position and angle are adjusted appropriately so that the difference in film tension between the left and right sides of the guide roll closest to the entrance of the oblique stretching tenter is equal, gripping by the gripping tool at the entrance of the film stretching apparatus is stable. In addition, the occurrence of obstacles such as removal of the gripping tool can be reduced, and the physical properties in the width direction of the film after oblique stretching by the film stretching apparatus can be stabilized.

  In order to cope with fine adjustments in the in-plane slow axis direction and product variations, it is necessary to adjust the angle between the film traveling direction at the entrance of the oblique stretching tenter and the film traveling direction at the exit of the oblique stretching tenter. In that case, it is preferable from a viewpoint of productivity or a yield to perform film forming and diagonal stretch continuously. When the film forming process, the oblique stretching process, and the winding process are successively performed, it is preferable that the film traveling direction in the film forming process and the winding process coincide with each other in that the width of the process can be reduced. For such a process, in order to change the film transport direction in order to guide the formed film to the oblique stretching tenter inlet and / or to return the film exiting from the oblique stretching tenter outlet to the winder direction. A method for changing the film transport direction is required. As a device for changing the film transport direction, a known method such as an air flow roll can be used. It is preferable that the apparatus (winder apparatus, accumulator apparatus, drive apparatus, etc.) after the obliquely extending tenter exit is slidable in the lateral direction.

  FIGS. 3 and 4 show manufacturing patterns of the oblique stretching according to the various inventions described above.

  In the drawing, a film feeding device 10, a transport direction changing device 11, a winding device 12, and a film forming device 13 are shown.

  The film feeding device 10 is slidable and pivotable so that the film can be fed at a predetermined angle with respect to the obliquely stretched tenter entrance, or the film feeding device 10 is slidable, and the transport direction changing device 11, it is preferable that the film can be sent out to the entrance of the obliquely stretched tenter. By configuring the film feeding device and the transport direction changing device as described above, it becomes possible to further narrow the width of the entire manufacturing apparatus, and to finely control the film feeding position and angle, It becomes possible to obtain a retardation film having small variations in film thickness and optical value. Further, by making the film feeding device and the transport direction changing device movable, it is possible to effectively prevent the left and right clips from being caught in the film.

  By forming the winding device 12 so that the film can be pulled at a predetermined angle with respect to the outlet of the obliquely stretched tenter, it is possible to finely control the film take-up position and angle, and there are variations in film thickness and optical value. A small retardation film can be obtained. Therefore, the generation of wrinkles in the film can be effectively prevented, and the winding property of the film is improved, so that the film can be wound up in a long length. In the present invention, the take-up tension T (N / m) of the stretched film needs to be adjusted between 100 N / m <T <300 N / m, preferably 150 N / m <T <250 N / m.

  When the take-up tension is 100 N / m or less, sagging and wrinkles of the film are likely to occur, and the retardation and the profile in the width direction of the in-plane slow axis direction θs also deteriorate. On the other hand, when the take-up tension is 300 N / m or more, the variation in the in-plane slow axis direction θ in the width direction is deteriorated, and the width yield (taking efficiency in the width direction) is deteriorated.

  In the present invention, it is necessary to control the fluctuation of the take-up tension T with an accuracy of less than ± 5%, preferably less than ± 3%. When the fluctuation of the take-up tension T is ± 5% or more, the variation in the optical characteristics in the width direction and the flow direction becomes large. As a method for controlling the fluctuation of the take-up tension T within the above range, general PID control is performed so that the load applied to the first roll at the tenter outlet, that is, the film tension is measured and the value is kept constant. A method of controlling the rotation speed of the take-up roll by a method is mentioned. Examples of the method for measuring the load include a method in which a load cell is attached to a bearing portion of a roll and a load applied to the roll, that is, a film tension is measured. As the load cell, a known tensile type or compression type can be used.

<Stretching in a direction at a predetermined angle with respect to the transport direction>
In the present invention, after stretching in an oblique direction so as to have an in-plane slow axis at an angle in the range of 10 to 45 ° with respect to the transport direction of the long film, both ends of the film are transported in the transport direction by gripping means. The film may be stretched at an angle in the range of -90 to -70 ° with respect to the stretching ratio and in a stretch ratio of 0 to 20%. Therefore, in the present invention, a stretching apparatus that can stretch in a direction orthogonal to the transport direction or in an oblique direction may be used.

  The stretching device can change the in-plane slow axis direction of the film freely by changing the rail pattern in various ways. A film stretching apparatus that can be oriented with high precision and that can control film thickness and retardation with high precision is preferable.

  The stretched film is released from the tenter outlet after being gripped by the gripper, and after being trimmed at both ends (both sides) of the film, the film is sequentially wound on a winding core (winding roll) to form a retardation film ( A stretched film).

  Moreover, you may trim the both ends of the film currently hold | gripped with the holding tool of a tenter before winding up to a winding roll as needed. Moreover, before winding up, in order to prevent blocking between films, a masking film may be piled up and wound up at the same time, or at least one of the retardation film (stretched film), preferably tape or the like at both ends. You may wind up while bonding. The masking film is not particularly limited as long as it can protect the film, and examples thereof include a polyethylene terephthalate film, a polyethylene film, and a polypropylene film.

  The variation of the in-plane retardation Ro of the retardation film (stretched film) of the present invention is 0.5 nm or less, preferably 0.3 nm or less, in at least 1300 mm in the width direction. By setting the variation of the in-plane retardation Ro within the above range, the display quality can be improved when used as a retardation film (stretched film) for a liquid crystal display device.

The optimum value of the in-plane retardation Ro of the retardation film (stretched film) of the present invention is selected depending on the design of the display device used. Incidentally, the Ro-plane slow axis direction of the refractive indices n _x and plane by a value obtained by multiplying the average thickness d of the film to the difference between the refractive index n _y in the direction perpendicular to the slow axis (Ro = (N _x -n _y ) × d).

  When incorporating the long retardation film (stretched film) of the present invention into a stereoscopic image display device, a λ / 4 plate having the following characteristics is preferable.

(Surface processed layer)
The retardation film of the present invention is characterized in that a hard coat layer is provided on the surface thereof.

  In the present invention, functional layers such as an antistatic layer, a backcoat layer, an antireflection layer, a slippery layer, an adhesive layer, an antiglare layer, and a barrier layer can be provided as the surface treatment layer.

<Hard coat layer>
The retardation film of the present invention is characterized in that a hard coat layer is provided on the surface thereof. The hard coat layer is preferably either a clear hard coat layer or an antiglare hard coat layer.

  As an embodiment of the present invention, it is preferable that the hard coat layer is a hard coat layer formed using a resin containing an active energy ray-curable resin from the viewpoint of manifesting the effects of the present invention. Furthermore, it is preferable that the hard coat layer is formed using a coating solution containing an acrylate ester having three or four acryloyl groups.

  When the hard coat layer is formed using a coating solution, the amount of solvent contained in the coating solution is preferably less than 10% by mass. Moreover, it is preferable that the solvent which the said coating liquid contains is ethanol or methanol. On the other hand, it is also preferable that the coating liquid does not contain water and an organic solvent.

  The hard coat layer used in the present invention is provided on at least one surface of the retardation film. In the present invention, it is also preferable that an antireflection layer including at least a low refractive index layer is provided on the hard coat layer. In particular, in the case of in-vehicle car navigation, in order to further improve the visibility, it is preferable to provide an antireflection layer on the antiglare hard coat layer.

  When the hard coat layer used in the present invention is anti-glare, it has a fine uneven shape on the surface. The fine uneven shape is formed by containing fine particles in the hard coat layer, and is as follows. It can be formed by containing fine particles having an average particle size of 0.01 to 4 μm in the hard coat layer. Further, as will be described later, as the surface roughness of the outermost surface of the antireflection layer provided on the antiglare hard coat layer, the centerline average roughness (Ra) defined by JIS B 0601 is 0.08. It is preferable to adjust to a range of ˜0.5 μm.

  In the case of the clear hard coat layer, it is a clear hard coat layer having a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 μm, and Ra is 0.002 to 0.05 μm. It is preferable. The center line average roughness (Ra) is preferably measured by an optical interference type surface roughness measuring instrument, and can be measured, for example, using a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.

  As particles contained in the antiglare hard coat layer used in the present invention, for example, inorganic or organic fine particles are used.

  Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate.

  The organic fine particles include polymethyl methacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicone resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, and polyfluoroethylene resin fine particles.

  In the present invention, silicon oxide fine particles or polystyrene resin fine particles are particularly preferable.

  The inorganic or organic fine particles described above are preferably used in addition to a coating composition containing a resin or the like used for producing an antiglare hard coat layer.

  In order to impart anti-glare properties to the anti-glare hard coat layer used in the present invention, the content of the inorganic or organic fine particles is set to 0.100 parts by mass with respect to 100 parts by mass of the resin for preparing the anti-glare hard coat layer. 1 mass part-30 mass parts are preferable, More preferably, it is mix | blending so that it may become 0.1 mass part-20 mass parts. In order to give a more preferable antiglare effect, it is preferable to use 1 part by mass to 15 parts by mass of fine particles having an average particle size of 0.1 μm to 1 μm with respect to 100 parts by mass of the resin for preparing the antiglare hard coat layer. . It is also preferable to use two or more kinds of fine particles having different average particle diameters.

The antiglare hard coat layer used in the present invention preferably contains an antistatic agent, and examples of the antistatic agent include Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, A conductive material containing at least one element selected from the group consisting of W and V as a main component and having a volume resistivity of 10 ⁷ Ω · cm or less is preferable.

  Examples of the antistatic agent include metal oxides and composite oxides having the above elements.

Examples of metal oxides are preferably ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or a composite oxide thereof. In particular, ZnO, In ₂ O ₃ , TiO ₂ and SnO ₂ are preferred. Examples of containing different atoms include, for example, addition of Al, In, etc. to ZnO, addition of Nb, Ta, etc. to TiO ₂ , and addition of Sb, Nb, halogen elements, etc. to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

In addition, the volume resistivity of these metal oxide powders having conductivity is 10 ⁷ Ω · cm or less, particularly 10 ⁵ Ω · cm or less.

  From the viewpoint of imparting sufficient durability and impact resistance, the film thickness of the clear hard coat layer or the antiglare hard coat layer is preferably in the range of 0.5 to 15 μm, more preferably 1.0 to 7 μm. .

(Active energy ray curable resin)
The hard coat layer used in the present invention preferably contains an active energy ray-curable resin that is cured by irradiation with active energy rays such as ultraviolet rays.

  The active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an active energy ray other than an ultraviolet ray or an electron beam may be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as methacrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Only acrylates are displayed as such), and can be easily obtained by reacting an acrylate monomer having a hydroxyl group (hydroxyl group) such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Corporation) described in JP-A-59-151110 is preferably used.

  The UV curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group (hydroxyl group) or a carboxyl group at the end of the polyester. JP, 59-151112, A).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group (hydroxyl group) of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.

  As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, useful epoxy-based active energy ray reactive compounds are shown.

(A) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by reaction of epichlorohydrin and bisphenol A)
(B) a compound having a glycidyl ether group by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs such as bisphenol A (c) glycidyl ether of 4,4'-methylenebisphenol (D) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin (e) Compound having alicyclic epoxide, for example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) ) Adipate, bis (3,4-epoxy-6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo Xanthcarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3', 4'-epoxy-1 ' -Methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3 ', 4'-epoxy-6'-methyl-1'-cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5 ', 5'-spiro-3 ", 4" -epoxy) cyclohexane-meta-dioxane (f) diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, diglycidyl Hexahydrophthalate, diglycidylf (G) Diglycidyl ether of glycol, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) di Glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (h) Glycidyl ester of polymer acid, for example, polyglycidyl ester of polyacrylic acid, polyester diglycidyl ester (i) Polyhydric alcohol Glycidyl ethers such as glycerin triglycidyl ether, trimethylolpropane triglycidyl Ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether (j) As the diglycidyl ether of 2-fluoroalkyl-1,2-diol, Similar to the compound examples given for the fluorine-containing epoxy compound of the fluorine-containing resin (k) As the fluorine-containing alkane-terminated diol glycidyl ether, the fluorine-containing epoxy compound of the fluorine-containing resin of the low refractive index substance can be exemplified. .

  The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.

  In the case where the above epoxy compound is cured with active energy rays, it is effective to use a compound having a polyfunctional epoxy group (h) or (i) in order to increase the hardness.

  The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy-based active energy ray-reactive compound is a compound capable of releasing a cationic polymerization initiator by irradiation with active energy rays, and particularly preferably a cation by irradiation. It is a group of double salts of onium salts that release Lewis acids capable of initiating polymerization.

  The active energy ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is not affected by oxygen in the reaction system, and is therefore a preferred active energy ray reactive resin.

  The active energy ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or a photosensitizer that releases a substance that initiates cationic polymerization upon irradiation with active energy rays. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  A typical example is a compound represented by the following general formula (a).

General formula (a): [(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{w +} [MeX _v ] ^w−
Wherein cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeX _v ] ^w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), tetra Examples thereof include fluoroarsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

  Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic halonium salts described in JP-A Nos. 50-151996 and 50-158680 are particularly useful. VIA group aromatic onium salts described in Kaikai 50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56-149402, Preference is given to oxosulfoxonium salts described in 57-192429 and the like, aromatic diazonium salts described in JP-B-49-17040, thiopyridium salts described in US Pat. No. 4,139,655 and the like. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  In the case of an active energy ray-reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photosensitizer and photoinitiator used for the active energy ray-reactive compound are sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet-reactive compound, and preferably Is 1 to 10 parts by mass. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the active energy ray-curable resin composition useful in the present invention, the polymerization initiator is generally used in an amount of 0.1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable epoxy resin (prepolymer). More preferably, addition in the range of 1 to 10 parts by mass is preferable.

  An epoxy resin can be used in combination with the urethane acrylate type resin, polyether acrylate type resin, or the like. In this case, it is preferable to use an active energy ray radical polymerization initiator and an active energy ray cationic polymerization initiator in combination.

  Moreover, an oxetane compound can also be used for the hard-coat layer used for this invention. The oxetane compound used is a compound having a three-membered oxetane ring containing oxygen or sulfur. Among them, a compound having an oxetane ring containing oxygen is preferable. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, or an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl -3 chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, 3,3-dimethyloxetane and the like. In the present invention, any of a monomer, an oligomer and a polymer may be used.

  As an embodiment of the present invention, it is preferable that the hard coat layer is a hard coat layer formed using a resin containing an active energy ray-curable resin from the viewpoint of manifesting the effects of the present invention. Furthermore, it is preferable that the hard coat layer is formed using a coating solution containing an acrylate ester having three or four acryloyl groups.

  When the hard coat layer used in the present invention contains an active energy ray-curable resin, the active energy ray irradiation method includes an antiglare hard coat layer and an antireflection layer (medium to high refractive index layer) on a support. In addition, the active energy ray may be irradiated after the coating of the low refractive index layer or the like, but the active energy ray is preferably irradiated when the hard coat layer is coated.

The active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, γ ray, etc., but ultraviolet ray and electron beam are preferable, especially easy handling and high energy. UV rays are preferred in that they can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated is preferably 20 mJ / cm ² or more, more preferably, a 50~10000mJ / cm ^2, particularly preferably 50~2000mJ / cm ^2.

  The ultraviolet irradiation may be performed every time one layer is provided for each of a plurality of layers (medium refractive index layer, high refractive index layer, low refractive index layer) constituting the hard coat layer and the antireflection layer described later. The film may be irradiated after lamination. Or you may irradiate combining these. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

  In order to initiate the photopolymerization or photocrosslinking reaction of the active energy ray-reactive compound used in the present invention, the active energy ray-reactive compound alone is initiated, but the polymerization induction period is long or the polymerization start is slow. Therefore, it is preferable to use a photosensitizer or a photoinitiator, which can accelerate the polymerization.

  When the hard coat layer used in the present invention contains an active energy ray-curable resin, a photoreaction initiator and a photosensitizer can be used during irradiation with active energy rays.

  Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. Moreover, when using a photoreactant for the synthesis | combination of an epoxy acrylate-type resin, sensitizers, such as n-butylamine, a triethylamine, a tri-n-butylphosphine, can be used. The amount of the photoreaction initiator and / or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying is preferably 1 to 10% by mass, particularly preferably 2%. .5 to 6% by mass.

  Moreover, when using ultraviolet curable resin as active energy ray curable resin, you may include the ultraviolet absorber mentioned later in the ultraviolet curable resin composition to such an extent that the photocuring of the said ultraviolet curable resin is not prevented.

  In order to increase the heat resistance of the hard coat layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  Examples of the ultraviolet curable resin include ADEKA OPTMER KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by ADEKA Corporation), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 )), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UC Corporation), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102 RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by DIC Corporation), Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sun Rad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), or other commercially available products can be used as appropriate.

  The coating composition containing the active energy ray-curable resin preferably has a solid content concentration of 10 to 95% by mass, and an appropriate concentration is selected depending on the coating method.

  The hard coat layer and antireflection layer used in the present invention also preferably contain a surfactant, and the surfactant is preferably a silicone-based or fluorine-based surfactant.

  As the silicone-based surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  A nonionic surfactant is a generic term for a system surfactant that does not have a group capable of dissociating into ions in an aqueous solution. In addition to a hydrophobic group, a hydroxyl group (hydroxyl group) of a polyhydric alcohol is used as a hydrophilic group. It has an oxyalkylene chain (polyoxyethylene) or the like as a hydrophilic group. The hydrophilicity increases as the number of alcoholic hydroxyl groups (hydroxyl groups) increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant according to the present invention is characterized by having dimethylpolysiloxane as a hydrophobic group.

  When a nonionic surfactant composed of a dimethylpolysiloxane having a hydrophobic group and a polyoxyalkylene having a hydrophilic group is used, unevenness of the antiglare hard coat layer and the low refractive index layer and antifouling property of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

  Specific examples of these nonionic surfactants include, for example, Nippon Unicar Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ- 2163, FZ-2164, FZ-2166, FZ-2191 and the like.

  Moreover, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a linear block copolymer. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle so as to cover the surface of the silica fine particle at a plurality of locations by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

  Specific examples thereof include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208 and the like manufactured by Nippon Unicar Co., Ltd.

  As the fluorine-based surfactant, a surfactant having a hydrophobic group having a perfluorocarbon chain can be used. As types, fluoroalkylcarboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, sodium 3- (fluoroalkyloxy) -1-alkylsulfonate, 3- (ω-fluoroalkanoyl-N-ethylamino) -1- Sodium propanesulfonate, N- (3-perfluorooctanesulfonamido) propyl-N, N-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonic acid Salt, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethyl Ruhonirugurishin salts, phosphoric acid bis (N- perfluorooctylsulfonyl -N- ethylamino ethyl) and the like. In the present invention, nonionic surfactants are preferred.

  These fluorosurfactants are commercially available under the trade names such as Megafac, F-Top, Surflon, Footagen, Unidyne, Florard, Zonyl and the like.

  A preferable addition amount is 0.01 to 3.0%, more preferably 0.02 to 1.0% per solid content contained in the coating liquid of the hard coat layer and the antireflection layer.

  Other surfactants can be used in combination. For example, anionic surfactants such as sulfonates, sulfates, phosphates, etc., and ethers having polyoxyethylene chain hydrophilic groups Type, ether ester type nonionic surfactants and the like may be used in combination.

  As the solvent for coating the hard coat layer according to the present invention, various solvents conventionally used for coating the hard coat layer can be used. In the present invention, a particularly preferred solvent is ethanol or methanol.

  The amount of solvent is preferably less than 10% by mass. More preferably, it is in the range of 5 to 8% by mass, or it is also preferred that no solvent is used and no solvent is used.

  When a monomer having 5 or more acrylic groups is used as the hard coat layer, streaks on the surface of the obliquely stretched retardation film are further emphasized. Further, when a nonpolar solvent such as acetone, PGME (propylene glycol monomethyl ether) or ethyl acetate is used, the residual stress in the oblique direction remaining in the obliquely stretched retardation film is strengthened to induce streaks on the film surface. In addition, when a wet heat durability test is performed on a film provided with a hard coat layer, a fluctuation value (maximum value) of the in-plane retardation Ro is obtained when a monomer having 5 or more acrylic groups or a nonpolar solvent as described above is used. The value of (minimum value) is wide and larger than 10 nm. This significantly deteriorates the display quality when the produced film is provided in a display device.

  As a coating method of the hard coat layer composition coating solution, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, an air doctor coater, a spray coat, an ink jet method can be used. . The coating amount is suitably 5 to 30 μm, preferably 10 to 20 μm in terms of wet film thickness. The coating speed is preferably 10 to 200 m / min.

  The hard coat layer composition is preferably applied and dried, and then irradiated with an active energy ray such as an ultraviolet ray or an electron beam and cured, but the irradiation time of the active energy ray is preferably 0.5 seconds to 5 minutes. More preferably, it is 3 seconds to 2 minutes in view of the curing efficiency, work efficiency, etc. of the ultraviolet curable resin.

<Antireflection layer>
The antireflection layer used in the present invention may have a single-layer structure composed of only a low refractive index layer, but it is also preferable to provide a multilayer refractive index layer. It has a hard coat layer on the retardation film, and can be laminated on the surface in consideration of the refractive index, the film thickness, the number of layers, the layer order, etc. so that the reflectance is reduced by optical interference. The antireflection layer is composed of a combination of a high refractive index layer having a higher refractive index than that of the support and a low refractive index layer having a lower refractive index than that of the support, and particularly preferably from three or more refractive index layers. An anti-reflection layer comprising three layers having different refractive indexes from the support side, a medium refractive index layer (having a higher refractive index than the support or the antiglare hard coat layer, and having a higher refractive index than the high refractive index layer). It is preferable that the layers are laminated in the order of (low layer) / high refractive index layer / low refractive index layer.

  Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.

  Examples of preferred layer structures of the antireflection layer used in the present invention are shown below. Here, / indicates that the layers are arranged in layers.

Retardation film / Clear hard coat layer / Low refractive index layer Retardation film / Clear hard coat layer / High refractive index layer / Low refractive index layer Retardation film / Clear hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Retardation film / Anti-glare hard coat layer / Low refractive index layer Retardation film / Anti-glare hard coat layer / High refractive index layer / Low refractive index layer Retardation film / Anti-glare hard coat layer / Medium Refractive Index Layer / High Refractive Index Layer / Low Refractive Index Layer An antifouling layer may be further provided on the outermost low refractive index layer so that dirt and fingerprints can be easily wiped off. As the antifouling layer, fluorine-containing organic compounds are preferably used.

As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. In the above layer structure, an intermediate layer may be provided as appropriate. For example, an antistatic layer containing conductive polymer fine particles (for example, crosslinked cation fine particles) or metal oxide fine particles (for example, SnO ₂ , ITO) is preferable.

<Low refractive index layer>
In the low refractive index layer used in the present invention, the following hollow spherical silica-based fine particles are preferably used.

(Hollow spherical silica-based fine particles)
The hollow spherical fine particles are: (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having a cavity inside, and the content is a solvent, gas or porous Cavity particles filled with a substance. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle diameter of such hollow spherical fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow spherical fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and are in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. Is desirable. These hollow spherical fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later. The inside of the composite particles may enter and the internal porosity may decrease, and the low refractive index effect may not be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. .

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. Moreover, components other than silica may be contained, and specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O _3. , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ and WO _3. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, a pore volume is small and particles having a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a material having a lower refractive index. is there.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Examples of the porous substance include those composed of the compounds exemplified for the porous particles. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow spherical fine particles, for example, the method for preparing complex oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow spherical fine particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound, or the like to a silicate solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. Can do. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using the seed particle dispersion, the pH of the seed particle dispersion is adjusted to 10 or more, and then the aqueous solution of the compound is added to the alkaline aqueous solution with stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and an inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to an oxide (MO _X ), and the molar ratio of MO _X / SiO ₂ is 0.05 to 2.0, Preferably it is in the range of 0.2-2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing the hollow particles, the molar ratio of MO _X / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  Further, when preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor comprising a silica protective film, a solvent in the silica protective film, and an undissolved porous solid, and the hollow particles When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organic silicon compound used for the silica protective film formed of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, such as acrylic group An alkoxysilane represented by a hydrocarbon group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or the ratio of water to the organic solvent is high, it is possible to form a silica protective film using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third step: Formation of silica coating layer In the third step, the porous particle dispersion prepared in the second step (in the case of hollow particles, the hollow particle precursor dispersion) contains a fluorine-substituted alkyl group-containing silane compound. By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, An alkoxysilane represented by a hydrocarbon group such as an acryl group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilanes, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particles (cavity particle precursor in the case of hollow particles) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the silica coating layer finally obtained has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of the hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. The refractive index of the low refractive index layer used in the present invention is preferably 1.30 to 1.50, and more preferably 1.35 to 1.44.

In the present invention, the commercially available SiO ₂ fine particles can be used. Specific examples of commercially available particles include P-4 manufactured by Catalytic Chemical Industry Co., Ltd.

  The content (mass) of the hollow spherical silica-based fine particles A having an outer shell layer and having a porous or hollow interior in the low refractive index layer coating solution is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass. % By mass.

(Tetraalkoxysilane compound or hydrolyzate thereof)
The low refractive index layer used in the present invention preferably contains a tetraalkoxysilane compound or a hydrolyzate thereof as a sol-gel material.

  As a material for the low refractive index layer used in the present invention, it is also preferable to use a silicon oxide having an organic group in addition to the inorganic silicon oxide. These are generally called sol-gel materials, but metal alcoholates, organoalkoxy metal compounds and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. Tetraalkoxysilane and its hydrolyzate are particularly preferable.

  In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  When hydrolyzing the tetraalkoxysilane, it is preferable to mix the inorganic fine particles in order to increase the film strength.

  The low refractive index layer used in the present invention preferably contains the silicon oxide and the following silane coupling agent.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Specific examples of the silane coupling agent include: Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-403, KBM-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE- 503, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-802, KBM-803 and the like.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  A specific method of surface treatment with a coupling agent is shown below.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the above-described silicon oxide particles and the surface of the silicon oxide having an organic group easily react, and a stronger film is formed. Moreover, you may add the hydrolyzed silane coupling agent in a coating liquid previously.

  The low refractive index layer can also contain a polymer in an amount of 5 to 50% by weight. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treating agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and by polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out by combining two or all of the above (1) to (3), and to carry out by combining (1) and (3) or (1) to (3) all combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out by chemical surface treatment alone or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the fine particles are made of SiO _{2, the} surface treatment with the above-described silane coupling agent can be carried out particularly effectively.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Examples thereof include esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

  Further, even if the low refractive index layer used in the present invention is a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”). Good.

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). In the latter case, it is possible to introduce a crosslinked structure by adding a compound having a group that reacts with a functional group in the polymer and one or more reactive groups after copolymerization. -147739. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is crosslinked by heating with a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, it is a thermosetting type. In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, the ionizing radiation curable type is used.

  In addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like. Moreover, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoro having a radical generating group at the terminal. It can be obtained by polymerization of the above monomer with a polyether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  About the usage-amount of each said monomer used in order to form the fluorine-containing copolymer before bridge | crosslinking, a fluorine-containing vinyl monomer becomes like this. Preferably it is 20-70 mol%, More preferably, it is a ratio of 40-70 mol%. . The monomer for imparting a crosslinkable group is preferably 1 to 20 mol%, more preferably 5 to 20 mol%. Furthermore, the other monomer used together is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR), etc. Can be mentioned.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  The low refractive index layer used in the present invention is applied by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (US Pat. No. 2,681,294). Can be formed. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).

  The film thickness of the low refractive index layer used in the present invention is preferably 50 to 200 nm, and more preferably 60 to 150 nm.

<High refractive index layer and medium refractive index layer>
In the present invention, it is preferable to provide a high refractive index layer between the hard coat layer and the low refractive index layer in order to reduce the reflectance. Alternatively, it is more preferable to provide a middle refractive index layer between the docoat layer and the high refractive index layer. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of the high refractive index layer and the middle refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 100 nm. The haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  The refractive index formed by applying and drying a coating solution containing a monomer, oligomer or hydrolyzate of an organotitanium compound represented by the following general formula (9) in the high refractive index layer used in the present invention. A layer having a rate of 1.55 to 2.5 is preferred.

General formula (9): Ti (OR ₁ ) ₄
In the formula, R ₁ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , and Ti (Oi−). C ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ dimer to 10-mer, Ti (Oi-C ₃ H ₇ ) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These can be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ 2-10 mer, 2-10 mer _{Ti (O-n-C 4} H 9) 4 are particularly preferred.

  Among the coating solutions for the high refractive index layer used in the present invention, it is preferable to add the organic titanium compound to a solution in which water and an organic solvent described later are sequentially added. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

  Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds from viewpoints, such as a hydrolysis and progress of superposition | polymerization. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount from a viewpoint of the temporal stability of a coating liquid.

  The organic solvent used in the present invention is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The organic titanium compound monomer, oligomer or hydrolyzate thereof used in the present invention preferably accounts for 50 to 98% by mass in the solid content contained in the coating solution. The solid content ratio is more preferably 50 to 90% by mass, and further preferably 55 to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and medium refractive index layer used in the present invention preferably contain metal oxide particles as fine particles, and further contain a binder polymer.

  When the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The weight average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent is most preferable.

  Two or more types of coupling agents may be used in combination, and in addition to the silane coupling agent, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are easy to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In this invention, you may process by combining 2 or more types of surface treatment. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The high refractive index layer and medium refractive index layer used in the present invention preferably use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of crosslinked polymers include polymers having saturated hydrocarbon chains such as polyolefin (hereinafter collectively referred to as “polyolefins”), crosslinked products such as polyethers, polyureas, polyurethanes, polyesters, polyamines, polyamides, and melamine resins. . Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Further, it is further preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, the anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated. The linking group that binds the anionic group and the polymer chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the ratio of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or the quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, and more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably a carbon number. 1 to 6 alkyl groups. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by a polymerization reaction at the same time as or after application of the coating solution by preparing a coating solution for forming a high refractive index layer and a medium refractive index layer by blending a monomer for generating a crosslinked polymer. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method of forming a crosslinked polymer by polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku Co., Ltd.) ) Ester, NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.) and the like. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of an anti-glare hard-coat layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, and alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

  In addition to the above-described components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the antireflection layer or coating liquid thereof includes a polymerization inhibitor, a leveling agent, a thickener, and an anti-coloring agent. An agent, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.

  In order to promote hydrolysis or hardening of the composition containing a metal alkoxide after coating of the medium to high refractive index layer and the low refractive index layer used in the present invention, it is preferable to irradiate active energy rays. More preferably, the active energy ray is irradiated every time each layer is coated.

The active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, and γ ray, but ultraviolet ray and electron beam are preferable, and handling is particularly simple and high energy. Ultraviolet rays are preferred because they can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably ²⁰ to 10,000 mJ / cm ² , more preferably 100 to 2,000 mJ / cm ² , and particularly preferably 400 to 2,000 mJ / cm 2. ² .

  When ultraviolet rays are used, the multilayer antireflection layer may be irradiated one by one, or may be irradiated after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

(Antireflection layer thickness)
The thickness of each refractive index layer constituting the antireflection layer is preferably in the range of 1 to 200 nm, more preferably 5 to 150 nm, but each film has an appropriate thickness depending on the refractive index of each layer. It is preferable to select.

(Reflectivity of antireflection layer)
The antireflection layer used in the present invention preferably has an average reflectance at 450 to 650 nm of 1% or less, particularly preferably 0.5% or less. Further, the minimum reflectance in this range is particularly preferably from 0.0 to 0.3%.

  The refractive index and film thickness of the antireflection layer can be calculated and calculated by measuring the spectral reflectance. Moreover, the reflective optical characteristic of the produced low reflection film can measure a reflectance on the conditions of a 5-degree regular reflection using a spectrophotometer. In this measurement method, after roughening the substrate surface on which the antireflection layer is not applied, a light absorption treatment is performed using a black spray to prevent reflection of light on the back surface of the film and reflectivity. Is measured.

  In the measurement, the transmittance at a transmittance of 550 nm is measured using a spectrophotometer with reference to air.

<Polarizing plate>
In the present invention, it is preferable to use a long polarizing plate formed by laminating a long retardation film (stretched film) on at least one surface of a long polarizer.

  The retardation film (stretched film) of the present invention is preferably a λ / 4 plate having the following characteristics.

(Λ / 4 plate)
The λ / 4 plate refers to a plate having a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). The λ / 4 plate is designed such that the in-plane retardation value Ro is about 1/4 with respect to a predetermined wavelength of light (usually in the visible light region). The retardation value Ro (550) measured at a wavelength of 550 nm is preferably in the range of 100 to 160 nm, more preferably 120 to 150 nm.

  Further, the λ / 4 plate is preferably a retardation plate having a retardation of approximately ¼ of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range. .

  The term “retardation of approximately ¼ in the wavelength range of visible light” means a retardation value represented by the following formula (i) measured at a wavelength of 450 nm, with a larger retardation at a wavelength of 400 to 700 nm. It is preferable that Ro (590) which is a retardation value measured at a certain Ro (450) and a wavelength of 590 nm satisfies 1 <Ro (590) / Ro (450) ≦ 1.6. Furthermore, in order to function effectively as a λ / 4 plate, Ro (450) is in the range of 100 to 125 nm, the retardation value Ro (550) measured at a wavelength of 550 nm is in the range of 125 to 142 nm, It is more preferable that Ro (590) is a retardation film in the range of 130 to 152 nm.

Formula _{(i): Ro = (n} x -n y) × d
Formula (ii): Rt = {(n _x + n _y ) / 2−n _z } × d
_{Wherein, n x,} n _y is, 23 ℃ · 55% RH, 450nm, say 550 nm, the maximum of the refractive index in the plane of the refractive index _{n x} (film in each of the 590 nm, also the slow axis direction of the refractive index. ), _Ny (refractive index in the direction orthogonal to the slow axis in the film plane), and d is the thickness (nm) of the film.

  Ro and Rt can be measured using an automatic birefringence meter. Using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments), Ro is calculated by birefringence measurement at each wavelength in an environment of 23 ° C. and 55% RH.

  A circularly polarizing plate is obtained by laminating so that the angle between the slow axis of the λ / 4 plate and the transmission axis of the polarizer described later is substantially 45 °. “Substantially 45 °” means 40 to 50 °. The angle between the slow axis in the plane of the λ / 4 plate and the transmission axis of the polarizer is preferably 41 to 49 °, more preferably 42 to 48 °, and 43 to 47 °. Is more preferable, and it is most preferable that it is 44-46 degrees.

  The polarizing plate of the present invention uses a stretched polyvinyl alcohol doped with iodine or a dichroic dye as a polarizer, and is a retardation film (stretched film) of the present invention, λ / 4 plate / polarizer / It can be manufactured by bonding with the configuration of a retardation film.

  In addition, when using the polarizing plate of this invention for the liquid crystal display device which is a stereoscopic video display device, the said (lambda) / 4 board is bonded by the visual recognition side.

  The retardation film is preferably a polymer film, preferably manufactured easily, optically uniform, and optically transparent. Any of these may be used, for example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate. Polyester film, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin Film, polymethylpentene film, polyetherketone film, Polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, a cycloolefin polymer film, a polyvinyl acetal resin film, there may be mentioned polymethyl methacrylate film, or an acrylic film or the like, but are not limited to.

  In the case of a cellulose ester film, cellulose acetate, plasticizer, ultraviolet absorber, antioxidant, retardation adjusting agent, matting agent, deterioration inhibitor, peeling aid used in the above-mentioned retardation film (stretched film), A surfactant or the like can be preferably used.

  Retardation films Ro and Rt defined by the above formula are 20 to 150 nm and 70 to 70 respectively for retardation films bonded to the surface opposite to the surface on which the λ / 4 plate is bonded to the polarizer. It is preferable that the retardation film is 400 nm, or 0 nm ≦ Ro ≦ 2 nm and −15 nm ≦ Rt ≦ 15 nm.

  As the retardation film, for example, a method of supporting a discotic liquid crystalline compound, which is a compound having negative uniaxiality, on a support (for example, see JP-A-7-325221), positive optical anisotropy. A method of supporting a nematic polymer liquid crystal compound having a hybrid orientation in which a pretilt angle of liquid crystal molecules changes in the depth direction on a support (see, for example, JP-A-10-186356), A nematic liquid crystal compound having positive optical anisotropy is formed into a two-layer structure on a support, and the orientation direction of each layer is set to approximately 90 ° to give pseudo-uniaxially similar optical characteristics. In place of a retardation film provided with an optically anisotropic layer on a support or a conventional TAC film (for example, see JP-A-8-15681) A retardation film having a retardation film function by stretching a cellulose derivative film, saponifying the cellulose derivative film, and laminating a PVA polarizer (see, for example, JP-A-2003-270442). In addition, an optical compensation film by a method of adding a retardation adjusting agent to a cellulose ester film to obtain a retardation film (see, for example, JP 2000-275434 A and JP 2003-344655 A) can be mentioned. It is not limited to these.

  For example, as a commercially available cellulose ester film, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC16UR, KC4UE, KC4UE, KC4FR, KC4FR-1 And the like) are also preferably used.

  The film thickness of the polarizer is 5 to 40 μm, preferably 5 to 30 μm, and particularly preferably 5 to 20 μm.

  The polarizing plate can be produced by a general method. The stretched film according to the present invention subjected to alkali saponification treatment is preferably bonded to at least one surface of a polarizer produced by immersing and stretching a polyvinyl alcohol film in an iodine solution by using a completely saponified polyvinyl alcohol aqueous solution. . It is preferable to paste the retardation film on the other surface.

  The polarizing plate can be constructed by further bonding a protective film on one surface of the polarizing plate and a separate film on the other surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection.

<Liquid crystal display device>
In the present invention, a sheet-like film formed by cutting a long retardation film (stretched film), and a sheet-like polarizing plate formed by cutting the long polarizing plate are provided. It can be set as the liquid crystal display device of an aspect. For example, the liquid crystal display device of the present invention can be produced by using the liquid crystal display device in which the polarizing plate according to the present invention is bonded to the surface on the viewing side of the liquid crystal cell.

  The polarizing plate according to the present invention is a reflective, transmissive, transflective LCD, super twisted nematic (STN) mode, twisted nematic (TN) mode, in-plane switching (IPS) mode, vertical alignment (VA) mode, bend. It is preferably used for a liquid crystal display device in a nematic (OCB: Optically Aligned Birefringence) mode and a hybrid alignment (HAN: Hybrid Aligned Nematic) mode.

  In the present invention, in particular, the liquid crystal display device is preferably a stereoscopic image display device. That is, the λ / 4 plate which is the retardation film (stretched film) of the present invention can be used in various modes in a stereoscopic image display device. For example, a stereoscopic image display device comprising a liquid crystal display device and liquid crystal shutter glasses, wherein the liquid crystal shutter glasses are provided with (1) a λ / 4 plate, a liquid crystal cell, and a polarizer in this order (FIG. 5). ), Or (2) a λ / 4 plate, a polarizer, a liquid crystal cell, and a polarizer are provided in this order (FIG. 6). Can do.

  In any case, the front polarizing plate of the liquid crystal display device has a configuration in which a λ / 4 plate, a polarizer, a retardation film, a cell, and a polarizer are provided in this order.

  In the present invention, with the above-described aspect and configuration, crosstalk or luminance reduction and color change when tilting the head when viewing a stereoscopic (3D) image can be reduced, and excellent visibility with respect to the use environment can be maintained. Therefore, a stereoscopic image display device with higher durability against the use environment can be obtained.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Synthesis of acrylic polymer)
A glass flask equipped with a stirrer, two dropping funnels, a gas introduction tube and a thermometer was charged with 28 g of methyl methacrylate, 12 g of N-vinylpyrrolidone, 2 g of mercaptopropionic acid as a chain transfer agent and 30 g of toluene, and the temperature was raised to 90 ° C. did. Thereafter, from one dropping funnel, 60 g of a mixed solution of 42 g of methyl methacrylate and 18 g of N-vinylpyrrolidone was dropped over 3 hours, and simultaneously 0.4 g of azobisisobutyronitrile dissolved in 14 g of toluene from the other funnel. Was added dropwise over 3 hours. Thereafter, 0.6 g of azobisisobutyronitrile dissolved in 56 g of toluene was added dropwise over 2 hours, and the reaction was further continued for 2 hours to obtain a polymer. The obtained polymer was solid at room temperature. Next, polymers having different molecular weights were prepared by changing the addition amount of the chain transfer agent mercaptopropionic acid and the addition rate of azobisisobutyronitrile. The weight average molecular weight of the polymer was 10,000 by the following measurement method.

(Weight average molecular weight)
The weight average molecular weight of the polymer was determined by GPC polystyrene conversion described above.

<Production Example 1>
<Preparation of roll-like long film A>
As described below, a roll-like long film A was prepared by melt casting using a cellulose ester and various additives.

Cellulose ester (DAC: acetyl group substitution degree 2.4, total substitution degree 2.4; number average molecular weight Mn = 59,500, weight average molecular weight Mw = 190,000, Mw / Mn = 3.19)
70 parts by mass Acrylic polymer prepared above 27.5 parts by mass IRGANOX-1010 (manufactured by BASF Japan) 0.5 parts by mass GSY-P101 (manufactured by Sakai Chemical Industry) 0.25 parts by mass Sumilizer GS (manufactured by Sumitomo Chemical ) 0.25 parts by mass TINUVIN 928 (manufactured by BASF Japan Ltd.) 1.5 parts by mass The cellulose ester was dried under reduced pressure at 70 ° C. for 3 hours and cooled to room temperature, and then the additives were mixed. The above mixture was melt-mixed at 230 ° C. using a twin-screw extruder and pelletized. In addition, the glass transition temperature Tg of this pellet was 135 degreeC.

  Using this pellet, it is melted at 250 ° C. in a nitrogen atmosphere, extruded from the casting die in the molten film production apparatus onto the first cooling roll, and the film is sandwiched between the first cooling roll and the touch roll to form. did. Further, silica particle Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd.) was added as a slip agent from the hopper opening in the middle of the extruder so as to be 0.5 parts by mass.

  The heat bolt was adjusted so that the gap width of the casting die was 0.5 mm within 30 mm from the width direction end of the film and 1 mm at other locations. Water at 80 ° C. was allowed to flow as cooling water inside the touch roll.

  The peripheral surface of the first cooling roller from the position where the resin extruded from the casting die contacts the first cooling roll to the upstream end position in the first cooling roll rotation direction of the nip between the first cooling roll and the touch roll The length along was set to 20 mm. Thereafter, the touch roll was separated from the first cooling roll, and the temperature of the melted part immediately before being pressed between the nips of the first cooling roll and the touch roll was measured.

  In the present embodiment, the temperature of the melted part immediately before being squeezed by the nip between the first cooling roll and the touch roll is 1 mm upstream from the nip upstream end, and a thermometer (HA manufactured by Anritsu Keiki Co., Ltd.). -200E).

  As a result of the measurement in this example, the temperature T was 141 ° C. The linear pressure of the touch roll against the first cooling roll was 14.7 N / cm. Furthermore, after introducing into a tenter and stretching 1.05 times in the width direction at 160 ° C, it was cooled to 30 ° C while relaxing 3% in the width direction, then released from the clip, the clip gripping part was cut off, and both ends of the film Was subjected to a knurling process with a width of 10 mm and a height of 5 μm, and wound on a winding core with a winding tension of 220 N / m and a taper of 40%.

  In addition, the extrusion amount and the take-up speed were adjusted so that the film had a thickness of 50 μm, and the finished film width was slit so that the finished film width was 2000 mm, thereby producing a roll-like long film A.

  The obtained long film A had a thickness unevenness in the longitudinal direction of 0.15 μm and a thickness unevenness in the width direction of 0.15 μm. Ro was 5 nm, Ro variation was 1 nm, and thickness direction retardation Rt was 3 nm.

<Example 1>
The roll-like long film A was set in a slidable feeding device of the device of FIG. 3A and supplied to an oblique stretching machine in which a rail pattern was set so that the angle θi = 60 °. At that time, the distance between the main shaft of the guide roll closest to the inlet of the oblique stretching apparatus and the gripping tool (clip gripping part) of the oblique stretching apparatus was 80 cm. A clip with a length of 2 inches in the conveying direction was used, and a guide roll with a diameter of 10 cm was used. Diagonal stretching is performed at a stretching temperature of 145 ° C. and a stretching ratio of 1.5 times with an oblique stretching tenter, and the oblique direction is such that the take-up tension at the tenter outlet is 200 N / m and the in-plane slow axis direction θ of the film F is 30 °. Stretching was performed. The stretched film was controlled so that the fluctuation in the take-up tension was less than 3% by performing feedback control in which the change in the tension measured with the first roll on the outlet side of the obliquely stretched tenter was reflected in the take-up motor rotation speed. Thereafter, both ends of the film are trimmed, the conveyance direction is changed by a conveyance direction changing device composed of an airflow roll, the film is wound by a slidable winding device, and a 2000 mm wide roll-like long stretched retardation film F1 is obtained. Obtained.

  The film moving speed during heating and stretching was 20 m / min. The temperature of the preheating zone was 145 ° C., and the temperature of the cooling zone was 130 ° C. When heating and stretching the film, the so-called “Boeing phenomenon” was eliminated, and stretching was performed with an optimal rail pattern so that the in-plane slow axis direction θ of the retardation film was 30 °. .

  Then, while holding both ends of the film F1 with clips, the film is stretched in the -90 ° direction with respect to the transport direction on the film surface at 173 ° C. and 1.1 times the stretching condition, and the retardation film (stretched film) 1 is obtained. Obtained.

  Moreover, it extended | stretched using the heating apparatus for temperature control over the width direction of a film. The heating device controlled the temperature so that the thickness of the film in the film width direction after stretching was approximately the same as the thickness direction film thickness distribution before stretching.

  The obtained long retardation film (stretched film) 1 was uniform in the longitudinal direction of the film. Table 1 shows the optical properties (in-plane slow axis direction θs, in-plane retardation Ro, thickness direction retardation Rt, etc.) of the obtained retardation film (stretched film) 1.

  The following hard coat layer was provided on the surface of the obtained retardation film (stretched film) 1 to produce a film of Example 1.

<Application of hard coat layer>
The following hard coat layer coating solution 1 was die coated, dried at 80 ° C., and then irradiated with 120 mJ / cm ² of ultraviolet light with a high pressure mercury lamp to provide a clear hard coat layer so that the film thickness after curing was 6 μm.

(Coating solution 1 for hard coat layer)
Ethanol 100 parts by mass Pentaerythritol triacrylate 100 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by BASF Japan Ltd.) 5 parts by mass 2-methyl-1- [4- (methylthio) phenyl] -2-monoforino -1-one (Irgacure 907, manufactured by BASF Japan) 3 parts by weight BYK-331 (silicone surfactant, manufactured by Big Chemie Japan Co., Ltd.)
5 parts by mass As shown in Table 1, the obtained retardation film of Example 1 is excellent in that the Ro fluctuation value in the width direction after the wet heat durability test treatment is suppressed, and there are no streaks on the hard coat layer. It was.

<Example 2>
<Production Example 2>
In Production Example 1, cellulose ester was converted into cellulose acetate propionate: (CAP: acetyl group substitution degree 1.5, propionyl group 0.9, total substitution degree 2.4; number average molecular weight Mn = 57,500, weight average molecular weight. A roll-like long film B was obtained in the same manner as in Production Example 1, except that the cellulose acetate was changed to Mw = 190,000, Mw / Mn = 3.30).

  In Example 1, the film F2 and the retardation film 2 were similarly produced except having changed the roll-like long film into the long film B. As shown in Table 1, the obtained retardation film 2 of Example 2 was excellent in that the fluctuation value of Ro in the width direction after the wet heat durability test treatment was suppressed, and there were no streaks on the hard coat layer.

<Example 3>
<Production Example 3>
<Preparation of roll-like long film C>
(Preparation of polyester A)
In a nitrogen atmosphere, 4.85 g of dimethyl terephthalate, 4.4 g of 1,2-propylene glycol, 6.8 g of p-toluic acid, and 10 mg of tetraisopropyl titanate were mixed and stirred at 140 ° C. for 2 hours. Stirring was carried out at ° C for 16 hours. Next, the temperature was lowered to 170 ° C., and unreacted 1,2-propylene glycol was distilled off under reduced pressure to obtain comparative polyester A.

Acid value: 0.1
Number average molecular weight: 490
Dispersity: 1.4
Component content of molecular weight 300-1800: 90%
Hydroxyl (hydroxyl) value: 0.1
Hydroxyl group (hydroxyl group) content: 0.04%
Polyester A has a terminal toluic acid ester because the monocarboxylic acid is used in an amount twice as much as that of the dicarboxylic acid.

<Fine particle dispersion 1>
Fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle addition liquid 1>
The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.

Methylene chloride 99 parts by mass Fine particle dispersion 1 5 parts by mass A main dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose ester, sugar ester compound, polyester A, TINUVIN 928, and fine particle additive solution 1 were charged into a pressure dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope solution was prepared by filtration using 244.

<Composition of main dope solution>
Methylene chloride 340 parts by mass Ethanol 64 parts by mass Cellulose ester (DAC: acetyl group substitution degree 2.4, total substitution degree 2.4; number average molecular weight Mn = 59,500, weight average molecular weight Mw = 190,000, Mw / Mn = 3.19)
100 parts by mass Sugar ester compound (Chemical Formula 2; 1-22) 7.0 parts by mass Polyester A 2.5 parts by mass TINUVIN 928 (manufactured by BASF Japan Ltd.) 1.5 parts by mass Fine particle additive solution 1 1 part by mass The dope solution was prepared by charging and dissolving with stirring. Next, an endless belt casting apparatus was used to uniformly cast the dope solution on a stainless steel belt support at a temperature of 33 ° C. and a width of 2000 mm. The temperature of the stainless steel belt was controlled at 30 ° C.

  On the stainless steel belt support, the solvent was evaporated until the residual solvent amount in the cast (cast) film became 75%, and then peeled off from the stainless steel belt support with a peeling tension of 110 N / m.

  The peeled cellulose ester film was stretched 5% in the width direction using a tenter while applying heat at 160 ° C. The residual solvent at the start of stretching was 15%.

  Next, drying was terminated while the drying zone was conveyed by a number of rolls. The drying temperature was 130 ° C. and the transport tension was 100 N / m.

  As described above, a roll-like long film C having a dry film thickness of 75 μm was obtained.

  The obtained long film C had a thickness unevenness in the longitudinal direction of 0.15 μm and a thickness unevenness in the width direction of 0.15 μm. When the in-plane retardation was measured by the above-mentioned method, Ro was 10 nm, Ro variation was 1 nm, and Rt (550) was 120 nm. The Tg of the film was 165 ° C.

  The film F3 and the retardation film 3 of Example 3 are produced in the same manner as in Example 1, except that the long film C is used as a roll-like long film and the feeding direction θi is changed to 80 °. did.

  As shown in Table 1, the obtained retardation film 3 of Example 3 was excellent in that the Ro fluctuation value in the width direction after the wet heat durability test treatment was suppressed, and there were no streaks on the hard coat layer.

<Example 4>
<Production Example 4>
In Production Example 3, the cellulose ester was converted into cellulose acetate propionate: (CAP: acetyl group substitution degree 1.5, propionyl group 0.9, total substitution degree 2.4; number average molecular weight Mn = 57,500, weight average molecular weight. A roll-like long film D was obtained in the same manner as in Production Example 2, except that the cellulose acetate was changed to Mw = 190,000, Mw / Mn = 3.30).

  A film F4 and a retardation film 4 of Example 4 were produced in the same manner as in Example 1 except that the long film D was used as the roll-like long film.

  As shown in Table 1, the obtained retardation film 4 of Example 4 was excellent in that the fluctuation value of Ro in the width direction after the wet heat durability test treatment was suppressed, and there were no streaks on the hard coat layer.

<Example 5>
In Example 3, the retardation film of Example 5 was produced in the same manner as in Example 1 except that the ethanol in the hard coat layer coating solution applied to the retardation film (stretched film) 3 was eliminated.

  As shown in Table 1, the obtained retardation film of Example 5 was excellent in that the Ro fluctuation value in the width direction after the wet heat durability test treatment was suppressed, and there were no streaks on the hard coat layer.

<Example 6>
In Example 3, Example 6 was carried out in the same manner as in Example 1 except that pentaerythritol triacrylate of the coating liquid for hard coat layer applied to the retardation film (stretched film) 3 was changed to pentaerythritol tetraacrylate. A retardation film was prepared.

  As shown in Table 1, the obtained retardation film of Example 6 was excellent in that the Ro fluctuation value in the width direction after the wet heat durability test treatment was suppressed, and there were no streaks on the hard coat layer.

<Comparative Example 1>
In Example 3, the pentaerythritol triacrylate of the hard coat layer coating solution applied to the retardation film (stretched film) 3 is a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (mass ratio 6: 4; Kyoeisha Chemical Co., Ltd.). A retardation film of Comparative Example 1 was produced in the same manner as in Example 1 except that the product was changed to “made by Co., Ltd.”.

  As shown in Table 1, the obtained retardation film of Comparative Example 1 had a large Ro fluctuation value in the width direction after the wet heat durability test treatment, and a streak failure on the hard coat layer was observed.

<Comparative example 2>
In Comparative Example 1, the retardation film of Comparative Example 2 was prepared in the same manner as in Comparative Example 1 except that the coating liquid for hard coat layer applied to the retardation film (stretched film) 3 was changed to the following coating liquid 2. Was made.

(Coating solution 2 for hard coat layer)
Acetone 45 parts by mass Ethyl acetate 45 parts by mass Propylene glycol monomethyl ether 10 parts by mass A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (mass ratio 6: 4; manufactured by Kyoeisha Chemical Co., Ltd.) 100 parts by mass 1 -Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by BASF Japan) 5 parts by mass 2-Methyl-1- [4- (methylthio) phenyl] -2-monoforino-1-one (Irgacure 907, manufactured by BASF Japan) ) 3 parts by mass BYK-331 (silicone surfactant, manufactured by Big Chemie Japan Co., Ltd.)
5 parts by mass As shown in Table 1, the obtained retardation film of Comparative Example 2 had a large Ro fluctuation value in the width direction after the wet heat durability test treatment, and a streak failure on the hard coat layer was observed.

<Comparative Example 3>
In Comparative Example 2, a retardation film of Comparative Example 3 was produced in the same manner as in Comparative Example 2, except that dipentaerythritol hexaacrylate in hard coat layer coating solution 2 was changed to pentaerythritol triacrylate.

  As shown in Table 1, the obtained retardation film of Comparative Example 3 had a large Ro fluctuation value in the width direction after the wet heat durability test treatment, and a streak failure on the hard coat layer was observed.

<Evaluation conditions>
The measurement / evaluation of the in-plane slow axis direction θ of the film F, the in-plane slow axis θs of the retardation film (stretched film), the in-plane direction retardation Ro of the film, and the thickness direction retardation Rt is measured by retardation. Using a measuring device (manufactured by Oji Scientific Co., Ltd., KOBRA-WXK), Ro is measured at intervals of 50 mm of the film in the width direction every 5 m in the film flow direction, and the average value of all data is calculated as the in-plane direction retardation Ro. did.

  Moreover, film thickness direction retardation Rt was computed using the following formula.

Formula _{(i): Ro = (n} x -n y) × d
Formula (ii): Rt = {(n _x + n _y ) / 2−n _z } × d
Wherein, _{n x} and _{n y,} respectively, 23 ℃ · 55% RH, the refractive indices _{n x} at 590 nm (maximum refractive index in the plane of the film, also referred to as a slow axis direction of the refractive index.), _{N y} (Refractive index in the direction perpendicular to the slow axis in the film plane), and d is the thickness (nm) of the film.

In order to measure the in-plane slow axis direction θ of the film F according to the present invention and the in-plane slow axis direction θs of the retardation film (stretched film), the film transport direction is set to the reference line ( = 0 °) and the phase difference is measured. The in-plane slow axis direction is the direction of the refractive index n _x. Thus using the phase difference measuring device,, combined reference line in the conveying direction and the device of the film can be the direction of n _x is measured.

<Measurement of retardation value Ro before and after wet heat durability test>
(Saponification treatment)
The prepared retardation film was immersed in a 2 mol / L potassium hydroxide solution at 40 ° C. for 30 seconds, then washed with water, dried in an oven at 60 ° C. (dry) for 5 minutes, and the retardation was measured by the following procedure. The initial value was used.

  A sample of 35 mm × 35 mm was cut out from the obtained retardation film, conditioned at 25 ° C. and 55% RH for 2 hours, and measured with an automatic birefringence meter (KOBRAWR, Oji Scientific Co., Ltd.) from the vertical direction at 590 nm. From the extrapolation value of the retardation value measured in the same manner while tilting the film surface, the following formula was used.

Formula _{(i): Ro = (n} x -n y) × d
(Wherein, n _x is a refractive index in a slow axis direction in the film plane, n _y is a refractive index in a fast axis direction in the film plane, d is the thickness of the film (nm) .)
The retardation value Ro was measured using KOBRA-21ADH (manufactured by Oji Scientific Instruments) at a temperature of 23 ° C. and a humidity of 55% RH at a wavelength of 590 nm.

(Wet heat durability test processing)
The saponified retardation film is placed in a thermostatic chamber set at a temperature of 60 ° C. and a relative humidity of 90% RH, taken out after 500 hours, and then the transverse direction retardation Ro is set at 1 cm intervals in the same manner as the initial value measurement. Measurements were made to calculate fluctuation values based on the in-plane retardation value Ro before storage at each point in the lateral direction, and the difference between the maximum value and the minimum value was calculated.

<Evaluation method of streaks>
A portion of 5 m from the end of winding was taken out of 5000 m of the prepared sample, and the presence or absence of streaks was visually measured under the following measurement conditions.
Evaluation rank of streak A: No generation of streak O: Slight streaking Δ: Streaking ×: Very large number of streaks The above evaluation results are summarized in Table 1.

  As is apparent from the results shown in Table 1, it can be seen that the retardation film of the present invention has no occurrence of streak failure and little change in the optical characteristics in the width direction in the environmental durability test.

(Examination of adaptability to stereoscopic image display device)
In order to contribute to an evaluation experiment of adaptability to a stereoscopic image display device to be described later, the following antireflection layer is further provided on each of the hard coat layers of the film of Example 3 and the film of Comparative Example 3 produced above. A retardation film Aar and a retardation film Bar were obtained.

<Application of antireflection layer>
(Application of medium refractive index layer)
The following medium refractive index layer coating solution is die-coated on the surface of the hard coat layer, dried at 80 ° C., and then irradiated with 120 mJ / cm ² of ultraviolet light with a high-pressure mercury lamp so that the cured film thickness becomes 110 nm. A medium refractive index layer was provided. The refractive index was 1.60.

<Medium refractive index layer coating solution>
<Preparation of particle dispersion A>
Methanol-dispersed antimony double oxide colloid (solid content 60%, zinc antimonate sol manufactured by Nissan Chemical Industries, Ltd., trade name: Celnax CX-Z610M-F2) 6.0 kg of isopropyl alcohol was gradually stirred with stirring. To prepare a particle dispersion A.

PGME (propylene glycol monomethyl ether) 40 parts by mass Isopropyl alcohol 25 parts by mass Methyl ethyl ketone 25 parts by mass Pentaerythritol triacrylate 0.9 parts by mass Pentaerythritol tetraacrylate 1.0 part by mass Urethane acrylate (trade name: U-4HA Shin-Nakamura Chemical 0.6 parts by mass Particle dispersion A 20 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by BASF Japan Ltd.) 0.4 parts by mass 2-methyl-1- [4- (methylthio) Phenyl] -2-monoforinopropan-1-one (Irgacure 907, manufactured by BASF Japan) 0.2 parts by mass 10% FZ-2207, propylene glycol monomethyl ether solution (manufactured by Nippon Unicar) 0.4 parts by mass Coating of the low refractive index layer)
On the medium refractive index layer, the following low refractive index layer coating solution is die-coated, dried at 80 ° C., and then irradiated with 120 mJ / cm ² of ultraviolet light with a high pressure mercury lamp so that the film thickness becomes 92 nm. A rate layer was provided to prepare an antireflection layer. The refractive index was 1.38.

(Low refractive index layer coating solution)
<Preparation of tetraethoxysilane hydrolyzate A>
After mixing 230 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol and adding 120 g of a 2% aqueous acetic acid solution thereto, the mixture is stirred for 26 hours at room temperature (25 ° C.). Silane hydrolyzate A was prepared.

Propylene glycol monomethyl ether 430 parts by mass Isopropyl alcohol 430 parts by mass Tetraethoxysilane hydrolyzate A 120 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 parts by mass Isopropyl alcohol dispersion Hollow silica sol (solid content 20%, silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209) 40 parts by mass Aluminum ethyl acetoacetate diisopropylate (manufactured by Kawaken Fine Chemicals) 3.0 parts by mass 10% FZ- 2207, propylene glycol monomethyl ether solution (manufactured by Nihon Unicar) 3.0 parts by mass <Preparation of retardation film 201>
<Fine particle dispersion 1>
Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle addition liquid 1>
The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.

Methylene chloride 99 parts by mass Fine particle dispersion 1 5 parts by mass A main dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose acetate was added to a pressurized dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope solution was prepared by filtration using 244.

<Composition of main dope solution>
Methylene chloride 340 parts by mass Ethanol 64 parts by mass Cellulose acetate having an acetyl group substitution degree of 2.4 (DAC: acetyl group substitution degree 2.4, total substitution degree 2.4; number average molecular weight Mn = 59,500, weight average molecular weight Mw = 190,000, Mw / Mn = 3.19) 100 parts by mass Sugar ester compound (Chemical Formula 2; 1-22) 10.0 parts by mass Polyester A 2.5 parts by mass Ultraviolet absorber (Tinbin 928 (BASF Japan ( Co., Ltd.))) 2.3 parts by mass Particulate additive liquid 1 1 part by mass The above composition was put into a closed container and dissolved while stirring to prepare a dope solution. Next, an endless belt casting apparatus was used to uniformly cast the dope solution on a stainless steel belt support at a temperature of 33 ° C. and a width of 2000 mm. The temperature of the stainless steel belt was controlled at 30 ° C.

  On the stainless steel belt support, the solvent was evaporated until the residual solvent amount in the cast (cast) film was 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.

  Thereafter, the film is stretched 1.4 times in the width direction by a tenter set at 170 ° C., then dried by being transported in a drying zone set at 130 ° C. for 30 minutes, trimmed at both ends, A retardation film 201 having a thickness of 40 μm having a knurling having a width of 1 cm and a height of 8 μm was prepared, and the film was wound up with a width of 2000 mm and 5000 m.

  The in-plane retardation value Ro (590) and thickness direction retardation Rt (590) of the retardation film 201 were 50 nm and 130 nm, respectively.

<Preparation of polarizing plates A and B>
A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times).

  This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizer.

  Next, in accordance with the following steps 1 to 5, the polarizer, the film Aar or film Bar, and the retardation film 201 on the back side are bonded with a roll-to-roll so as to match the longitudinal direction, and polarizing plates A and B are attached. Produced.

  Step 1: It was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to obtain a film Aar or a film Bar having a saponified side to be bonded to a polarizer.

  Process 2: The said polarizer was immersed in the polyvinyl alcohol adhesive tank of 2 mass% of solid content for 1-2 seconds.

  Step 3: Excess adhesive adhered to the polarizer in Step 2 was gently wiped off and placed on the retardation film Aar or retardation film Bar processed in Step 1.

Step 4: The retardation film Aar or retardation film Bar, the polarizer, and the retardation film 201 laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm ² and a conveyance speed of about 2 m / min.

  Step 5: A sample obtained by bonding the polarizer prepared in Step 4 and the retardation film Aar or the retardation film Bar and the retardation film 201 in a drier at 80 ° C. is dried for 2 minutes, and each of the retardation films Aar Alternatively, polarizing plates A and B corresponding to the retardation film Bar were prepared.

<Production of liquid crystal display device>
A liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  Remove the pre-bonded front plate of Sony 60-type display BRAVIA LX900, remove the filler between the front plate and the polarizing plate on the front of the panel, and peel off the pre-bonded front polarizing plate of the panel And the produced said polarizing plates A and B were each bonded on the front surface of the glass surface of a liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is absorbed so that the surface of the retardation film (stretched film) of the present invention is on the viewing side and in the same direction as the polarizing plate previously bonded. The liquid crystal display devices A and B corresponding to the polarizing plates A and B were respectively produced so that the axes were directed.

(3D glasses)
The film Aar was bonded to the panel side of the Sony 3D glasses TDG-BR100.

  Streaks during 3D video viewing were observed for the manufactured liquid crystal display device.

<Evaluation of streaks when viewing 3D video>
Immediately after turning on the backlight of each liquid crystal display device in an environment of 23 ° C. and 55% RH, 3D glasses were worn and 3D images were viewed, and streaks were evaluated according to the following criteria.
○: No streak at all ×: Streak is visible Table 2 shows the above evaluation results.

  As is clear from the results shown in Table 2, it can be seen that the liquid crystal display device using the retardation film (stretched film) of the present invention is excellent without any streak failure.

DESCRIPTION OF SYMBOLS 1 Original film 2-1 Right film holding start point 2-2 Left film holding start point 3-1 Trajectory of right film holding means 3-2 Trajectory of left film holding means 4 Tenter 5-1 Right film Holding end point 5-2 Left film holding end point 6 Obliquely stretched film 7-1 Film feeding direction 8-1 Tenter inlet side guide roll 8-2 Tenter outlet side guide roll 9 Film stretching direction DR1 Feeding direction DR2 Winding direction θi Feeding angle (angle formed by feeding direction and winding direction)
CR, CL Gripping device Wo Width of film before stretching W Width of film after stretching A Liquid crystal shutter glasses A1, A4 Polarizer A2 Liquid crystal cell A3 λ / 4 plate B Liquid crystal display device (for example, television (TV))
C polarizing plate C1 λ / 4 plate C2 polarizer C3 retardation film C4 polarizer protective film D liquid crystal cell E polarizing plate F backlight HC hard coat layer AR antireflection layer a absorption axis b slow axis

Claims (11)

  A retardation film provided with a hard coat layer, wherein (1) the direction of the slow axis of the retardation film is different from the long direction and the width direction of the film, and exists between both directions, 2) The in-plane retardation value Ro measured at a measurement wavelength of 590 nm at a temperature of 23 ° C. and a relative humidity of 55% RH is in the range of 120 to 170 nm, and (3) the retardation film is heated to a temperature of 60 ° C. and a relative humidity. When the in-plane retardation value Ro in the transverse direction is measured under the same conditions as the above measurement for the retardation film after storage in an environment of 90% RH for 500 hours, the in-plane retardation value before storage A retardation film, wherein a difference between a maximum value and a minimum value of fluctuation values based on Ro is in a range of 1 to 10 nm.   The retardation film according to claim 1, wherein the hard coat layer is formed using a resin containing an active energy ray-curable resin.   The retardation film according to claim 1, wherein the hard coat layer is formed using a coating solution containing an acrylate ester having three or four acryloyl groups.   The retardation film according to claim 3, wherein the amount of solvent contained in the coating solution is less than 10% by mass.   The retardation film according to claim 3 or 4, wherein the solvent contained in the coating solution is ethanol or methanol.   The retardation film according to claim 3, wherein the coating liquid does not contain an organic solvent.   The said retardation film contains the cellulose ester in which the acetyl group substitution degree exists in the range of 2.0-2.6, The any one of Claim 1- Claim 6 characterized by the above-mentioned. Retardation film.   It is a manufacturing method of the retardation film which manufactures the retardation film as described in any one of Claim 1- Claim 7, Comprising: Within the range of 10-45 degrees with respect to the conveyance direction of a elongate film. After stretching in an oblique direction so as to have an in-plane slow axis at an angle, both ends of the long film are held at an angle in the range of −90 to −70 ° with respect to the transport direction by the gripping means, and 0 A method for producing a retardation film, wherein the film is stretched at a stretching ratio in a range of ˜20%.   A long polarizing plate formed by laminating the retardation film according to any one of claims 1 to 7 on at least one surface of a long polarizer.   It is formed by cutting the sheet-like film formed by cutting the retardation film according to any one of claims 1 to 7, or the long polarizing plate according to claim 9. A liquid crystal display device comprising a single sheet polarizing plate.   The liquid crystal display device according to claim 10, wherein the liquid crystal display device is a stereoscopic image display device.

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