JP2006349728A - Manufacturing method of phase difference film, phase difference film, polarizing plate and liquid crystal display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phase difference film which is a thin film and is excellent in continuous productivity and a film anti-peeling property and to provide its manufacturing method and a liquid crystal display apparatus using the phase difference film. <P>SOLUTION: The manufacturing method of the phase difference film is characterized in that, (1) film thickness is 30-60 μm, (2) the film is peeled after flow-casting of a solution, (3) in an drawing process, amount of residual solvents (Z1) at the beggining of drawing is 0.1 to 5.0 mass%, a ratio (H1) of good solvents contained in the residual solvents is 0 to 40 mass% and temperature (T1) of the film at the beggining of drawing is 30°C to 180°C, (4) in a cutting process, amount of residual solvents (Z3) contained in the film is 0.1 to 4.0 mass% and a ratio (H2) of good solvents in the residual solvents contained in the film is 0 to 35 mass%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a retardation film, a retardation film, a polarizing plate, and a liquid crystal display device, and more particularly, to a method for producing a roll-shaped belt-like retardation film.

  Generally, a polarizing plate of a liquid crystal display device is obtained by sandwiching and bonding a polarizer made of stretched polyvinyl alcohol between two polarizing plate protective films.

  As a polarizing plate protective film, it is known to use a retardation film, for example, a cellulose ester film having an appropriate retardation, in order to enlarge the viewing angle.

  As a method for obtaining a retardation film, for example, a method for reducing the acyl group substitution degree of cellulose ester, a method for adding a compound having a retardation increasing function called a retardation increasing agent to cellulose ester (Patent Documents 1 and 2). See).

  On the other hand, with the progress of thinning and lightening of liquid crystal display devices in recent years, there is an increasing demand for thinning and lightening of a polarizing plate protective film for expanding a viewing angle as a member used for the liquid crystal display device. Yes.

  However, the method for obtaining the above retardation film is insufficient to meet the recent demand for reduction in thickness and weight.

That is, when the above-described method for obtaining the retardation film is simply applied, there is a problem in that the probability of breaking during production increases as the film is thinned, which may cause an obstacle to continuous productivity. In addition, in order to bond the cellulose ester film with the polarizer, it is usually necessary to saponify the cellulose ester film, but this causes unevenness of adhesion, which may be caused by the non-uniformity of this processing, and the polarizing plate protective film and the polarizing film There is a problem that the adhesion with the polarizer becomes non-uniform, and the polarizing plate protective film may peel off from the polarizer with time.
JP 2002-131538 A JP 2003-57444 A

  An object of the present invention is to provide a retardation film which is a thin film and has excellent continuous productivity and excellent film peeling prevention property, a production method for producing the same, and a liquid crystal display device using the same.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A method for producing a retardation film comprising a stretching step of stretching a strip-shaped film to be conveyed in the width direction, and a cutting step of cutting both ends of the strip-shaped film stretched in the stretching step,
(1) The film thickness of the retardation film is 30 μm to 60 μm,
(2) The belt-like film to be conveyed is a belt-like film containing the polymer material, which is peeled off from the support after casting a dope containing the polymer material on the support.
(3) Stretching in the stretching step is performed by a stretching apparatus having a gripping means for gripping the belt-like film, and the residual solvent amount (Z1) at the start of stretching is 0.1 to 5.0% by mass, The ratio (H1) of the good solvent contained in the residual solvent is 0 to 40% by mass, the temperature (T1) of the belt-like film at the start of stretching is 30 to 180 ° C.,
(4) In the cutting step, the residual solvent amount (Z3) contained in the strip film is 0.1 to 4.0% by mass, and the good solvent ratio (H2) in the residual solvent contained in the strip film is It is 0-35 mass%, The manufacturing method of retardation film characterized by the above-mentioned.

(Claim 2)
The gripping means is composed of left and right gripping means for gripping both left and right ends of the transported film, and at least one of the gripping position and the moving speed of the left and right gripping means can be controlled independently on the left and right. The method for producing a retardation film according to claim 1, wherein:

(Claim 3)
3. The method for producing a retardation film according to claim 2, wherein, in the stretching step, each of the left and right gripping means has a plurality of gripping members, and each of the gripping members is 40 to 150 pieces.

(Claim 4)
The method for producing a retardation film according to claim 2 or 3, wherein an interval between grip portions of the grip member is 1 to 20 mm.

(Claim 5)
The method for producing a retardation film according to claim 3 or 4, wherein a length of the grip portion of the grip member is 50 to 150 mm.

(Claim 6)
The length of the said strip | belt-shaped film in the said extending process is 2-10 m, The manufacturing method of the phase difference film of any one of Claims 1-5 characterized by the above-mentioned.

(Claim 7)
The residual solvent amount (Z1) at the start of stretching has a relationship represented by the following formula (1) with the residual solvent amount (Z2) at the end of strip-shaped film stretching. The method for producing a retardation film according to claim 1.

Formula (1) 0.5 <= Z2 / Z1 <= 1
(Claim 8)
The retardation film according to any one of claims 1 to 7, wherein a stretching speed in the width direction of the strip film in the stretching step is 1.6 to 13.3% / second. Production method.

(Claim 9)
The method for producing a retardation film according to any one of claims 2 to 8, wherein the grip length of the left and right grip means is independently controlled on the left and right sides of the belt-like film.

(Claim 10)
The method for producing a retardation film according to claim 9, wherein the grip timing at the start or end of gripping at the grip start position or grip end position by the left and right gripping means is controlled independently on the left and right.

(Claim 11)
The method for producing a retardation film according to claim 9, wherein the left and right gripping means are respectively on a moving endless track rail, and a moving speed of each of the left and right gripping means is controlled independently on the left and right. .

(Claim 12)
The method for producing a retardation film according to any one of claims 2 to 11, wherein the stretching speed of the left and right gripping means in the width direction is independently controlled on the left and right.

(Claim 13)
The retardation film is in a roll shape, and before being wound into a roll shape, the orientation angle of the strip film is measured online, and the gripping length is independently controlled on the left and right sides of the strip film based on the measurement result. The method for producing a retardation film according to any one of claims 9 to 12, wherein:

(Claim 14)
It is retardation film manufactured with the manufacturing method of retardation film of any one of Claims 1-13, Comprising: Ro (Retardation in a film surface) shown by following General formula (1) is 30-. A retardation film having a thickness of 70 nm and an Rt (retardation in the film thickness direction) represented by the following general formula (2) of 80 to 250 nm.
Ro = (Nx−Ny) × d General formula (1)
Rt = ((Nx + Ny) / 2−Nz) × d General formula (2)
[In the formula, Nx is the refractive index in the width direction of the film, Ny is the refractive index in the longitudinal direction of the film, Nz is the refractive index in the film thickness direction, and d is the film thickness (nm). ]
(Claim 15)
The retardation film according to claim 14, wherein the retardation film is a cellulose ester film.

(Claim 16)
A polarizing plate comprising the retardation film according to claim 14.

(Claim 17)
A liquid crystal display device comprising the polarizing plate according to claim 16.

  According to the above configuration of the present invention, a retardation film that is a thin film and has excellent continuous productivity and excellent film peeling prevention property, a manufacturing method for manufacturing the retardation film, and a liquid crystal display device using the retardation film can be provided.

The present invention is a method for producing a retardation film having a stretching step of stretching the strip-shaped film to be conveyed in the width direction, and a cutting step of cutting both ends of the strip-shaped film stretched in the stretching step,
(1) The film thickness of the retardation film is 30 μm to 60 μm,
(2) The belt-like film to be conveyed is a belt-like film containing the polymer material, which is peeled off from the support after casting a dope containing the polymer material on the support.
(3) Stretching in the stretching step is performed by a stretching apparatus having a gripping means for gripping the belt-like film, and the residual solvent amount (Z1) at the start of stretching is 0.1 to 5.0% by mass, The ratio (H1) of the good solvent contained in the residual solvent is 0 to 40% by mass, the temperature (T1) of the belt-like film at the start of stretching is 30 to 180 ° C.,
(4) In the cutting step, the residual solvent amount (Z3) contained in the strip film is 0.1 to 4.0% by mass, and the good solvent ratio (H2) in the residual solvent contained in the strip film is It is 0 to 35% by mass.

  In the present invention, in particular, by carrying out the stretching step and the cutting step under the specific conditions as described above, a retardation film that is a thin film and has excellent continuous productivity and excellent film peeling prevention properties, and manufacturing the same. A method and a liquid crystal display device using the method can be provided.

  The retardation film according to the present invention is a film having an optical retardation, and is preferably optically uniform, transparent and easy to manufacture.

  Examples of retardation films include cellulose ester films, polyester films, polycarbonate films, polyarylate films, polysulfone (including polyethersulfone) films, polyethylene terephthalate, polyester films such as polyethylene naphthalate, and polyethylene films. , 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, polyetherketone Bromide films, polyamide films, fluorocarbon resin film, a nylon film, a cycloolefin polymer film, polymethyl methacrylate film, or an acrylic film or the like can be mentioned, but is not limited thereto.

  The strip-shaped film according to the present invention is a strip-shaped film of a polymer material obtained by casting a dope solution containing the polymer material constituting the above-described film on a support and peeling off the support from the support.

  The belt-like film used in the production method of the present invention may be a belt-like film obtained by casting and peeling as described above, and is a belt-like film immediately after obtaining the casting and peeling step. Alternatively, it may be a belt-like film that has been manufactured in this step and has been aged, or a belt-like film that has been once impregnated with a solvent after this step has been obtained.

  As the polymer material according to the present invention, cellulose ester, polycarbonate, polysulfone (including polyethersulfone) and cycloolefin polymer are preferable from the viewpoint of production, cost, transparency, uniformity, adhesiveness and the like. That is, the retardation film of the present invention is preferably a cellulose ester film, a polycarbonate film, a polysulfone (including polyether sulfone) film, or a cycloolefin polymer film.

  A cellulose ester film that is preferably used as a belt-like film will be described.

  As a method for producing a cellulose ester film, a dope (a solution in which cellulose is dissolved) prepared by dissolving a cellulose ester is cast on a support (stainless belt or the like) and formed into a film. It is obtained by a solution casting film forming method that is peeled off (also referred to as peeling).

  The solution casting film forming method will be described below. The longitudinal direction (may be abbreviated as MD in some cases) represents the machine conveyance direction and the dope casting direction, and the width direction (TD) represents the direction orthogonal to the longitudinal direction in the film plane.

<< Solution casting film forming method >>
(A) Dissolution process: Cellulose ester and additives are stirred in a dissolution vessel in an organic solvent mainly composed of a good solvent for cellulose ester (flakes, powders or granules (preferably particles having an average particle size of 100 μm or more)). It is a process of dissolving while forming a dope.

  There are various dissolution methods, such as a method performed at normal pressure, a method performed below the boiling point of the good solvent, a method performed under pressure above the boiling point of the good solvent, a method performed using the cooling dissolution method, and a method performed at high pressure. After dissolution, the dope is filtered with a filter medium, defoamed, and sent to the next process with a pump.

  Said dope is the solution which melt | dissolved the cellulose ester and the additive mentioned later in the organic solvent.

(Cellulose ester)
As the polymer material according to the present invention, cellulose that is a raw material of cellulose ester that is preferably used is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.

Cellulose esters use an organic acid such as acetic acid or an organic solvent such as methylene chloride when the acylating agent of the cellulose raw material is an acid anhydride (acetic anhydride, propionic anhydride, or butyric anhydride). The reaction is carried out using a novel protic catalyst. When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst.

  Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. In the cellulose ester, the acyl group reacts with the hydroxyl group of the cellulose molecule. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution. For example, cellulose triacetate has an acetyl group bonded to all three hydroxyl groups of the glucose unit.

  Although there is no limitation in particular in the cellulose ester which can be used as a strip | belt-shaped film of this invention, what satisfy | fills following formula (1) and (2) simultaneously is preferable.

(1) 2.5 ≦ X + Y ≦ 2.95
(2) 1.3 ≦ X ≦ 2.95
In the formula, X is the degree of substitution of the acetyl group, and Y is the degree of substitution of the propionyl group and / or butyryl group. Those satisfying the above two formulas are suitable for producing a cellulose ester film exhibiting excellent optical properties that meet the object of the present invention, and are excellent in heat resistance and as a retardation film, having good wavelength dispersion and good. With a good retardation.

  From the viewpoint of obtaining a film having uniform optical characteristics during width-stretching, in particular, less retardation distribution unevenness, 2.5 ≦ X + Y ≦ 2.9 is more preferable, and 2.5 ≦ X + Y ≦ 2.7 is more preferable. .

  As the cellulose ester, a cellulose ester to which a propionate group or a butyrate group is bonded in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, or cellulose acetate propionate butyrate is preferably used. Note that butyrate includes iso- in addition to n-. Cellulose acetate propionate having a large degree of substitution of propionate groups is characterized by excellent water resistance.

  The measuring method of the substitution degree of an acyl group can be measured according to ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably in the range of 60,000 to 300,000 because the mechanical strength of the resulting film is strong. Furthermore, the thing of 70000-200000 is used preferably.

  The number average molecular weight of the cellulose ester can be measured as follows.

  Measured by high performance liquid chromatography under the following conditions.

Solvent: Acetone Column: MPW × 1 (manufactured by Tosoh Corporation)
Sample concentration: 0.2 (mass / volume)%
Flow rate: 1.0 ml / min Sample injection volume: 300 μl
Standard sample: polymethyl methacrylate (weight average molecular weight Mw = 188,200)
Temperature: 23 ° C.

(Organic solvent)
Organic solvents useful for forming a dope that dissolves cellulose ester 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. Non-chlorine organic solvents 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-tetrafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1, Examples include 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 a main effect is shown in the dissolution, and an organic solvent used in a large amount is referred to as a main organic solvent or a main organic solvent. . The good solvent in the present invention is a solvent that dissolves 5 g or more of cellulose ester in 100 g of the solvent at 25 ° C.

  In addition to the organic solvent, the dope according to the present invention preferably contains 1% by mass to 40% by mass of an alcohol having 1 to 4 carbon atoms.

  After casting the dope on the metal support, the solvent begins to evaporate and the alcohol becomes higher, and the web gels, making the web strong and easy to peel off from the metal support. In addition, 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, tert-butanol and the like. Of these, ethanol is preferred because it has excellent dope stability, has a relatively low boiling point, good drying properties, and no toxicity. Since these organic solvents are poorly soluble in cellulose esters by themselves, they fall into the category of poor solvents. The poor solvent is a solvent that dissolves less than 5 g of cellulose ester in 100 g of solvent at 25 ° C.

  From the viewpoint of improving the film surface quality, the concentration of the cellulose ester in the dope is preferably adjusted to 15% by mass to 40% by mass, and the dope viscosity is preferably adjusted in the range of 10 Pa · s to 50 Pa · s.

  For the dope according to the present invention, the following various materials may be used.

<Additive>
The dope according to the present invention preferably contains a plasticizer, an ultraviolet ray inhibitor, an antioxidant, a dye, a matting agent, a retardation increasing agent and the like.

  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.

《Retardation increasing agent》
As the retardation increasing material, a retardation increasing agent composed of an aromatic compound having at least two aromatic rings is preferably used.

  The aromatic compound is preferably used in the range of 0.1 to 15 parts by mass and more preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate.

  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.

  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 bond relationship between two aromatic rings can be classified into (a) a condensed ring, (b) a direct bond with a single bond, and (c) a bond through a linking group (for aromatic rings). Spiro bonds cannot be formed). The connection relationship may be any of (a) to (c).

  Preferred examples of the condensed ring (a condensed ring of two or more aromatic rings) of (a) include an indene ring, naphthalene ring, azulene ring, fluorene ring, phenanthrene ring, anthracene ring, acenaphthylene ring, naphthacene ring, 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 Murrell. A naphthalene ring, an azulene ring, an indole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a benzotriazole ring and a quinoline ring can be mentioned.

  A preferred example of the single bond (b) is a bond between carbon atoms of two aromatic rings. Two aromatic rings may be bonded with 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, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group). Examples of alkyl groups (including substituted alkyl groups) 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, 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 increasing agent is preferably 300 to 800.

  As the aromatic compound, the following rod-shaped compound or a discotic compound such as a compound having a 1,3,5-triazine ring is particularly preferably used.

<Bar compound>
A rod-shaped compound is a compound having a linear molecular structure. The linear molecular structure means that the molecular structure of the rod-shaped compound is linear in the thermodynamically most 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 (1).

General formula (1) Ar ¹ -L ¹ -Ar ²
In formula (1), 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 heterocycle 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 Rings, pyridazine rings, pyrimidine rings, pyrazine rings, and 1,3,5-triazine rings are included. 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 the general formula (1), 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. Most preferred is 2 (vinylene or ethynylene). 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 (1), 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 (2) is more preferable.

General formula (2) Ar ¹ -L ² -XL ³ -Ar ²
In the general formula (2), 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 (1).

In General Formula (2), 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 the general formula (2), X is 1,4-cyclohexylene, vinylene or ethynylene. Specific examples of the compound represented by the general formula (1) are shown below.

  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-shaped compound 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-shaped compound can be synthesized with reference to methods described in the 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).

<Disc-shaped compound>
As the discotic compound, a compound having a 1,3,5-triazine ring can be preferably used.

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

In the general formula (3), 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 (3) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (3), 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 a hydrogen atom.

  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 carmoyl 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, sulfonamide 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.

When X ¹ , X ² or X ³ is —NR—, —O— or —S—, the heterocyclic group 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, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.

  The hetero atom in the heterocyclic ring is preferably each 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.

  The molecular weight of the compound having a 1,3,5-triazine ring is preferably 300 to 2,000. The boiling point of the compound is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Electronics Industry Co., Ltd.).

  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 (4) 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 (3).

  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 On} -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 O-n-C 4 H 9
^{MP-122: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-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 O-n-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 O-n-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.

《Plasticizer》
It is preferable to add a compound known as a plasticizer to the dope used in the present invention for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor permeability, adjusting retardation, etc. For example, phosphoric acid esters and carboxylic acid esters are preferably used.

  Further, a polymer obtained by polymerizing an ethylenically unsaturated monomer having a weight average molecular weight of 500 to 10,000 described in Japanese Patent Application No. 2001-198450, an acrylic polymer, an acrylic polymer having an aromatic ring in the side chain, or cyclohexyl An acrylic polymer having a group in the side chain is also preferably used. 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 phthalate, dicyclohexyl phthalate, dioctyl phthalate, and diethyl hexyl phthalate, and examples of the citrate ester include acetyltriethyl citrate and Mention may be made of acetyltributyl citrate. In addition, butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, triacetin, trimethylolpropane tribenzoate and the like can also be mentioned. 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, methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, Octyl phthalyl octyl glycolate is preferable, and ethyl phthalyl ethyl glycolate is particularly preferably used. Two or more of these alkylphthalylalkyl glycolates may be used in combination.

  The addition amount of these compounds is preferably 1% by mass to 20% by mass with respect to the cellulose ester from the viewpoints of achieving the desired effect and suppressing bleeding out from the film. Further, since the heating temperature during stretching and drying rises to about 200 ° C., the plasticizer preferably has a vapor pressure of 1333 Pa or less at 200 ° C. in order to suppress bleed out.

<Ultraviolet absorber>
Examples of ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like, but less benzotriazole compounds. Compounds are preferred. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 and polymer ultraviolet absorbers described in JP-A-6-148430 are preferably used. As an ultraviolet absorber, from the viewpoint of preventing the deterioration of polarizers and liquid crystals, it has an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of liquid crystal display properties, it has little absorption of visible light having a wavelength of 400 nm or more. Is preferred.

  Specific examples of the benzotriazole ultraviolet absorber 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-butyl Phenyl) -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'-tert-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 Examples include, but are not limited to, a mixture of -5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate. As commercially available products, TINUVIN 109, TINUVIN 171 and TINUVIN 326 (all manufactured by Ciba Specialty Chemicals) can be preferably used.

  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 are not limited thereto.

  As the ultraviolet absorber that can be used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber, which are highly transparent and excellent in preventing the deterioration of a polarizing plate and a liquid crystal element, are preferable, and unnecessary coloring occurs. Less benzotriazole-based UV absorbers are particularly preferably used.

  The UV absorber can be added to the dope without limitation as long as the UV absorber is dissolved in the dope, but in the present invention, the UV absorber is cellulose such as methylene chloride, methyl acetate, and dioxolane. Dope by dissolving in a good solvent for ester, or in a mixed organic solvent of a good solvent and a poor solvent such as lower aliphatic alcohol (methanol, ethanol, propanol, butanol, etc.) and mixed in a 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 as close as possible to each other. Content of a ultraviolet absorber is 0.01 mass%-5 mass%, especially 0.5 mass%-3 mass%.

"Antioxidant"
As the antioxidant, a hindered phenol compound is preferably used, and 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-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 -Di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-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) -isocyanurate, etc. Can be mentioned. 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 to be added is preferably 1 ppm to 1.0%, more preferably 10 ppm to 1000 ppm in terms of mass ratio with respect to the cellulose ester.

《Matting agent》
In this invention, it can make it easy to convey and wind up by containing a mat agent in a cellulose-ester film. The matting agent is preferably as fine as possible. Examples of the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples thereof include inorganic fine particles such as magnesium silicate and calcium phosphate, and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film.

  In many cases, fine particles such as silicon dioxide are surface-treated with an organic substance, but such particles are preferred because they can reduce the haze of the film.

  Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes, silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the sliding effect, and the smaller the average particle size, the better the transparency. The average particle size of the secondary particles of the fine particles is in the range of 0.05 μm to 1.0 μm. The average particle size of secondary particles of preferable fine particles is preferably 5 nm to 50 nm, more preferably 7 nm to 14 nm. These fine particles are preferably used in the cellulose ester film in order to produce irregularities of 0.01 μm to 1.0 μm on the surface of the cellulose ester film. The content of the fine particles in the cellulose ester is preferably 0.005% by mass to 0.3% by mass with respect to the cellulose ester.

  As the fine particles of silicon dioxide, Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc. manufactured by Nippon Aerosil Co., Ltd. can be mentioned, preferably Aerosil 200V, R972, R972V, R974, R202, and R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, such as Aerosil 200V and R972V, can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.

  When an alignment layer or a liquid crystal layer is applied, if the alignment is hindered by the unevenness of the matting agent, the matting agent can be contained only in the surface layer on one surface. Alternatively, a coating liquid containing these matting agents and cellulose ester (diacetyl cellulose, cellulose acetate propionate, etc.) can be applied to reduce the coefficient of friction and improve the slipperiness.

《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. Furthermore, an antistatic agent, a flame retardant, a lubricant, an oil agent, etc. may be added.

  (B) Casting step: A casting position on a metal support such as an endless metal belt, such as a stainless steel belt, or a rotating metal drum, in which the dope is fed to a pressure die through a pressurized metering gear pump and transferred indefinitely. And a step of casting a dope from a pressure die. The surface of the metal support is a mirror surface. Other casting methods include a doctor blade method in which the film thickness of the cast dope film is adjusted with a blade, or a reverse roll coater method in which the film is adjusted with a reverse rotating roll, but the slit shape of the die part is prepared. A pressure die that can be easily made uniform in film thickness is preferable. Examples of the pressure die include a coat hanger die and a T die, and any of them is preferably used. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked.

  (C) Solvent evaporation step: The web can be peeled from the metal support by heating the web (referred to as a web or a belt-like film after the dope is cast on the metal support) on the metal support. This is a step of evaporating the solvent until. In order to evaporate the solvent, there are a method of blowing air from the web side and / or a method of transferring heat from the back side of the metal support by a liquid, a method of transferring heat from the front and back by radiant heat, and the like. Is preferable in terms of drying efficiency. A method of combining them is also preferable.

  In order to increase the film forming speed, a method of increasing the web temperature on the metal support is effective. However, since excessive heat supply causes foaming from the inside of the web due to the solvent contained in the web, a preferable drying rate is defined by the composition of the web. A method of casting on a belt-like metal support is also preferably used in order to increase the film forming speed. When casting is performed using a belt-like support, the casting speed can be increased by increasing the belt length. However, increasing the belt length promotes deflection due to the belt's own weight. In order to cause vibration during film formation and make the film thickness non-uniform during casting, the belt length is preferably 40 m to 120 m.

  (D) Peeling step: This is a step of peeling the web in which the solvent has evaporated on the metal support at the peeling position. The peeled web is sent to the next process. If the residual solvent amount of the web at the time of peeling is too large, peeling is difficult, or conversely, if it is peeled off after sufficiently drying on the metal support, a part of the web is peeled off.

  There is a gel casting method (gel casting) as a method for increasing the film forming speed (the film forming speed can be increased because the film is peeled off while the residual solvent amount is as large as possible).

  For example, a poor solvent for the cellulose ester is added to the dope, and the dope is cast and then gelled, and the temperature of the metal support is lowered to gel. By gelling on a metal support and increasing the strength of the film at the time of peeling, peeling can be accelerated and the film forming speed can be increased.

  In this invention, it is preferable to adjust the temperature in the peeling position on this metal support body to 10 to 40 degreeC, More preferably, it is adjusting to 15 to 30 degreeC. Moreover, it is preferable that the amount of residual solvent of the web in a peeling position shall be 5 mass%-120 mass%. In the present invention, the residual solvent amount can be expressed by the following formula (10).

Formula (10): Residual solvent amount (% by mass) = {(MN) / N} × 100
[In formula, M is the mass at the time of measurement of a web, N is a mass when the web which measured M was dried at 110 degreeC for 3 hours. ]
When the film is formed on the belt-like support, the increase in speed promotes the above-described belt vibration. In consideration of the residual solvent amount at the time of peeling, the belt length, and the like, the film forming speed is preferably 10 m / min to 120 m / min, and more preferably 15 m / min to 60 m / min.

  (E) Drying step: After peeling, generally, the web is dried using a drying device that alternately conveys the web through rolls arranged in a staggered manner.

  As a drying means, hot air is generally blown on both sides of the web, but there is also a means for heating by applying a microwave instead of the wind. Too much drying tends to impair the flatness of the finished film. Throughout, the drying temperature is usually in the range of 30 to 250 ° C. The drying temperature, the amount of drying air, and the drying time differ depending on the solvent used, and the drying conditions may be appropriately selected according to the type and combination of the solvents used.

(F) Stretching process (also called tenter process)
The stretching process according to the present invention includes a process A for gripping the belt-shaped film by the gripping means, a process B for stretching the strip-shaped film, and a process C until the gripping by the gripping means after stretching is released.

  The stretching process according to the present invention will be described with reference to FIG.

  In FIG. 2, in step A, the belt-shaped film transported from the belt-shaped film transport step (not shown) is gripped by the gripping means, and in the next step B, the film is stretched in the width direction at a stretching angle as shown in FIG. 1. The film is stretched in a direction (perpendicular to the traveling direction of the film), and in the process C, the stretching is completed, the film is conveyed while being gripped, and the grip is released.

  Stretching in the stretching step according to the present invention is performed by a stretching apparatus having a gripping means for gripping the belt-like film, and the residual solvent amount (Z1) at the start of stretching is 0.1 to 5.0% by mass, and the residual The ratio (H1) of the good solvent contained in the solvent is 0 to 40% by mass, and the temperature (T1) of the belt-like film at the start of stretching needs to be 30 to 180 ° C.

  The residual solvent amount (Z1) at the start of stretching is the amount of the total solvent contained in the dope remaining in the belt-like film at the time when the step B is started. It is necessary to be mass%. The amount of residual solvent can be determined according to the general formula (10).

  Moreover, the ratio (H1) of the good solvent contained in the residual solvent is the ratio of the amount of the good solvent remaining at the time when the step B is started to the Z1. The amount of the remaining good solvent can be determined according to the general formula (10). The amount of the good solvent can be obtained by sampling a sample of the belt-shaped film at the place to be measured, collecting the solvent under reduced pressure, and measuring by gas chromatography.

  The ratio (H1) of the good solvent needs to be 0 to 40% by mass, more preferably 0 to 20% by mass, from the viewpoint of preventing film breakage starting from the part gripped by the gripping means, and preferably 0 to 10%. % Is particularly preferred.

  Further, the amount of residual solvent (Z1) at the start of stretching has a relationship represented by the following formula (11) with the amount of residual solvent (Z2) at the end of stretching of the strip-shaped film. From the viewpoint of preventing retardation of film properties and film properties from becoming non-uniform.

Formula (11) 0.5 ≦ Z2 / Z1 ≦ 1
The residual solvent amount (Z2) at the end of the stretching of the belt-shaped film is the amount of the total solvent remaining at the time when the step B is completed.

  The temperature (T1) of the belt-like film at the start of stretching is the temperature of the belt-like film at the time when the step B is started and needs to be 30 to 180 ° C. The temperature (T1) of the belt-like film at the start of stretching is more preferably 100 to 180 ° C, and particularly preferably 130 to 180 ° C.

  Stretching according to the present invention is performed by a stretching apparatus (also referred to as a tenter) having a gripping means for gripping the belt-like film. The gripping means is preferably composed of left and right gripping means for gripping the left and right ends of the conveyed belt-like film, and the left and right gripping means each preferably have a plurality of gripping members.

  In the stretching step, the number of gripping members of the left and right gripping means is preferably 40 to 150 on the left and right in terms of stretching uniformity, and the distance between these gripping members is preferably 1 to 20 mm. It is.

  The interval between the gripping members is preferably 1 to 10 mm, more preferably 2 to 9 mm, from the viewpoint of not causing non-stretched portions and not causing interference between the stretched portions of each gripping member. 3 to 7 mm is particularly preferable.

  The interval between the gripping members is the distance between the adjacent portions gripped by the gripping member of the belt-like film, and is the distance between the adjacent end portions of the gripped portions.

  In the stretching step, it is a preferable aspect that the length of the grip portion is 50 to 150 mm. The length of the gripping portion refers to the length in which the belt-like film is held by one gripping portion in the A step, the B step, and the C step.

  In the stretching step of the present invention, the stretching is performed in the width direction of the belt-like film, and the stretching speed in the width direction is 1. from the viewpoint of maintaining the retardation value of the belt-shaped film and the uniformity of film properties. It is preferably 6 to 13.3% / second (% is the ratio of the stretched length to the length (full width) in the width direction of the belt-like film).

  The right and left gripping means can control the position or moving speed for gripping the belt-like film independently on the left and right, and the orientation angle (the slow axis (orientation axis in the film plane) with respect to the width direction and the longitudinal direction. ) Direction relative to the width direction, which can be measured with an automatic birefringence meter.

  By using such a gripping means, in the manufacturing method of the present invention, it is preferable that the grip lengths of the left and right gripping means are controlled independently on the left and right sides of the belt-like film.

  The gripping length refers to the length of the strip film that is gripped by a plurality of gripping members from step A to step C.

  As a method of controlling the gripping position independently, a method of controlling the gripping start position or the gripping end position independently on the left and right sides is preferable.

  Further, as a method for independently controlling the moving speed, a method in which the left and right gripping means are each in the shape of an endless track rail for movement, and the moving speed of each of the left and right gripping means is preferably controlled independently on the left and right.

  Moreover, it is a preferable aspect that the stretching speed of the gripping means according to the present invention in the width direction is controlled independently from the left and right in terms of the uniformity of the orientation angle with respect to the width direction.

  In the present invention, the retardation film according to the present invention is in a roll shape, and before winding into a roll shape, the orientation angle of the strip film is measured online, and the gripping length is determined based on the result of this measurement on the left and right sides of the strip film. It is preferable from the standpoint of maintaining the uniformity of the orientation angle.

  The roll shape is a state where the film is wound so that the surface of the film and the opposite surface (back surface) are in contact with each other.

  Measuring on-line and controlling the gripping length independently on the left and right sides of the strip film based on the result of this measurement means that the gripping length is continuously measured based on the result of this measurement in the process of continuous stretching and winding. The grip length of the belt-like film is controlled independently.

  Thus, the retardation film which is more excellent in the uniformity of an orientation angle can be obtained by the method of feeding back the measured result online.

  FIG. 3 schematically shows an embodiment of the stretching apparatus according to the present invention.

  The belt-like film 101 is held by a large number of left-side holding members 2a and right-side holding members 2b (only some of them are shown), and is conveyed in the direction of the arrow.

  The stretching device 10 includes gripping means including gripping members 2a (clips) and 2b (clips), and further includes a left ring chain 1a and a right ring chain 1b for moving the grip members 2a and 2b. .

  The gripping members 2a and 2b are gripped by the left gripping member closer 3a and the right gripping member closer 3b on the left and right, respectively, and the gripping is released by the left gripping member opener 4a and the right gripping member opener 4b.

  The gripping members 2a and 2b have a clip shape and are gripped by sandwiching a belt-like film.

  In the example of FIG. 3, the left and right gripping member closers 3a and the right gripping member closer 3b are shifted from the corresponding left and right positions (shifted from the positions at both ends in the width direction orthogonal to the longitudinal direction) to thereby correspond to the corresponding left and right positions. The grip length is controlled independently on the left and right sides by controlling the timing at which the position is gripped.

(G) Cutting process (also called slitting process)
In the stretching step, portions where the belt-shaped film is deformed are generated at both ends of the belt-shaped film by gripping the gripping member.

  The cutting step according to the present invention is a step mainly intended to cut the deformed portions of the strip-like film produced at both ends, and is a step of cutting both ends of the strip-like film after the stretching step.

  The cutting is preferably performed after the stretching step and before the strip film is made into a roll, and can be performed before the drying step for further drying the strip film, simultaneously with the drying step, or after the drying step.

  The cutting can be performed with a slide cutter, a rotary cutter or the like.

  As the cutting position, a range from the both ends of the belt-like film to a position 300 mm inside from both ends is preferable depending on the shape of the gripping member. As a conveyance speed in a cutting process, 10-120 m / min is preferable.

  In the cutting step of the present invention, the amount of residual solvent (Z3) contained in the belt-like film is 0.1 to 4.0% by mass from the viewpoint of preventing cutting failure, and the good solvent ratio in the residual solvent contained in the belt-like film ( It is necessary that H2) is 0 to 35% by mass.

  Further, the residual solvent amount (Z3) contained in the belt-like film is 0.3 to 3.0% by mass, and the good solvent ratio (H2) in the residual solvent contained in the belt-like film is 1 to 20% by mass. It is preferable.

  In the above-mentioned cutting step, it means a point of time when cutting is started by the cutter for cutting, and the residual solvent amount (Z3) contained in the belt-like film and the good solvent ratio (H2 in the residual solvent contained in the belt-like film) ) Can be obtained in the same manner as (Z1) and (H1).

<Phase difference film>
The film thickness of the retardation film according to the present invention is 30 to 60 μm. In order to make the film thickness within this range, the thickness of the strip-like film before stretching is preferably 35 to 120 μm on the basis of non-stretching (the stretching ratio in the width direction and the longitudinal direction is 0). 40-60 μm is preferable.

  In order to make it the thickness of this range, it can carry out by preparing the manufacturing conditions of the process before an above-described extending process.

  The film thickness in the present invention refers to the average value of the values measured by slitting the film in the width direction and measuring it at intervals of 2 cm in the width direction.

The retardation film according to the present invention is a film obtained by the above production method, and Ro (retardation in the film plane) represented by the following general formula (1) is 30 to 70 nm. Rt (retardation in the film thickness direction) represented by 2) is preferably 80 to 250 nm.
Ro = (Nx−Ny) × d General formula (1)
Rt = ((Nx + Ny) / 2−Nz) × d General formula (2)
[In the formula, Nx is the refractive index in the width direction of the film, Ny is the refractive index in the longitudinal direction of the film, Nz is the refractive index in the film thickness direction, and d is the film thickness (nm). ]
The retardation film of the present invention can be used as a retardation film (also referred to as a retardation plate) for expanding the viewing angle of a liquid crystal display device by itself.

  The polarizing plate of this invention is comprised as what laminated | stacked the retardation film of this invention on the at least one side of the polarizer.

  A conventionally well-known thing can be used as a polarizer used for a polarizing plate. For example, a film made of a hydrophilic polymer such as polyvinyl alcohol is treated with a dichroic dye such as iodine and stretched, or a plastic film such as vinyl chloride is treated and oriented. The polarizer thus obtained is laminated with a retardation film.

  When using a polarizer using polyvinyl alcohol, the retardation film of the present invention is particularly preferably a cellulose ester from the viewpoint of adhesiveness.

  The liquid crystal display device of the present invention can be obtained by incorporating the polarizing plate thus obtained. The polarizing plate may be provided on one side of the liquid crystal display device liquid crystal cell or on both sides. In any case, the liquid crystal display device of the present invention can be obtained by attaching the retardation film of the present invention to the polarizer closer to the liquid crystal cell.

  By incorporating the polarizing plate of the present invention into a liquid crystal display device, the liquid crystal display device of the present invention having various visibility can be produced.

  When the retardation film of the present invention is installed in a liquid crystal display device, an upper polarizer and a lower polarizer arranged on the upper and lower sides of a pair of substrates located on both sides of the driving liquid crystal cell are usually configured. When at least one polarizing plate of the present invention is installed between the substrate and either the upper or lower polarizer, or between the substrate and the upper and lower polarizers, when observed from the front direction The retardation film of the present invention is provided between the polarizer on the observer side and the substrate on the drive cell side in the case of a display device from the viewpoint of color shift (color shift) when observed from an oblique direction to the color of the present invention. It is preferable to install two sheets.

  When the liquid crystal display device is a twisted nematic type (TN type) liquid crystal display device in particular, a retardation film is bonded in a direction in which the cellulose ester film support surface of the optical compensation film is in contact with the substrate closest to the TN type liquid crystal cell. And the objective of this invention can be expressed effectively that the maximum refractive index direction of retardation film is bonded in the direction substantially orthogonal to the orientation direction of the nematic liquid crystal of the board | substrate nearest to the said liquid crystal cell. “Substantially orthogonal” means 90 ° ± 5 °, preferably 90 °.

  The retardation film of the present invention is a reflective type, transmissive type, transflective type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. Preferably used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
<< Production of cellulose ester film >>
As described below, a dope solution and an ultraviolet absorber solution were prepared, and a cellulose ester film was produced using them.

(Preparation of dope)
100 parts by weight of cellulose ester A described below, 2 parts by weight of ethylphthalylethyl glycolate, 8.5 parts by weight of triphenyl phosphate, 290 parts by weight of methylene chloride, and 60 parts by weight of ethanol are placed in a sealed container, and the mixture is slowly stirred. While gradually raising the temperature, the temperature was raised to 45 ° C. over 60 minutes for dissolution. The inside of the container was 1.2 atm. This dope was added to Azumi Filter Paper No. After filtration using 244, the foam in the dope was removed after standing for 24 hours.

Cellulose ester A: Degree of acetyl substitution 2.0, degree of propionyl substitution, 0.5, degree of polymerization 350
(Preparation of UV absorber solution)
Separately, 5 parts by mass of the above cellulose ester A, 6 parts by mass of Tinuvin 326 (manufactured by Ciba Specialty Chemicals Co., Ltd.), 4 parts by mass of Tinuvin 109 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Tinuvin 171 5 parts by mass (manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed with 94 parts by mass of methylene chloride and 8 parts by mass of ethanol and dissolved by stirring to prepare an ultraviolet absorber solution.

  After adding 2 parts by weight of the UV absorbent solution to 100 parts by weight of the dope, the mixture was sufficiently mixed by a static mixer, and then cast from a die onto a stainless steel belt at a dope temperature of 30 ° C. and a width of 1.6 m. .

  After drying for 1 minute on a stainless steel belt whose temperature is controlled by contacting hot water at a temperature of 25 ° C. from the back surface of the stainless steel belt, and further holding 15 ° C. cold water on the back surface of the stainless steel belt for 15 seconds, Peeled from the stainless steel belt.

  Then, under the conditions shown in Table 1 below, the following operation was performed to prepare a retardation film, and evaluation was performed by the following evaluation method. The results are shown in Table 1.

  Both ends of the peeled web were gripped with clips using a tenter and stretched in the width direction (the number of gripping members was 100). After stretching the web with a tenter, the film edge was cut using a slitter.

  The obtained cellulose ester film was wound around a glass fiber reinforced resin core having a core diameter of 200 mm into a film roll having a width of 1.4 m and a length of 1000 m by a taper tension method. At this time, an embossing ring having a temperature of 250 ° C. was pressed against the end of the film, and the thickness was processed to prevent adhesion between the films.

[Evaluation methods]
Continuous productivity: A dope was cast, a retardation film was produced, and a continuous production time was measured without causing any film breakage. This time was used as an index of continuous productivity.

Film peeling prevention: The film was treated with a 2 mol / L-NaOH solution, and the contact angle was measured using pure water using a contact meter. 100 measurement points were taken in the width direction, the standard deviation of the data was obtained, the uniformity of the saponification treatment was measured, and this was used as an index for preventing film peeling.
◎: Less than 5 ○: 5 or more, less than 10 ×: 10 or more

  From Table 1, it can be seen that the production method of the present invention provides a retardation film that is excellent in continuous productivity and excellent in prevention of film peeling.

Example 2
A retardation film was prepared and evaluated in the same manner as in Example 1 except that the number of gripping members (the number of clips) at the time of stretching was changed under the conditions of Sample A3 in Example 1.

The results are shown below.
Remarks The present invention The present invention The present invention The present invention Comparative sample B1 B2 B3 B4 B5 A5
Number of clips (pieces) 35 40 100 150 160 100
Film peeling prevention ○ ◎ ◎ ◎ ○ ×
Continuous productivity (hr) 5 10 11 11 5 1
From the above results, it can be seen that the production method of the present invention provides a retardation film that is excellent in continuous productivity and excellent in prevention of film peeling.

Example 3
A retardation film was prepared and evaluated in the same manner as in Example 2 except that the interval between the gripping members was changed under the conditions of Sample B3 in Example 2. The results are shown below.
Remarks Present Invention Present Invention Present Invention Present Invention Sample C1 C2 C3 C4 C5
Clip interval (mm) 1 2 10 20 25
Film peeling prevention ○ ◎ ◎ ◎ ○
Continuous productivity 10 19 20 20 10
From the above results, it can be seen that the production method of the present invention provides a retardation film that is excellent in continuous productivity and excellent in prevention of film peeling.

Example 4
A retardation film was produced and evaluated in the same manner as in Example 3 except that the residual solvent ratio was changed under the conditions of Sample C3 in Example 3. The results are shown below.
Remarks The present invention The present invention The present invention sample D1 D2 D3 D4
Z2 / Z1 0.4 0.5 0.8 1.0
Film peeling prevention ○ ◎ ◎ ◎
Continuous productivity 20 49 50 50
From the above results, it can be seen that the production method of the present invention provides a retardation film that is excellent in continuous productivity and excellent in prevention of film peeling.

Example 5
A retardation film was prepared and evaluated in the same manner as in Example 4 except that the stretching speed of the gripping member was changed as described below under the conditions of Sample D3 in Example 4. The results are shown below.

The present invention The present invention The present invention The present invention sample E1 E2 E3 E4 E5
Stretching speed (% / sec) 1.5 1.6 10 13.3 14
Film peeling prevention ○ ◎ ◎ ◎ ○
Continuous productivity 50 100 110 100 52
From the above results, it can be seen that the production method of the present invention provides a retardation film that is excellent in continuous productivity and excellent in prevention of film peeling.

Example 6
A retardation film was prepared and evaluated in the same manner as in Example 5 except that the control of the gripping member was changed as described below under the conditions of Sample E3 in Example 5. The results are shown below.

The present invention The present invention The present invention The present invention The present invention sample F1 F2 F3 F4 F5 F6
Clip control / opener position independent control off on on on on
・ Closer position independent control off on on on on
Left and right grip length control off off on on on on
Left / right speed control off off on on on
Online measurement feedback / Orientation angle feedback off off off off on on
・ Phase difference feedback off off off off on
Film peeling prevention ○ ◎ ◎ ◎ ◎ ◎
Continuous productivity 100 200 250 280 290 300
From the above results, it can be seen that the production method of the present invention provides a retardation film that is excellent in continuous productivity and excellent in prevention of film peeling.

Example 7 (Production of viewing angle widening polarizing plate and liquid crystal display device)
Using the produced cellulose ester films F6 (present invention) and A5 (comparative example), a polarizing plate and a liquid crystal display device were produced in the following manner.

<< Production of Polarizing Plates P101 and P102 >>
Using the produced cellulose ester film samples F6 and A5, the alkali saponification treatment and polarizing plates P101 and P102 described below were produced.

<Alkali saponification treatment>
Saponification process 2 mol / L-NaOH 50 ° C. 90 seconds Water washing process Water 30 ° C. 45 seconds Neutralization process 10% HCl 30 ° C. 45 seconds Water washing process Water 30 ° C. 45 seconds Water treatment, neutralization, water washing It performed in order and then dried at 80 degreeC.

<Production of polarizer>
A 120 μm-thick long roll polyvinyl alcohol film was immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched in the transport direction 6 times at 50 ° C. to form a polarizing film.

  KC8UX2M manufactured by Konica Minolta Opto Co., Ltd., which was similarly saponified on one side of the polarizer, and the alkali saponified cellulose ester film and cycloolefin polymer film on the opposite side were completely saponified polyvinyl alcohol 5% aqueous solution. Are bonded to each other by roll-to-roll so that the transmission axis of the polarizer and the in-plane slow axis of the film are parallel to each other, and dried to produce polarizing plates P101 (present invention) and P102 (comparative example) did.

<< Production of liquid crystal display devices A and B >>
About the obtained polarizing plate P101 (present invention) and P102 (comparative example), in combination with the liquid crystal panel LL-T1620 manufactured by Sharp, the polarizing plate previously bonded to the liquid crystal panel is peeled off, and on both sides of the liquid crystal cell, A polarizing plate was bonded via an adhesive so as to be in the same direction as the transmission axis of the polarizing plate that had been bonded in advance, to prepare liquid crystal display devices A (present invention) and B (comparative example).

  The obtained polarizing plate and liquid crystal display device were treated for 300 h under the conditions of 60 ° C. and relative humidity of 90% Rh, and the polarizing plate was visually examined.

  As a result, no particular change was observed in the polarizing plate P101 and the liquid crystal display device A of the present invention. However, in the polarizing plate P102 and the liquid crystal display device B of the comparative example, peeling of the polarizing plate was observed and there was a problem.

It is a figure explaining the extending | stretching angle in an extending | stretching process. It is the schematic which shows an example of the extending | stretching process which concerns on this invention. It is a schematic plan view which shows typically one embodiment of the extending | stretching apparatus which concerns on this invention.

Explanation of symbols

1a Left ring chain (rotary drive)
1b Right wheel chain (rotary drive)
2a Left grip member 2b Right grip member 3a Left grip member closer 3b Right grip member closer 4a Left grip member opener 4b Right grip member opener 10 Stretching device

Claims (17)

A method for producing a retardation film comprising a stretching step of stretching a strip-shaped film to be conveyed in the width direction, and a cutting step of cutting both ends of the strip-shaped film stretched in the stretching step,
(1) The film thickness of the retardation film is 30 μm to 60 μm,
(2) The belt-like film to be conveyed is a belt-like film containing the polymer material, which is peeled off from the support after casting a dope containing the polymer material on the support.
(3) Stretching in the stretching step is performed by a stretching apparatus having a gripping means for gripping the belt-like film, and the residual solvent amount (Z1) at the start of stretching is 0.1 to 5.0% by mass, The ratio (H1) of the good solvent contained in the residual solvent is 0 to 40% by mass, the temperature (T1) of the belt-like film at the start of stretching is 30 to 180 ° C.,
(4) In the cutting step, the residual solvent amount (Z3) contained in the strip film is 0.1 to 4.0% by mass, and the good solvent ratio (H2) in the residual solvent contained in the strip film is It is 0-35 mass%, The manufacturing method of retardation film characterized by the above-mentioned. The gripping means is composed of left and right gripping means for gripping both left and right ends of the transported film, and at least one of the gripping position and moving speed of the left and right gripping means can be controlled independently on the left and right. The method for producing a retardation film according to claim 1, wherein: 3. The method for producing a retardation film according to claim 2, wherein, in the stretching step, each of the left and right gripping units has a plurality of gripping members, and each of the gripping members is 40 to 150 pieces. The method for producing a retardation film according to claim 2 or 3, wherein an interval between grip portions of the grip member is 1 to 20 mm. The method for producing a retardation film according to claim 3 or 4, wherein a length of the grip portion of the grip member is 50 to 150 mm. The length of the said strip | belt-shaped film in the said extending process is 2-10 m, The manufacturing method of the phase difference film of any one of Claims 1-5 characterized by the above-mentioned. The residual solvent amount (Z1) at the start of stretching has a relationship represented by the following formula (1) with the residual solvent amount (Z2) at the end of strip-shaped film stretching. The method for producing a retardation film according to claim 1.
Formula (1) 0.5 <= Z2 / Z1 <= 1 The retardation film according to any one of claims 1 to 7, wherein a stretching speed in a width direction of the strip-shaped film in the stretching step is 1.6 to 13.3% / second. Production method. The method for producing a retardation film according to any one of claims 2 to 8, wherein the grip length of the left and right grip means is independently controlled on the left and right sides of the belt-like film. The method for producing a retardation film according to claim 9, wherein the grip timing at the start or end of gripping at the gripping start position or gripping end position by the left and right gripping means is controlled independently on the left and right. The method for producing a retardation film according to claim 9, wherein the left and right gripping means are each on an endless track rail for movement, and the moving speed of each of the left and right gripping means is controlled independently on the left and right. . The method for producing a retardation film according to any one of claims 2 to 11, wherein the stretching speed in the width direction of the left and right gripping means is independently controlled on the left and right sides. The retardation film is in a roll shape, and before being wound into a roll shape, the orientation angle of the strip film is measured online, and the grip length is independently controlled on the left and right sides of the strip film based on the measurement result. The method for producing a retardation film according to any one of claims 9 to 12, wherein: It is retardation film manufactured with the manufacturing method of retardation film of any one of Claims 1-13, Comprising: Ro (Retardation in a film surface) shown by following General formula (1) is 30-. A retardation film having a thickness of 70 nm and an Rt (retardation in the film thickness direction) represented by the following general formula (2) of 80 to 250 nm.
Ro = (Nx−Ny) × d General formula (1)
Rt = ((Nx + Ny) / 2−Nz) × d General formula (2)
[In the formula, Nx is the refractive index in the width direction of the film, Ny is the refractive index in the longitudinal direction of the film, Nz is the refractive index in the film thickness direction, and d is the film thickness (nm). ] The retardation film according to claim 14, wherein the retardation film is a cellulose ester film. A polarizing plate comprising the retardation film according to claim 14. A liquid crystal display device comprising the polarizing plate according to claim 16.

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