KR101973884B1 - Method for producing oblique stretched film - Google Patents

Abstract

A method of producing an obliquely-drawn film is a method of holding a film at both ends in the width direction with a pair of gripping portions, relatively advancing one of the waveguide segments and relatively delaying the other waveguide segments, And an oblique stretching step of stretching the film in an oblique direction with respect to the width direction by bending the film in an arc shape. In the oblique stretching process, the temperature of the film is changed in the width direction at the time when the arcuate curvature of the conveying path for stretching in the oblique direction starts at the earliest point in the width direction of the film.

Description

Method for producing oblique stretched film

The present invention relates to a method of producing an obliquely-drawn film in which a film is stretched in an oblique direction with respect to a width direction.

2. Description of the Related Art Conventionally, a self-emission type display device such as an organic EL (Electro-Luminescence) display device which is also called an OLED (Organic light-Emitting Diode) attracts attention. In the OLED, since a reflector such as an aluminum plate is provided on the back side of the display in order to increase the light extraction efficiency, the external light incident on the display is reflected by the reflector, thereby lowering the contrast of the image.

Therefore, it is known that a circular polarizer is formed by joining a stretched film and a polarizer in order to improve the contrast of light and shade by preventing reflection of external light, and this circular polarizer is disposed on the surface side of the display. At this time, the circularly polarizing plate is formed by bonding a polarizer and a stretched film so that the in-plane slow axis in the stretched film is inclined at a desired angle with respect to the transmission axis of the polarizer.

However, a general polarizer (polarizing film) is obtained by stretching at a high magnification in the longitudinal direction, and its transmission axis coincides with the width direction. In addition, the conventional retardation film is produced by longitudinal drawing or transverse stretching, and in principle, the slow axis in the plane is at 0 ° or 90 ° with respect to the longitudinal direction of the film. Thus, in order to tilt the transmission axis of the polarizer and the slow axis of the stretched film to a desired angle as described above, it is not necessary to employ a batch formula in which the long polarizing film and / or the stretched film are cut at a specific angle and the film pieces are bonded one by one And productivity was deteriorating.

On the other hand, the film is stretched in the direction of the desired angle (in the oblique direction) with respect to the longitudinal direction, and the direction of the slow axis is controlled by the long oblique stretching Various methods for producing a film have been proposed. For example, in the manufacturing method of Patent Document 1, the resin film is led out from a direction different from the winding direction of the stretched film, and both ends of the resin film are gripped and transported by the pair of wave earths. By changing the conveying direction of the resin film in the middle, the resin film is stretched in the oblique direction. Thereby, a long obliquely-drawn film having a slow axis at a desired angle exceeding 0 DEG and less than 90 DEG with respect to the longitudinal direction is produced.

By using such a long oblique stretched film, it is possible to produce a circular polarizer plate by joining a long polarizer film and a long obliquely stretched film by a roll-to-roll method, and the productivity of the circular polarizer plate is remarkably improved.

However, in recent years, there is a growing demand for large-sized and high-definition OLEDs, and for obliquely stretched films applied to circularly polarizing plates of OLEDs, it is increasingly desired to reduce variations in optical characteristics. In view of this point, in the above-described Patent Document 1, in order to reduce variations in optical characteristics, a film whose film thickness is changed in the width direction in advance is prepared, and the film is subjected to oblique stretching, So that it is attempted to equalize.

JP-A-2010-173261 (claim 1, paragraphs 0006, 0010, 1 to 4, etc.)

However, when an oblique stretched film described in Patent Document 1 is used for an OLED which requires a higher contrast than a liquid crystal display device, color unevenness may occur. In particular, a film having a large thickness difference in the width direction And the film having the maximum thickness increased by 3% or more of the minimum thickness in the width direction of the film) was used, and it was found that the tendency was strong. As a factor of the color unevenness, it was found that the orientation angle of the optical axis (slow axis) in the width direction of the warp stretched film was uneven. As a result of further investigation, it was found that unevenness of the optical axis was caused by uneven stretching (= film thickness unevenness). That is, it has been found that even when the method of Patent Document 1 is used, unevenness in stretching in the width direction in the warp stretched film is reduced, and the unevenness of the orientation angle can not be reduced. The reason is presumed as follows.

When an obliquely-stretched film is produced using a so-called bending type warp stretching device in which the conveying path of the film is bent in the middle as shown in Patent Document 1, the film is stretched in the width direction as shown in Fig. 15, And the stretching behavior is decreased. Therefore, a factor that is effective for stretching non-uniformity is increased by one factor (film shrinkage in the carrying direction also becomes a factor that affects the thickness unevenness) than ordinary transverse stretching (stretching only in the width direction). As a result, when oblique stretching is performed using a film whose film thickness is largely changed in the width direction, stretching unevenness in the width direction due to the difference in elongation / shrinkage behavior due to the thickness difference in the width direction is apt to occur, It is considered that the variation of the optical axis in the width direction, that is, the unevenness of the orientation angle, is likely to occur.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-described problems, and it is an object of the present invention to provide an OLED that is capable of reducing the unevenness of the orientation angle in the film width direction even when oblique stretching is performed by bending the conveying path, It is possible to reduce color unevenness when applied.

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

A method of producing an obliquely-drawn film according to one aspect of the present invention is a method of producing an obliquely-drawn film by holding both ends in the width direction of a film with a pair of gripping portions, relatively delaying one of the waveguide regions, And a warp stretching step of stretching the film in an oblique direction with respect to the width direction by bending the conveying path of the film in an arc shape together with the conveying tray,

In the oblique stretching step, the temperature of the film is changed in the width direction at the time when the arcuate curvature of the conveying path for elongating in the oblique direction starts at the earliest point in the width direction of the film.

In the oblique stretching process, at the time when the oblique stretching is started at the earliest point, that is, when the arcuate curvature of the film transport path for stretching in the oblique direction starts at the earliest point in the width direction of the film, It is possible to reduce occurrence of uneven stretch in the width direction due to shrinkage of the film in the transport direction which occurs during oblique stretching, and it is possible to reduce occurrence of unevenness of the orientation angle in the width direction. As a result, even when the oblique stretched film thus produced is applied to a circularly polarizing plate for preventing reflection of external light of the organic EL display device (OLED), the color unevenness caused by the unevenness of the orientation angle can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view schematically showing a schematic configuration of an apparatus for producing an oblique-drawn film according to an embodiment of the present invention. Fig.
2 is a plan view schematically showing an example of a rail pattern of a stretching portion of the production apparatus.
3 is an explanatory view schematically showing a state in which the conveying path of the film in the stretching portion is bent in the middle.
Fig. 4 is an explanatory view showing another example of the drawing method of the stretching portion. Fig.
5 is an explanatory diagram schematically showing an example of a detailed configuration of the stretching portion.
Fig. 6 is an explanatory diagram schematically showing another example of the configuration of the elongating portion. Fig.
Fig. 7 is an explanatory diagram schematically showing another configuration example of the stretching portion. Fig.
8 is an explanatory view schematically showing another example of the configuration of the elongating portion.
Fig. 9 is an explanatory view schematically showing another configuration example of the stretching portion. Fig.
10 is a cross-sectional view showing a schematic structure of an organic EL image display apparatus to which the obliquely stretched film is applied.
11 is a cross-sectional view showing a schematic configuration of a liquid crystal display device to which the oblique stretched film is applied.
12 is a graph showing an example of the temperature distribution in the width direction of the warp stretched film of the comparative example.
13 is a graph showing an example of the temperature distribution in the width direction of the obliquely-drawn film of the embodiment.
14 is a graph showing another example of the temperature distribution.
Fig. 15 is an explanatory view showing the behavior of the film in the transverse direction and the transport direction in transverse stretching and warp stretching.

An embodiment of the present invention will be described with reference to the drawings as follows. In the present specification, when numerical ranges are denoted by A to B, values of lower limit A and upper limit B are included in the numerical range.

A method of producing a long obliquely-drawn film according to the present embodiment is a method of producing a long obliquely-stretched film by stretching a long-shaped raw film including a thermoplastic resin in an oblique direction with respect to the width direction and the longitudinal direction, .

The orientation direction of the long oblong stretched film, that is, the direction of the slow axis, is a direction that is greater than 0 DEG and less than 90 DEG with respect to the width direction of the film in the film plane (in the plane perpendicular to the thickness direction) (The direction of the film is also in the direction of more than 0 ° and less than 90 ° with respect to the longitudinal direction of the film). Since the slow axis is usually expressed in the stretching direction or the direction perpendicular to the stretching direction, stretching is performed in a direction exceeding 0 DEG and less than 90 DEG with respect to the width direction of the film to produce a long warp stretched film having such a slow axis . The angle formed by the width direction and the slow axis of the long oblong stretched film, that is, the orientation angle can be arbitrarily set to a desired angle in a range exceeding 0 degrees and less than 90 degrees.

In the present embodiment, the term "long" means that the film has a length of at least about 5 times or more, preferably 10 times or more, more specifically, It is conceivable to have a length enough to be transported (film roll).

The long warp stretched film may be produced by forming a long unoriented film and winding it on a winding core to form a wound body (raw film), and supplying the raw film to the oblique stretching process from the wound body, The long film after the film formation may be supplied to the oblique stretching step continuously from the film forming step without taking up the long film. The film-forming step and the oblique stretching step are preferably performed in succession because the desired film-elongated film can be obtained by changing the film-forming conditions by feeding back the results of film thickness and optical value of the stretched film. In addition, by continuously producing a long warp stretched film, a long warp stretched film having a desired length can be obtained.

As the thermoplastic resin included in the fabric film, an alicyclic olefinic polymer resin (COP), a polycarbonate resin (PC), a cellulose ester resin, or the like can be used. Among them, the cellulose ester resin is easy to absorb moisture, and the orientation angle? Is likely to fluctuate due to the humidity variation accompanying long-time use. Therefore, the cellulose ester- The effect of the embodiment becomes larger.

Further, the warp stretched film obtained by obliquely stretching the raw film can be applied to a liquid crystal display device which can be visually recognized by wearing polarized sunglasses. That is, a circularly polarizing plate is constituted by joining an obliquely stretched film to the viewer side of the polarizer of the viewer side polarizing plate rather than the liquid crystal layer. At this time, they are bonded so that the slow axis of the warp stretched film and the transmission axis of the polarizer become 45 degrees. In this configuration, the linearly polarized light emitted from the liquid crystal layer and transmitted through the polarizer on the viewing side is converted into circularly polarized light from the obliquely drawn film (serving as QWP). Therefore, in the case where the observer attaches the polarizing sunglasses and observes the display image of the liquid crystal display device, even if the angle between the transmission axis of the polarizer and the transmission axis of the polarizing sunglass is parallel to the transmission axis of the polarizing sunglass, And guided to the eyes of the observer to observe the display image. Therefore, it is possible to suppress the display image from being hardly seen (depending on the direction of the transmission axis of the polarizing sunglass) depending on the viewing angle. In particular, by forming the warp stretched film using the raw film of this embodiment, unevenness of the orientation angle? In the film width direction can be suppressed. Therefore, even if the liquid crystal display device is used for a long time, Can be observed through polarized sunglasses.

As described above, when the oblique stretched film is applied to the circularly polarizing plate of the liquid crystal display device corresponding to polarized sunglasses, it is preferable to form a hard coat layer for protecting the obverse-side stretched film on the viewer side of the obliquely stretched film.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.

<Cellulose ester-based resin>

The cellulose ester based resin film used in the raw film of the present embodiment is preferably a film containing a cellulose acylate satisfying the following formulas (1) and (2) and containing a compound represented by the following formula (A) .

 2.0 < / RTI &gt; &lt; RTI ID =

 (2) 0? X <3.0

(In the formulas (1) and (2), Z1 represents the total acyl substitution degree of the cellulose acylate, and X represents the sum of the propionyl substitution degree and the butyryl substitution degree of the cellulose acylate)

Hereinafter, general formula (A) will be described in detail. In formula (A), L ₁ and L ₂ each independently represent a single bond or a divalent linking group. Examples of L ₁ and L ₂ include the following structures (in the following, R represents a hydrogen atom or a substituent).

L ₁ and L ₂ are preferably -O-, -COO-, and -OCO-.

R ₁ , R ₂ and R ₃ each independently represent a substituent. Specific examples of the substituent represented by R ₁ , R ₂ and R ₃ include a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), an alkyl group (methyl group, ethyl group, n- Cyclohexyl group, cyclopentyl group, 4-n-dodecylhexyl group, etc.), alkenyl group (vinyl group, allyl group, etc.) (Such as a phenyl group, a p-tolyl group, or a naphthyl group), an alkenyl group (e.g., an isopropyl group, an n-butyl group, , A heterocyclic group (such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group or a 2-benzothiazolyl group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, Butoxy group, 2-methoxyethoxy group, etc.), an aryloxy group (phenoxy group, 2-methylphenoxy group, 4-tert- Phenoxy group, 2- Acyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group and the like), amino group (amino group , An acylamino group (formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group and the like), an amino group such as a methylamino group, a dimethylamino group, an anilino group, Alkyl and arylsulfonylamino groups such as methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group and p-methylphenylsulfonylamino group, mercapto group, alkylthio group (Methylthio group, ethylthio group, n-hexadecylthio group and the like), arylthio group (phenylthio group, p-chlorophenylthio group and m-methoxyphenylthio group), sulfamoyl group Sulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N- (N'-phenylcarbamoyl) sulfamoyl group, etc.), a sulfo group, an acyl group (such as an acetyl group, a pivaloylbenzoyl group, etc.) ), Carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) ).

R ₁ and R ₂ are preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclohexyl group, more preferably a phenyl group having a substituent or a cyclohexyl group having a substituent, A phenyl group having a substituent at the 4-position, and a cyclohexyl group having a substituent at the 4-position.

R ₃ is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a cyano group or an amino group, Is a hydrogen atom, a halogen atom, an alkyl group, a cyano group, or an alkoxy group.

Wa and Wb represent a hydrogen atom or a substituent,

(I) Wa and Wb may combine with each other to form a ring,

(II) at least one of Wa and Wb may have a cyclic structure, or

(III) At least one of Wa and Wb may be an alkenyl group or an alkynyl group.

Specific examples of the substituent represented by Wa and Wb include a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, (Vinyl group, allyl group and the like), cycloalkenyl group (2-ethylhexyl group and the like), cycloalkyl group (cyclohexyl group, cyclopentyl group, (Such as a phenyl group, a p-tolyl group, or a naphthyl group), a heterocyclic group (such as a cyclopenten-1-yl group or a 2-cyclohexene-1-yl group), an alkynyl group (an ethynyl group or a propargyl group) A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (a methoxy group, an ethoxy group, an isopropoxy group, an isopropoxy group, an isopropoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-methoxyphenoxy group, Tetradeca An aminophenoxy group and the like), an acyloxy group (formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group and p-methoxyphenylcarbonyloxy group) An amino group, an amino group, a dimethylamino group, an anilino group, an N-methyl-anilino group and a diphenylamino group), an acylamino group (formylamino group, acetylamino group, pivaloylamino group, lauroylamino group and benzoylamino group) (Methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, etc.), mercapto group, alkylthio group (E.g., methylthio, ethylthio, n-hexyldecylthio etc.), arylthio groups (phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group etc.), sulfamoyl groups Di-, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethyl sulf (E.g., an acetyl group, a pivaloylbenzoyl group, etc.), a sulfonyl group, an acyl group, an acyl group, an acyl group, an acyl group, (Carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group and the like) .

The substituent may also be substituted with such a group.

(I) When Wa and Wb are bonded to each other to form a ring, the ring is preferably a nitrogen-containing 5-membered ring or a sulfur-containing 5-membered ring. The compound represented by the formula (A) is particularly preferably a compound represented by the following formula (1) or (2).

In the general formula (1), A ₁ and A ₂ each independently represent -O-, -S-, -NRx- (Rx represents a hydrogen atom or a substituent) or -CO-. Examples of the substituent represented by Rx are the same as the specific examples of the substituent represented by Wa and Wb. Rx is preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

In the general formula (1), X represents a nonmetal atom of Groups 14 to 16. X is preferably = O, = S, = NRc, = C (Rd) Re. Here, Rc, Rd and Re represent substituents, and examples thereof are the same as the specific examples of the substituent represented by Wa and Wb. _{L 1, L 2, R 1} , R 2, R 3, n , is _{L 1, L 2, R 1} , R 2, R 3, n and copper in the formula (A).

In the general formula (2), Q ₁ represents -O-, -S-, -NRy- (Ry represents a hydrogen atom or a substituent), -CRaRb- (wherein Ra and Rb represent a hydrogen atom or a substituent) CO-. Here, Ry, Ra and Rb represent a substituent, and examples thereof are the same as the specific examples of the substituent represented by Wa and Wb.

Y represents a substituent. Examples of the substituent represented by Y are the same as the specific examples of the substituent represented by Wa and Wb. Y is preferably an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group.

Examples of the aryl group represented by Y include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

Examples of the heterocyclic group include a heterocyclic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group , A furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, and a thiazolyl group are preferable.

The aryl group or the heterocyclic group may have at least one substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, An alkylthio group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms , An N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms, and the like.

_{L 1, L 2, R 1} , R 2, R 3, n , is _{L 1, L 2, R 1} , R 2, R 3, n and copper in the formula (A).

(II) Specific examples of the case where at least one of Wa and Wb in the general formula (A) has a ring structure is preferably the following general formula (3).

In the general formula (3), Q ₃ represents ═N- or ═CRz- (Rz represents a hydrogen atom or a substituent), and Q ₄ represents a nonmetal atom of Groups 14 to 16. Z represents a group of nonmetal atoms forming a ring together with Q ₃ and Q ₄ .

The ring formed of Q ₃ , Q _4, and Z may be further ring-bound to a separate ring. The ring formed of Q ₃ , Q ₄ and Z is preferably a nitrogen-containing 5-membered ring or 6-membered ring condensed with a benzene ring.

_{L 1, L 2, R 1} , R 2, R 3, n , is _{L 1, L 2, R 1} , R 2, R 3, n and copper in the formula (A).

(III) When at least one of Wa and Wb is an alkenyl group or an alkynyl group, they are preferably a vinyl group or an ethynyl group having a substituent.

Among the compounds represented by the general formulas (1), (2) and (3), the compound represented by the general formula (3) is particularly preferable.

The compound represented by the general formula (3) is superior in heat resistance and light resistance to the compound represented by the general formula (1), and has a solubility in an organic solvent and a higher solubility in an organic solvent than the compound represented by the general formula (2) Compatibility is good.

The compound represented by the general formula (A) may be contained in an amount suitable for imparting the desired wavelength dispersibility and anti-smudge property. The amount of the compound to be added is preferably 1 to 15% by mass relative to the cellulose derivative , Particularly preferably from 2 to 10 mass%. Within this range, it is possible to impart sufficient wavelength dispersibility and anti-smudge property to the cellulose derivative.

The compounds represented by the general formula (A), the general formula (1), the general formula (2) and the general formula (3) can be obtained by referring to a known method. Specifically, Journal of Chemical Crystallography (1997); 27 (9); 512-526), JP-A-2010-31223, JP-A-2008-107767, and the like.

(With respect to cellulose acylate)

The cellulose acylate film according to this embodiment contains cellulose acylate as a main component. For example, the cellulose acylate film according to the present embodiment contains cellulose acylate in an amount of preferably 60 to 100% by mass relative to the total mass (100% by mass) of the film. The degree of substitution of the cellulose acylate with respect to the total acyl group is preferably 2.0 or more and less than 3.0, and more preferably 2.2 to 2.7.

Examples of the cellulose acylate include cellulose ester and esters of an aliphatic carboxylic acid and / or aromatic carboxylic acid having about 2 to 22 carbon atoms. Especially, an ester of cellulose and a lower fatty acid having 6 or less carbon atoms is preferable.

The acyl group bonded to the hydroxyl group of cellulose may be linear or branched or may form a ring. Further, a substituent may be substituted. When the number of carbon atoms is the same, the number of carbon atoms is preferably selected from acyl groups having 2 to 6 carbon atoms, and the total sum of propionyl substitution degree and butyryl substitution degree is from 0 to less than 3.0 to be. The cellulose acylate preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.

Concretely, examples of the cellulose acylate include a cellulose acylate mixed with a cellulose having a propionate group, a butyrate group or a phthalyl group bonded in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate or cellulose acetate phthalate Fatty acid esters can be used. The butyryl group forming the butyrate may be linear or branched.

In the present embodiment, cellulose acetate, cellulose acetate butyrate, or cellulose acetate propionate is particularly preferably used as the cellulose acylate.

The cellulose acylate preferably satisfies the following formulas (i) and (ii) simultaneously.

(I) 2.0? X + Y < 3.0

(Ii) 0? X <3.0

Wherein Y represents the degree of substitution of the acetyl group and X represents the substitution degree of the propionyl group or the butyryl group or mixture thereof.

In addition, in order to obtain optical characteristics suitable for the purpose, resins having different degrees of substitution may be mixed and used. The mixing ratio at that time is preferably 1:99 to 99: 1 (mass ratio).

Of the above, cellulose acetate propionate is particularly preferably used as the cellulose acylate. In cellulose acetate propionate, it is preferable that 0? Y? 2.5 and 0.5? X? 3.0 (however, 2.0? X + Y? 3.0), 0.5? Y? 2.0 and 1.0? However, it is more preferable that 2.0? X + Y < 3.0). The degree of substitution of the acyl group can be measured in accordance with ASTM-D817-96, which is one of standards developed and issued by the American Society for Testing and Materials (ASTM).

The number average molecular weight of the cellulose acylate is preferably in the range of from 60000 to 300000 because the mechanical strength of the obtained film is increased. More preferably, a cellulose acylate having a number average molecular weight of 70,000 to 200,000 is used.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose acylate are measured using gel permeation chromatography (GPC). The measurement conditions are as follows. The present measurement method can also be used as a method for measuring other polymers in the present embodiment.

Solvent: methylene chloride;

Column: Three Shodex K806, K805 and K803G (manufactured by Showa Denko K.K.) are connected and used;

Column temperature: 25 캜;

Sample concentration: 0.1 mass%;

Detector: RI Model 504 (manufactured by GL Science);

Pump: L6000 (manufactured by Hitachi Seisakusho Co., Ltd.);

Flow rate: 1.0 ml / min

Calibration curve: standard polystyrene STK standard A calibration curve of 13 samples of polystyrene (manufactured by Tosoh Corporation) Mw = 1000000 to 500 is used. 13 samples are used at almost equal intervals.

The residual sulfuric acid content in the cellulose acylate is preferably in the range of 0.1 to 45 mass ppm in terms of sulfur element. They are thought to be contained in salt form. If the content of residual sulfuric acid exceeds 45 mass ppm, it tends to be easily broken at the time of heat stretching or slitting after thermal stretching. The residual sulfuric acid content is more preferably in the range of 1 to 30 mass ppm. The residual sulfuric acid content can be measured by the method specified in ASTM-D817-96.

The free acid content in the cellulose acylate is preferably 1 to 500 mass ppm. If it is in the above range, it is preferable that it is difficult to break as in the above. Further, the free acid content is preferably in the range of 1 to 100 mass ppm, and it is more difficult to break. And particularly preferably in the range of 1 to 70 mass ppm. The free acid content can be determined by the method specified in ASTM-D817-96.

The residual alkaline earth metal content, the residual sulfuric acid content, and the residual acid content can be set within the above-mentioned range by more thoroughly washing the synthesized cellulose acylate as compared with the solution used in the solution casting method.

Cellulose as a raw material of cellulose acylate is not particularly limited, but cotton linter, wood pulp, kenaf and the like can be mentioned. Further, the cellulose acylates obtained therefrom may be mixed and used in any ratio.

The cellulose acylate can be produced by a known method. Specifically, it can be synthesized with reference to the method described in, for example, Japanese Patent Application Laid-Open No. 10-45804.

The cellulose acylate is also influenced by the trace metal components in the cellulose acylate. These trace metal components are considered to be related to the water used in the production process, and it is preferable that few components that can become insoluble nuclei. Particularly, metal ions such as iron, calcium, magnesium and the like may form an insoluble matter by forming a salt with a decomposition product of a polymer, which may contain an organic acidic group. The calcium (Ca) component can easily form an acidic component such as a carboxylic acid or a sulfonic acid and also many ligands and a coordination compound (that is, a complex), and can be used as a scum derived from a large amount of insoluble calcium ) May be formed.

Specifically, the content of the iron (Fe) component in the cellulose acylate is preferably 1 mass ppm or less. The content of the calcium (Ca) component in the cellulose acylate is preferably 60 mass ppm or less, and more preferably 0 to 30 mass ppm. The content of the magnesium (Mg) component in the cellulose acylate is preferably 0 to 70 mass ppm, more preferably 0 to 20 mass ppm, because the content of the magnesium (Mg) component is insufficient.

The content of the metal component such as the content of the iron (Fe) component, the content of the calcium (Ca) component and the content of the magnesium (Mg) component can be controlled by adjusting the amount of the cellulose acylate, Nitric acid, pretreated by alkali melting, and then analyzed using an ICP-AES (inductively coupled plasma emission spectrometer).

<Alicyclic Olefin Polymerization Resin>

Examples of the alicyclic olefin polymerization-type resin used in the raw film of the present embodiment include a cyclic olefin random multi-component copolymer disclosed in Japanese Patent Application Laid-Open No. 05-310845, A hydrogenated polymer, a thermoplastic dicyclopentadiene ring-opening polymer described in Japanese Patent Application Laid-Open No. 11-124429, a hydrogenated product thereof, and the like.

The alicyclic olefinic polymer resin is a polymer having an alicyclic structure such as a saturated alicyclic hydrocarbon (cycloalkane) structure or an unsaturated alicyclic hydrocarbon (cycloalkene) structure. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but usually ranges from 4 to 30, preferably from 5 to 20, and more preferably from 5 to 15. When the mechanical strength, heat resistance, The formability properties are highly balanced and suitable.

The proportion of the repeating unit containing an alicyclic structure in the alicyclic olefin polymer may be appropriately selected, but is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. When the proportion of the repeating unit having an alicyclic structure in the alicyclic polyolefin resin is within this range, the transparency and heat resistance of the optical material such as the retardation film obtained from the long oblong drawn film of the present embodiment are improved, which is preferable.

Examples of the olefin polymerization resin having an alicyclic structure include a norbornene resin, a monocyclic cycloolefin resin, a cyclic conjugated diene resin, a vinyl alicyclic hydrocarbon resin, and hydrides thereof. Among them, the norbornene resin can be suitably used because of its good transparency and moldability.

As the norbornene resin, for example, a ring-opening polymer of a monomer having a norbornene structure or a ring-opening copolymer of a monomer having a norbornene structure and another monomer or a hydride thereof, an adduct of a monomer having a norbornene structure Or addition copolymers of monomers having a norbornene structure with other monomers, or hydrides thereof. Among them, the ring-opened (co) polymer hydride of a monomer having a norbornene structure can be suitably used particularly in view of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability and light weight.

As a method for molding a long film (textile film) using the norbornene resin as described above, a solution casting method or a melt extrusion method is preferable. As the melt extrusion method, an inflation method using a die and the like can be mentioned. However, a method using a T-die is preferable in view of productivity and thickness accuracy.

As an extrusion molding method using a T die, a method of maintaining a molten thermoplastic resin in a stable state when it is brought into close contact with a cooling drum as described in Japanese Patent Application Laid-Open No. 2004-233604, It is possible to manufacture a long film having small variations in optical characteristics such as angle.

Specifically, 1) a method in which, when a long film is produced by the melt extrusion method, the sheet-like thermoplastic resin extruded from the die is brought into close contact with the cooling drum under a pressure of 50 kPa or less to induce the drawing; 2) When a long film is produced by a melt extrusion method, the distance from the die opening to the cooling drum which is initially in close contact with the surrounding member is set to 100 mm or less from the surrounding member to the die opening or the cooling drum Way; 3) a method of warming the temperature of the atmosphere of 10 mm or less from the sheet-like thermoplastic resin extruded from the die opening to a specific temperature when producing a long film by the melt extrusion method; 4) a method in which the sheet-like thermoplastic resin extruded from the die is brought into close contact with the cooling drum under a pressure of 50 kPa or less to induce the drawing; 5) When a long film is produced by a melt extrusion method, a method of spraying a wind having a speed difference of not more than 0.2 m / s from the pulling speed of a cooling drum which is initially in close contact with a sheet- .

The long film may be a single layer or a laminated film of two or more layers. The laminated film can be obtained by a known method such as a coextrusion molding method, a shared softening molding method, a film lamination method, and a coating method. Of these, the co-extrusion molding method and the shared mold forming method are preferable.

<Polycarbonate-based resin>

As the polycarbonate resin used in the raw film of this embodiment, various resins can be used without particular limitation, and aromatic polycarbonate resins are preferable from the viewpoints of chemical properties and physical properties, and bisphenol A polycarbonates Nate resin is preferable. Among them, it is more preferable to use a bisphenol A derivative having a benzene ring, a cyclohexane ring and an aliphatic hydrocarbon group introduced into bisphenol A. Particularly preferred is a polycarbonate resin having a structure in which anisotropy in the unit molecule is reduced, obtained by using a derivative in which the functional group is introduced asymmetrically to the central carbon of bisphenol A. Examples of such polycarbonate resins include those obtained by substituting two methyl groups of the central carbon of bisphenol A with benzene rings and one hydrogen of each benzene ring of bisphenol A asymmetrically with respect to the central carbon with a methyl group or a phenyl group A polycarbonate resin obtained by using a substituted polycarbonate resin is particularly preferable.

Specifically, they are obtained from 4,4'-dihydroxydiphenylalkane or a halogen substituent thereof by a phosgene method or an ester exchange method, and examples thereof include 4,4'-dihydroxydiphenyl methane, 4,4 ' Dihydroxydiphenyl ethane, 4,4'-dihydroxydiphenyl butane, and the like. Further, for example, Japanese Patent Application Laid-Open Nos. 2006-215465, 2006-91836, 2005-121813, 2003-167121, and Japanese Patent Polycarbonate resins described in JP-A-2009-126128, JP-A-2012-31369, JP-A-2012-67300, and WO00 / 26705.

The polycarbonate resin may be used in combination with a transparent resin such as polystyrene type resin, methyl methacrylate type resin and cellulose acetate type resin. Further, a resin layer containing a polycarbonate resin may be laminated on at least one surface of a resin film formed using a cellulose acetate resin.

The polycarbonate resin preferably has a glass transition point (Tg) of 110 DEG C or more and a water absorption rate (value measured at 23 DEG C under water for 24 hours) of 0.3% or less. It is more preferable that the Tg is 120 ° C or more and the water absorption rate is 0.2% or less.

The polycarbonate resin film that can be used in the present embodiment can be formed by a known method, and among these, the solution casting method and the melt casting method are preferable.

<Additives>

The raw material film of this embodiment may contain an additive. Examples of the additives include plasticizers, ultraviolet absorbers, retardation-adjusting agents, antioxidants, deterioration inhibitors, release aids, surfactants, dyes, and fine particles. In the present embodiment, additives other than the fine particles may be added at the time of preparing the dope liquid or may be added at the time of preparing the fine particle dispersion.

(Plasticizer)

Examples of the plasticizer to be added to the fabric film include phthalate ester, fatty acid ester, trimellitate ester, phosphate ester, polyester, sugar ester, and acrylic polymer. Among these, a plasticizer of a polyester-based or sugar ester-based polymer is preferably used from the viewpoint of moisture permeability.

The polyester-based plasticizer is superior to the phthalate ester-based plasticizer such as dioctyl phthalate in non-planarity and extrusion resistance. Depending on the application, these plasticizers may be selected or used in combination for a wide range of applications. As the acrylic polymer, homopolymers or copolymers of acrylic acid or alkyl methacrylate are preferable. Examples of the monomer of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-), acrylonitrile (n-, i-), myristyl acrylate (n- , i-), acrylic acid (2-ethylhexyl), acrylic acid (? -caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl) Hydroxybutyl), acrylic acid (2-methoxyethyl), acrylic acid (2-ethoxyethyl) and the like, or the acrylic acid ester is replaced with methacrylic acid ester . The acrylic polymer is a homopolymer or a copolymer of the above-mentioned monomers, but preferably contains 30 mass% or more of acrylic acid methyl ester monomer units and more preferably 40 mass% or more of methacrylic acid methyl ester monomer units. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.

The polyester plasticizer is a reaction product of a mono- to tetravalent carboxylic acid with a mono- to hexavalent alcohol, but mainly one obtained by reacting a divalent carboxylic acid with a glycol is used. Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, and sebacic acid. The polyester plasticizer is preferably an aromatic terminal ester plasticizer. The aromatic terminal ester plasticizer is preferably an ester compound having a structure obtained by reacting phthalic acid, adipic acid, at least one benzene monocarboxylic acid, and at least one alkylene glycol having 2 to 12 carbon atoms. The structure of the final compound may be an adipic acid residue and a phthalic acid residue as long as it is a structure of the final compound, and may be reacted as an acid anhydride or esterified product of a dicarboxylic acid.

Examples of the benzene monocarboxylic acid component include benzoic acid, para-tert-butylbenzoic acid, orthotoluenic acid, meta-toluic acid, paratoluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propylbenzoic acid, aminobenzoic acid, and acetoxybenzoic acid , And benzoic acid. These may be used alone or as a mixture of two or more kinds.

Examples of the alkylene glycol component having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, Propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2- Propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1-n-butyl- Hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, 1,12-octadecanediol, and the like. Among these, 1,2-propylene glycol is particularly preferable. These glycols may be used alone or as a mixture of two or more thereof.

The aromatic terminal ester plasticizer may be any of oligoester and polyester, and the molecular weight is preferably in a range of from 100 to 10000, and more preferably in a range of from 350 to 3000. The acid value is not more than 1.5 mg KOH / g and the hydroxy (hydroxyl value) is not more than 25 mg KOH / g, more preferably the acid value is not more than 0.5 mg KOH / g and the hydroxy (hydroxyl group) is not more than 15 mg KOH / g.

Specific examples thereof include, but are not limited to, the following compounds.

The sugar ester compound is an ester other than a cellulose ester and is a compound obtained by esterifying all or a part of the OH group of a sugar such as the following monosaccharides, 2 sugars, 3 sugars or oligosaccharides. More specific examples include compounds represented by the general formula (4) And compounds to be displayed.

In the formulas, R ₁ to R ₈ represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon atoms. R ₁ to R ₈ may be the same or different.

Hereinafter, the compound represented by the general formula (4) is more specifically shown (Compound 1-1 to 1-23), but is not limited thereto. In the following table, when the average degree of substitution is less than 8.0, any of R ₁ to R ₈ represents a hydrogen atom.

These plasticizers are preferably added in an amount of 0.5 to 30 parts by mass based on 100 parts by mass of the cellulose ester film.

(Retardation adjusting agent)

As a compound to be added for adjusting the retardation, an aromatic compound having two or more aromatic rings as described in European Patent No. 911,656A2 can be used.

Two or more kinds of aromatic compounds may be used in combination. It is particularly preferable that the aromatic ring of the aromatic compound contains an aromatic heterocycle in addition to the aromatic hydrocarbon ring. The aromatic heterocycle is generally an unsaturated heterocycle. Among them, 1,3,5-triazine ring is particularly preferable.

(Polymer or oligomer)

The textile film of the present embodiment is a polymer or oligomer of a vinyl compound having a cellulose ester and a substituent selected from a carboxyl group, a hydroxyl group, an amino group, an amide group and a sulfonic acid group and having a weight average molecular weight of 500 to 200,000 . The mass ratio of the content of the cellulose ester to the polymer or oligomer is preferably in the range of 95: 5 to 50:50.

(Made by Matt)

In the present embodiment, fine particles can be contained in the raw material film as a mat agent, whereby the raw material film and the long obliquely drawn film produced using the raw material film can be easily transported or wound.

The particle size of the mat agent is preferably 10 to 0.1 mu m of primary particles or secondary particles. A substantially spherical mat material having a needle aspect ratio of primary particles of 1.1 or less is preferably used.

As the fine particles, those containing silicon are preferable, and silicon dioxide is particularly preferable. Examples of the fine particles of silicon dioxide which are preferable in the present embodiment include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50 and TT600 (manufactured by Nippon Aerosil Co., ), And aerosil 200V, R972, R972V, R974, R202 and R812 can be preferably used. Examples of the fine particles of the polymer include a silicone resin, a fluororesin and an acrylic resin. Silicone resin is preferable, and it is particularly preferable to have a three-dimensional network structure. Examples of such resins include Tospearl 103, Copper 105, Copper 108, Copper 120, Copper 145, Copper 3120 and Copper 240 (manufactured by Toshiba Silicone Co., Ltd.).

The fine particles of silicon dioxide preferably have a primary mean particle diameter of 20 nm or less and an apparent specific gravity of 70 g / L or more. More preferably, the primary particles have an average diameter of 5 to 16 nm, more preferably 5 to 12 nm. The smaller the average diameter of the primary particles is, the lower the haze is. The apparent specific gravity is preferably 90 to 200 g / L or more, more preferably 100 to 200 g / L or more. As the apparent specific gravity is larger, it becomes possible to produce a dispersion liquid of a high concentration of fine particles, and haze and agglomerates are not generated, which is preferable.

The amount of the matting agent to be added in the present embodiment is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and still more preferably 0.08 to 0.16 g per 1 m2 of the fabric film.

(Other additives)

In addition, heat stabilizers such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide and alumina, and salts of alkaline earth metals such as calcium and magnesium may be added. Further, a surfactant, a peeling accelerator, an antistatic agent, a flame retardant, a lubricant, an emulsion or the like may be added.

(Tension softening point)

The fabric film of this embodiment is required to be able to withstand use under a higher temperature environment. For this reason, the tensile softening point of the fabric film is preferably from 105 캜 to 145 캜 because it exhibits sufficient heat resistance, and more preferably from 110 캜 to 130 캜.

As a specific measuring method of the tensile softening point, a sample film is cut to 120 mm (length) x 10 mm (width) using, for example, a Tensilon tester (RTC-1225A manufactured by ORIENTEC) The temperature was maintained at a heating rate of 30 DEG C / min while being stretched at a tensile force of 10 N, and the temperature at the time when the temperature became 9 N was measured three times, and the average value was obtained.

(Dimensional change rate)

When the film after obliquely stretching the raw film of the present embodiment is applied to an organic EL image display apparatus, problems such as variations in thickness, a change in retardation value, and a reduction in contrast or color irregularity occur due to a dimensional change caused by moisture absorption , The dimensional change rate (%) of the obliquely drawn film is preferably less than 0.5%, more preferably less than 0.3%.

(fault)

It is preferable that the raw material film of the present embodiment has few defects in the film. Here, the defect means defects such as voids (foaming defects) in the film caused by the rapid evaporation of the solvent in the drying process of the solution film formation, foreign matter (foreign matter defect) in the film due to foreign matters mixed in the film forming solution, .

Concretely, it is preferable that defects with a diameter of 5 탆 or more in the film plane are 1/10 cm square or less. More preferably at most 0.5 / 10 cm square, further preferably at most 0.1 / 10 cm square.

The diameter of the defect refers to the diameter when the defect has a circular shape, and when the defect is not circular, the range of the defect is determined by observing with a microscope by the following method, and the maximum diameter is defined as the diameter of the circumscribed circle.

The range of the defect is the size of the shadow when the defect is observed as the transmitted light of the differential interference microscope when the defect is bubble or foreign matter. When the defect is a change in surface shape such as a transfer of a roll scratch or a scratch, the size is confirmed by observing the defect as reflected light of a differential interference microscope.

In the case of observing with reflected light, if the size of the defect is unclear, aluminum or platinum is deposited on the surface and observed. In order to obtain a film having excellent durability represented by such defect frequency with high productivity, it is necessary to perform high-precision filtration of the polymer solution just before the pouring, to increase the degree of cleanliness around the pore, and to set the drying conditions after the pouring stepwise, It is effective to make the drying effective by suppressing foaming.

If the number of defects is more than 1/10 cm square, for example, when a tension is applied to the film at the time of processing in a subsequent process, the film may be broken from the defect as a starting point, and the productivity may be lowered. When the diameter of the defect is 5 mu m or more, it can be confirmed visually by observing the polarizing plate or the like, and a bright spot may be generated when used as an optical member.

(Total light transmittance)

The raw film of the present embodiment preferably has a total light transmittance of 90% or more, more preferably 93% or more. The practical upper limit of the total light transmittance is about 99%. In order to achieve the excellent transparency expressed by the total light transmittance, it is necessary to prevent introduction of an additive or a copolymerizable component that absorbs visible light, remove foreign matters in the polymer by high-precision filtration, and reduce light diffusion or absorption inside the film . Further, it is possible to reduce the surface roughness of the film contacting portion (cooling roll, calender roll, drum, belt, coating liquid in the solution film forming process, conveying roll, etc.) at the time of film formation to reduce the surface roughness of the film surface, It is effective to reduce reflection.

&Lt; Method of forming a fabric film &

The raw film of the present embodiment containing the above-described resin can be formed by any one of solution casting film forming method and melt casting film forming method described below. Here, the case where the fabric film includes a cellulose ester-based resin is explained, but the case where other resin is included is also applied.

When the fabric film is produced by the solution casting method, the dope, which is the raw material solution of the raw material film of the cellulose ester resin, is softened on the support including the rotating metal endless belt by the flexible die. The dope film, that is, the web formed on the support by the softening, is peeled off by the peeling roll when it is about one turn on the support. The peeled web (film) is then introduced into a stretching apparatus including a tenter.

In the extrusion method using a T-die, a polymer is melted at a melting temperature and extruded from a T-die onto a cooling drum in a film form (sheet form), cooled and solidified, The film is peeled off. The peeled film is then introduced into a stretching apparatus including a tenter.

 Hereinafter, the details of each film-forming method will be described.

[Solution flexible film-forming method]

In the method for producing a raw fabric film by the solution softening method, the solid concentration of the dope as the cellulose ester solution is usually about 10 to 40 mass%, and the dope viscosity in the softening step is in the range of 1 to 200 poise &Lt; / RTI &gt;

Here, first, the cellulose ester is dissolved by a means such as a stirring dissolving method, a heating dissolving method, an ultrasonic melting method and the like in a melting pot. Usually, the cellulose ester is melted in a range where the boiling point of the solvent is higher than the boiling point at normal pressure, , And dissolving with stirring is more preferable because it prevents the occurrence of a massive undissolved product called gel or agglomerate. Further, the cooling dissolution method disclosed in Japanese Patent Application Laid-Open No. 9-95538 or the method disclosed in Japanese Patent Application Laid-Open No. 11-21379 may be used.

A method in which the cellulose ester is mixed with a poor solvent, wetted or swelled, and then mixed with a two-component agent and dissolved is also preferably used. At this time, the apparatus for mixing cellulose ester with a poor solvent to wet or swell the apparatus and the apparatus for mixing and dissolving the two agents may be separately provided.

The kind of the pressure vessel used for dissolving the cellulose ester is not particularly limited, but it is only required to be able to withstand a predetermined pressure and to be heated and stirred under pressure. Instrumentation such as a gauge, a pressure gauge, and a thermometer is appropriately placed in the pressure vessel. Pressurization may be performed by a method of pressurizing an inert gas such as nitrogen gas or by raising the vapor pressure of the solvent by heating. Heating is preferably performed from the outside, and for example, a jacket type is preferable because temperature control is easy.

The heating temperature in the case of adding a solvent is higher than the boiling point of the solvent to be used and in the case of two or more mixed solvents, the temperature is raised to the boiling point of the lower boiling point solvent, . If the heating temperature is too high, the required pressure is increased and the productivity is deteriorated. The preferred range of the heating temperature is 20 to 120 占 폚, more preferably 30 to 100 占 폚, and still more preferably 40 to 80 占 폚. Further, the pressure is adjusted so that the solvent does not boil at the set temperature.

In addition to the cellulose ester and the solvent, additives such as necessary plasticizers and ultraviolet absorbers may be previously mixed with the solvent, dissolved or dispersed, and then added to the solvent before the cellulose ester dissolution, or may be added to the dope after the dissolution of the cellulose ester.

After the dissolution of the cellulose ester, the cellulose ester is taken out of the vessel while being cooled, or extracted from the vessel by a pump or the like, cooled in a heat exchanger or the like, and provided for film formation of the dope of the obtained cellulose ester.

When the mixture of the cellulose ester raw material and the solvent is dissolved in a dissolver having a stirrer, it is preferable that the stirring speed of the stirring blades is at least 0.5 m / sec or more and the mixture is stirred for 30 minutes or more to dissolve.

Foreign matter contained in the cellulose ester dope (particularly foreign matter mistakenly recognized as an image in a liquid crystal display device) must be removed by filtration. The quality of the optical film may be determined by this filtration.

It is preferable that the filtration material used for filtration has a small absolute filtration accuracy. However, if the absolute filtration precision is too small, clogging of the filter material tends to occur, and the filtration material must be frequently exchanged. For this reason, the filter material used for the cellulose ester dope preferably has an absolute filtration accuracy of 0.008 mm or less, more preferably 0.001 to 0.008 mm, and even more preferably 0.003 to 0.006 mm.

The material of the filter medium is not particularly limited and a normal filter medium can be used. However, a filter material made of plastic fibers such as polypropylene or Teflon (registered trademark) or a metal filter material made of stainless steel fibers and the like is preferable .

The filtration of the cellulose ester dope can be carried out by a usual method, but a method of filtration while heating under pressure at a temperature in the range of the boiling point of the solvent at normal pressure and at a temperature not boiling the solvent, ) Is small, which is preferable.

A preferable range of the filtration temperature is 45 to 120 캜, more preferably 45 to 70 캜, still more preferably 45 to 55 캜.

The filtration pressure is preferably 3500 kPa or less, more preferably 3000 kPa or less, and still more preferably 2500 kPa or less. The filtration pressure can be controlled by appropriately selecting the filtration flow rate and the filtration area.

In order to produce a cellulose ester based resin film, firstly, the cellulose ester is dissolved in a mixed solvent of a good solvent and a poor solvent, and the above plasticizer or ultraviolet absorber is added thereto to prepare a cellulose ester solution (dope).

The dope can be flexible on the support at temperatures in the range of from 0 ° C to below the boiling point of the solvent and can be flexible on the support in the temperature range from 5 ° C to the solvent boiling point of -5 ° C, It is more preferred to be flexible on the support in the temperature range. At this time, it is necessary to control the surrounding atmosphere humidity to be equal to or higher than the dew point.

The dope adjusted so as to have a viscosity of 1 to 200 poises is softened to have a substantially uniform film thickness on the support from the flexible die and when the amount of the residual solvent in the flexible film is more than 200% (Web) is dried with the drying air so that the temperature of the flexible film is in the range of the solvent boiling point + 20 占 폚 or less until the residual solvent amount is less than or equal to 200%.

Here, the residual solvent amount can be expressed by the following formula.

Amount of residual solvent (mass%) = {(M-N) / N} 100

In the formula, M is the weight of the web at any point in time, and N is the weight of the weight when dried at 110 ° C for 3 hours.

On the support, the amount of residual solvent in the web is preferably dried to 150% by mass or less, more preferably 50% to 120%, in order to dry and solidify the web until the peelable film strength is reached from the support.

The web temperature at which the web is peeled from the support is preferably 0 to 30 占 폚. Further, since the temperature of the web rapidly lowers immediately after the peeling from the support, the temperature temporarily lowers by the evaporation of the solvent from the side close to the support, and the volatile components such as steam and solvent vapor in the atmosphere are likely to condense. To 30 &lt; 0 &gt; C.

In the drying process of the web (or film), a method of drying while conveying the web by a roll suspension system, a pin tenter system or a clip tenter system is generally employed.

The web after peeling is introduced into, for example, a primary drying apparatus. In the primary drying apparatus, the web is conveyed serially by a plurality of conveying rolls arranged in a zigzag manner when seen from the side, while the web is blown from the ceiling of the drying apparatus, Lt; / RTI &gt;

Subsequently, the obtained film (sheet) is stretched in the uniaxial direction. The molecules are oriented by stretching. The stretching method is not particularly limited, but a well-known pin tenter or clip-type tenter can be preferably used. The stretching direction may be a longitudinal direction, a width direction, or any direction (oblique direction), but it is preferable that the stretching direction of the raw film is easy to adjust by making the stretching direction to be the width direction.

In particular, in the drying step after peeling from the support, the web tends to shrink in the width direction by evaporation of the solvent. The shrinkage increases with drying at high temperature. It is preferable to dry the film while suppressing the shrinkage as much as possible in order to improve the flatness of the finished film. In this respect, for example, a method of drying the entire drying process or a part of processes disclosed in Japanese Patent Application Laid-Open No. 62-46625, while keeping both ends of the width of the web wide by a clip in the width direction (tenter method) is preferable .

As the stretching condition of the raw material film, the temperature and the magnification can be selected so that the desired elongation at break characteristic can be obtained. Generally, the stretching magnification is 1.1 to 2.0 times, preferably 1.2 to 1.5 times, and the stretching temperature is usually from -40 占 폚 to Tg + 50 占 폚 of the glass transition temperature (Tg) of the resin constituting the sheet, Lt; RTI ID = 0.0 &gt; 40 C &lt; / RTI &gt; If the stretch ratio is too small, desired stretch elongation characteristics may not be obtained. On the other hand, if the stretch ratio is too large, breakage may occur. If the stretching temperature is too low, it may break, and if it is too high, the desired stretch elongation characteristics may not be obtained.

In the case of modifying the breaking elongation property of the thermoplastic resin film produced by the above method to a desired characteristic according to the purpose, the film may be stretched or shrunk in the longitudinal direction or the width direction. In order to contract in the longitudinal direction, for example, there is a method in which the film is shrunk by temporarily releasing the widthwise stretching to relax in the longitudinal direction, or by gradually narrowing the interval between adjacent clips of the transverse stretching device. The latter method can be carried out by a method in which a common simultaneous biaxial stretching device is used to smoothly narrow the interval between adjacent longitudinally spaced clips by driving the clip portion with, for example, a pantograph method or a linear drive method.

The holding and stretching in the tenter can be carried out anywhere from 50 to 150 mass% of the residual solvent amount of the film immediately after the peeling to 0 mass% of the actual residual solvent amount immediately before the winding, but the residual solvent amount is preferably in the range of 5 to 10% .

It is also often common to divide the tenter into several temperature zones in the running direction of the base. The temperature at which the desired physical properties and planarity are obtained is selected as the temperature at the time of stretching. However, the temperature of the drying zone before and after the tenter may also be selected to be different from the temperature at the time of stretching for various reasons. For example, when the atmospheric temperature of the drying zone before the tenter is different from the temperature in the tenter, it is generally preferable to set the temperature of the zone near the entrance of the tenter to a temperature intermediate the temperature of the drying zone before the tenter and the temperature of the center of the tenter . Similarly, when the temperature in the tenter aftertenter is different, the temperature of the zone close to the tenter outlet is set to the intermediate temperature between the temperature in the tenter and the temperature in the tenter. The temperature of the drying zone before and after the tenter is generally 30 to 120 DEG C, preferably 50 to 100 DEG C, the temperature of the drawing portion in the tenter is 50 to 180 DEG C, preferably 80 to 170 DEG C, The negative temperature is appropriately selected at their intermediate temperature.

The pattern of the stretching, that is, the trajectory of the gripping clip is selected from optical properties and planarity of the film as in the case of temperature, but varies in a certain width after the start of grinding, Is often used. In the vicinity of the end of the clip grip near the tenter outlet, width reduction is generally performed in order to suppress the base vibration by opening the grip.

The drawing pattern is also related to the drawing speed, but the drawing speed is generally 10 to 1000 (% / min), preferably 100 to 500 (% / min). This stretching speed is not constant when the clip trajectory is a curve, but gradually changes in the running direction of the base.

Further, the web (film) after drying by the tenter system is continuously introduced into the secondary drying apparatus. In the secondary drying apparatus, the web is conveyed serially by a plurality of conveying rolls arranged in a zigzag manner when viewed from the side, during which the web is blown from the ceiling of the secondary drying apparatus, And is wound around a winder as a raw film of a cellulose ester resin.

As means for drying the web, hot air, infrared rays, heating rolls, microwaves, etc. are generally used without particular limitation. From the viewpoint of simplicity, it is preferable to dry with hot air. The drying temperature is preferably 40 to 150 占 폚, and more preferably 80 to 130 占 폚 because planarity and dimensional stability are improved.

As described above, in the drying process of the web, the web peeled from the support is further dried, and the amount of the residual solvent is finally adjusted to 3 mass% or less, preferably 1 mass% or less, more preferably 0.5 mass% or less , And is preferable for obtaining a film having good dimensional stability.

The process from softening to post-drying may be performed in an air atmosphere, or in an inert gas atmosphere such as nitrogen gas. In this case, it goes without saying that the drying atmosphere is carried out in consideration of the explosive limit concentration of the solvent.

In addition, embossing is carried out on both side edge portions of the cellulose ester resin-made resin film by the embossing device at the front end to be introduced into the winding step of the cellulose ester resin finished film after completion of the conveying and drying process It is preferable to perform processing. As the embossing apparatus, for example, an apparatus described in Japanese Patent Application Laid-Open No. 63-74850 can be used.

The winding machine relating to the production of the cellulose ester resin-based raw material film can be wound by a winding method such as a normal tension method, a constant torque method, a taper tension method and a program tension control method with a constant internal stress .

Though the film thickness of the raw fabric film after winding is different depending on the purpose of use, the film thickness range is 20 to 200 占 퐉, and in recent thinness tendency, it is preferably in the range of 30 to 120 占 퐉, more preferably in the range of 40 to 100 占 퐉 desirable.

When the raw material film of the present embodiment is produced by the melt softening film forming method, the ultraviolet absorber which can be used may be substantially the same as that used in the method for producing a raw material film by the solution casting film forming method.

The blending amount of these ultraviolet absorbers is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the thermoplastic resin. If the amount is too small, the ultraviolet absorbing effect may be insufficient. On the other hand, if the amount is too large, the transparency of the film may be deteriorated. The ultraviolet absorber preferably has high thermal stability.

It is preferable to add fine particles to the fabric film in order to impart the slidability of the film. As the fine particles to be used, any of an inorganic compound or an organic compound may be used if it has heat resistance at the time of melting. Examples of the inorganic compound include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, Calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate are preferable, and an inorganic compound containing zirconium or zirconium oxide is more preferable. Among them, silicon dioxide is particularly preferably used in that the haze can be suppressed small. Even when the fabric film is produced by the melt soft-film-forming method, as the matting agent to be used, substantially the same materials as those used in the manufacturing method of the raw film by the solution casting method can be used.

Examples of the melt soft-film-forming method include a melt-extrusion method such as a method using a T-die or an inflation method, a calendering method, a hot pressing method, and an injection molding method. Among them, a method using a T-die, which is small in thickness unevenness, easy to be processed to a thickness of about 50 to 500 탆, and capable of reducing unevenness in film thickness and unevenness of retardation, is preferable. The extrusion method using a T die is a method in which a polymer is melted at a melting temperature and extruded from a T die onto a cooling drum in a film form (sheet form), cooled and solidified, and peeled off from the cooling drum. And can be preferably used.

The melt extrusion can be carried out under the same conditions as those used for other thermoplastic resins such as polyester. For example, the cellulose ester which has been dried under a hot air, a vacuum or a reduced pressure is melted at an extrusion temperature of about 200 to 300 DEG C by using a uniaxial or biaxial extruder, filtered with a filter such as a leaf disk type filter, (Sheet shape) from the T die and solidified on the cooling drum. When introduced into the extruder from the feed hopper, it is preferable to prevent the oxidative decomposition or the like under an atmosphere of reduced pressure or inert gas.

The extrusion flow rate is preferably stabilized by introducing a gear pump. In addition, a stainless steel fiber sintered filter is preferably used as a filter used for removing foreign matters. The stainless steel fiber sintering filter is obtained by forming a state in which the stainless steel fiber sieve is intricately intertwined with each other, compressing the sintered stainless steel fiber sieve, and sintering the contact portions so as to integrate them. The filtration accuracy can be adjusted by changing the density depending on the thickness of the fibers and the amount of compression . It is preferable that the filtration precision is a multilayer body obtained by repeating a plurality of times continuously by a coarse and a mill. In addition, it is preferable to adopt a configuration in which the filtration accuracy is gradually increased, or the filtration accuracy is adjusted and the repetition of the filtration is repeated, so that the filtration life of the filter is prolonged and the replenishment precision of foreign matters and gels can be improved.

When scratches or foreign matter adhere to the die, a stripe-shaped defect may occur. Such a defect is called a die line. In order to reduce defects on the surface of a die line or the like, it is preferable that the pipe from the extruder to the die has a structure in which the retention portion of the resin is minimized. In addition, it is preferable to use the die without any scratches or the like on the inside or the lip of the die. The volatile component is precipitated from the resin around the die, which may cause die lines. Therefore, it is preferable to suck the atmosphere containing the volatile component. In addition, since it may precipitate in an apparatus such as an electrostatic attraction, it is preferable to apply alternating current or prevent precipitation by another heating means.

Additives such as plasticizers may be mixed with the resin in advance, or may be put in the middle of the extruder. In order to uniformly add it, it is preferable to use a mixing device such as a static mixer.

The temperature of the cooling drum is preferably not higher than the glass transition temperature of the thermoplastic resin. In order to adhere the resin to the cooling drum, it is preferable to use a method of tightly adhering by a static electricity, a method of tightly adhering by wind pressure, a method of tightly adhering to the entire width or end,

Unlike the raw film formed by the solution softening method, the raw film of the thermoplastic resin molded by the melt softening film forming method has a feature that the retardation in the thickness direction (Rt) is small, and the stretching condition In some cases. In some cases, stretching in the film advancing direction and stretching in the film width direction may be carried out simultaneously or sequentially in order to obtain desired optical properties. In some cases, the film may be stretched only in the film width direction. The molecules are oriented by this stretching operation, and the film is adjusted to a necessary retardation value.

<Specification of fabric film>

The thickness of the raw film in this embodiment is preferably 1 to 400 占 퐉, preferably 20 to 200 占 퐉, more preferably 30 to 120 占 퐉, particularly preferably 40 to 100 占 퐉. Further, in this embodiment, the thickness unevenness sigma m in the flow direction (transport direction) of the raw film fed to the stretching zone described later can be obtained by maintaining the pulling tension of the film at the entrance of the oblique stretching tenter, It is required to be less than 0.30 mu m, preferably less than 0.25 mu m, and more preferably less than 0.20 mu m from the viewpoint of stabilizing the optical characteristics such as the optical characteristics. When the thickness unevenness? M in the flow direction of the raw material film is 0.30 占 퐉 or more, variations in optical characteristics such as retardation and orientation angle of the long oblong drawn film are remarkably deteriorated.

In addition, in the present embodiment, it is preferable that the thickness unevenness in the width direction of the fabric film is small in order to suppress occurrence of the orientation angle variation in the width direction due to the thickness unevenness in the width direction by the warp stretching. For example, in the width direction of the raw fabric film, the difference in thickness between the end on the thick side and the end on the thin side is less than 2.0%, preferably less than 1.0%, more preferably less than 0.5% Of the total weight of the composition.

The width of the raw film is not particularly limited, but may be 500 to 4000 mm, preferably 1000 to 2000 mm.

The modulus of elasticity at the stretching temperature at the time of warp stretching of the fabric film is expressed by the Young's modulus and is from 0.01 MPa to 5000 MPa, more preferably from 0.1 MPa to 500 MPa. When the modulus of elasticity is too low, the shrinkage ratio after stretching is lowered, and wrinkles are less likely to disappear. When the modulus of elasticity is too high, the tensile force at the time of stretching becomes large, so that it is necessary to increase the strength of the portion for holding both side edge portions of the film, and the load on the tenter in the subsequent step is increased.

As the raw material film, there may be used a non-oriented film or a film having a predetermined orientation. Further, if necessary, the distribution in the width direction of the orientation of the raw material film may be arcuate, so-called bowing. The orientation of the raw film can be adjusted so that the orientation of the film at the position where the drawing of the subsequent process is completed can be desired.

&Lt; Method of manufacturing oblique stretched film &

Next, a description will be given of a method and an apparatus for producing an obliquely-stretched film in which the long film is stretched in an oblique direction with respect to the width direction to produce a long obliquely-stretched film.

(Overview of the device)

1 is a plan view schematically showing a schematic configuration of an apparatus 1 for producing an obliquely-drawn film. The manufacturing apparatus 1 comprises a film feeding portion 2, a feeding direction changing portion 3, a guide roll 4, a stretching portion 5, (6), a transport direction changing section (7), and a film winding section (8). A film cutting device may be provided between the transport direction changing portion 7 and the film winding portion 8 to cut the film after the warp stretching to a desired length and wind it on the film winding portion 8. Details of the stretching portion 5 will be described later.

The film feeding portion 2 uncovers the long film described above and feeds it to the stretching portion 5. The film feeder 2 may be formed separately from the film forming apparatus of the long film, or may be integrally formed. In the case of the former, a long film is fed from the film feeding portion 2 by winding the long film on the winding core after film formation and winding the film (long film material) into the film feeding portion 2. On the other hand, in the latter case, after film formation of the long film, the film feed portion 2 is fed to the stretching portion 5 without winding the long film.

The transport direction changing section 3 changes the transport direction of the long film fed out from the film feed section 2 to the direction toward the entrance of the stretching section 5 as the warp stretching tent. The carrying direction changing section 3 includes a turn bar for changing the carrying direction by, for example, folding while transporting the film, and a rotary table for rotating the turn bar in a plane parallel to the film.

By changing the conveying direction of the long film in the conveying direction changing section 3 as described above, the width of the entire manufacturing apparatus 1 can be made narrower, and furthermore, the conveying position and angle of the film can be finely controlled It becomes possible to obtain a warp stretched film having a small variation in film thickness and optical value. When the film feeding portion 2 and the conveying direction changing portion 3 are movable (slidable and pivotable), the stretching portion 5 is provided with the right and left clips It is possible to effectively prevent the badness of the film against the film.

The film feed portion 2 may be slidable and pivotable so that a long film can be fed to the entrance of the stretching portion 5 at a predetermined angle. In this case, it is also possible to adopt a configuration in which the installation of the transport direction changing section 3 is omitted.

At least one guide roll 4 is provided on the upstream side of the stretching portion 5 in order to stabilize the trajectory during traveling of the long film. Further, the guide roll 4 may be constituted by a pair of upper and lower rolls sandwiching the film therebetween, or may be constituted by a plurality of pairs of rolls. The guide roll 4 closest to the entrance of the stretching portion 5 is a driven roll for guiding the running of the film and is rotatably supported by a bearing portion (not shown). As the material of the guide roll 4, a known one can be used. Further, in order to prevent scratches on the film, it is preferable to reduce the weight of the guide roll 4 by applying a ceramic coating to the surface of the guide roll 4, or chrome plating the light metal such as aluminum.

It is preferable that one of the rolls on the upstream side of the guide roll 4 closest to the entrance of the stretching section 5 is nipped by pressing the rubber roll. By using such a nip roll, it is possible to suppress variations in the tension force in the film flow direction.

A pair of bearing portions at both ends (right and left) of the guide roll 4 closest to the entrance of the stretching portion 5 are provided with a film tension detecting device for detecting a tension generated in the film in the roll, Device, and a second tension detector are provided, respectively. As the film tension detecting device, for example, a load cell can be used. As the load cell, a known type of tensile or compression type can be used. The load cell is a device that converts a load acting on a point of contact into an electric signal by a strain gauge provided on a strain body and detects the load.

The load cell is provided on the right and left bearing portions of the guide roll 4 closest to the entrance of the stretching portion 5 so that the force exerted by the film during running on the roll, The tension is detected independently in the left and right direction. Further, a strain gauge may be provided directly on a support constituting the bearing portion of the roll, and the load, that is, the film tension may be detected based on the strain generated in the support. The relationship between the generated strain and the film tension is measured in advance and is assumed to be known.

When the position and transport direction of the film supplied from the film feed portion 2 or the transport direction changing portion 3 to the stretching portion 5 are shifted from the position toward the entrance of the stretching portion 5 and the transport direction, A difference occurs in the tension in the vicinities of both side edges of the film in the guide roll 4 closest to the entrance of the stretching section 5 depending on the amount of displacement. Therefore, by detecting the tension difference by installing the film tension detecting device as described above, it is possible to determine the degree of the deviation. That is, the load acting on the guide roll 4 becomes substantially equal at both ends in the axial direction when the conveying position and the conveying direction of the film are appropriate (the position and direction toward the inlet of the stretching section 5) Otherwise, difference in film tension occurs between right and left.

Therefore, in order to equalize the difference in film tension between the left and right sides of the guide roll 4 closest to the entrance of the stretching section 5, for example, the position of the film and the conveying direction (stretching section 5) is appropriately adjusted, the holding of the film by the waveguide of the entrance portion of the stretching portion 5 is stabilized, and the occurrence of troubles such as deviation from the waveguide can be reduced. In addition, it is possible to stabilize the physical properties of the film in the width direction after the warp stretching by the stretching portion (5).

At least one guide roll 6 is provided on the downstream side of the stretching section 5 in order to stabilize the trajectory at the time of running of the obliquely stretched film in the stretching section 5.

The carrying direction changing portion 7 changes the carrying direction of the film after being drawn from the stretching portion 5 in the direction toward the film winding portion 8.

Here, the film advancing direction at the entrance of the stretching section 5 and the film advancing direction at the exit of the elongating section 5 are set so as to correspond to the fine adjustment of the orientation angle (the direction of the in-plane slow axis in the film) It is necessary to adjust the angle. In order to adjust the angle, the direction in which the film is formed is changed by the transporting direction changing portion 3 to guide the film to the inlet of the stretching portion 5, and the film from the outlet of the stretching portion 5 It is necessary to change the traveling direction of the film by the carrying direction changing portion 7 to return the film to the direction of the film winding portion 8.

In addition, it is preferable to continuously perform film formation and warp stretching in terms of productivity and yield. When the film forming process, the warp stretching process, and the winding process are continuously performed, the film advancing direction is changed by the carrying direction changing portion 3 and / or the carrying direction changing portion 7, As shown in Fig. 1, the moving direction of the film fed from the film feeding portion 2 and the film advancing direction immediately before being wound by the film winding portion 8 Winding direction), it is possible to reduce the width of the entire device with respect to the film advancing direction.

It is not necessary that the film advancing direction in the film forming process and the winding process necessarily coincides with each other, but the direction of the film conveying direction changing section 3 and / or the film winding direction changing section 3 is set such that the film feeding section 2 and the film winding section 8 do not interfere with each other. Or the carrying direction changing portion 7 to change the traveling direction of the film.

The above-described transport direction changing unit 3 · 7 can be realized by a known method such as using an air flow roll or an air turn bar.

The film winding portion 8 is for winding a film conveyed from the stretching portion 5 through the conveying direction changing portion 7 and is constituted by, for example, a winder device, an algebraic device, a drive device or the like. It is preferable that the film take-up unit 8 is a structure that can slide in the lateral direction so as to adjust the winding position of the film.

The film take-up portion 8 is capable of finely controlling the take-in position and angle of the film so that the film can be pulled at a predetermined angle with respect to the exit of the stretching portion 5. [ This makes it possible to obtain a long oblong stretched film having a small variation in film thickness and optical value. In addition, the occurrence of wrinkles of the film can be effectively prevented, and the winding-up property of the film is improved, so that the film can be wound up in a long length.

The film winding portion 8 constitutes a pulling portion for pulling the film stretched and conveyed by the stretching portion 5 with a predetermined tension. Between the stretching portion 5 and the film winding portion 8, a take-up roll for pulling the film at a constant tension may be provided. Further, the guide roll 6 described above may have a function as the take-up roll.

In the present embodiment, the film pulling tension T (N / m) after stretching is preferably adjusted to be within the range of 100 N / m <T <300 N / m, preferably 150 N / m <T <250 N / m. When the pulling tension is 100 N / m or less, the film tends to relax or wrinkle, and the profile of retardation and orientation angle in the film width direction also deteriorates. On the other hand, when the pulling tension is 300 N / m or more, the orientation angle of the film is worsened in the width direction and the width yield (picking efficiency in the width direction) is deteriorated.

In the present embodiment, it is preferable to control the fluctuation of the take-up tension T at an accuracy of less than ± 5%, preferably less than ± 3%. If the fluctuation of the take-up tension T is ± 5% or more, fluctuation of the optical characteristics in the width direction and the flow direction (transport direction) becomes large. As a method of controlling the fluctuation of the take-up tension T within the above range, the load applied to the first roll (guide roll 6) on the exit side of the stretching portion 5, that is, the tensile force of the film is measured, A method of controlling the rotation speed of the take-up roll of the take-up roll or the film take-up unit 8 by a general PID control method may be mentioned. As a method of measuring the load, there is a method of measuring the load applied to the guide roll 6, that is, the tensile force of the film, by providing a load cell on the bearing portion of the guide roll 6. As the load cell, a known type of tensile type or compression type can be used.

The film after stretching is released from the outlet of the stretching section 5 by the gripping of the stretching section 5 and released from the exit of the stretching section 5. After both ends (both sides) of the film held by the gripping section are trimmed, (Winding roll) to form a winding body of a long warp stretched film. The trimming may be performed as necessary.

Further, before winding the long oblong stretched film, for the purpose of preventing blocking between the films, the masking film may be wound on the long oblong stretched film and wound at the same time, or at least one of the long oblong stretched films Tape or the like may be wound while being joined to the ends of both ends). The masking film is not particularly limited as long as it can protect the long warp stretched film. Examples of the masking film include a polyethylene terephthalate film, a polyethylene film, and a polypropylene film.

Further, before winding the long warp stretched film, at both end portions in the width direction of at least one surface (preferably both surfaces) of the film, a portion thicker than the film surface called the knurling portion or the emboss portion ) May be formed so as to prevent the films from being blocked from each other when the film is wound. Further, the height and shape of the knurled portion may be different at both end portions in the width direction (may be asymmetric).

(Details of extension section)

Next, the above-described elongating unit 5 will be described in detail. 2 is a plan view schematically showing an example of a rail pattern of a stretching portion 5. Fig. However, this is merely an example, and the configuration of the extending portion 5 is not limited to this.

The long oblong stretched film in this embodiment is produced by using a tenter stretchable tenter (warp stretching machine) as the stretching portion 5. This tenter is a device for heating a long film to an arbitrary stretchable temperature and obliquely stretching it. This tenter is constituted by a plurality of wave cores Ci · Co (in the case of FIG. 2, only one gripping zone is referred to as a "zone") for traveling the heating zone Z, a pair of rails Ri and Ro on the left and right, . Details of the heating zone Z will be described later. Each of the rails Ri and Ro is constituted by connecting a plurality of rail portions by connecting portions (the white circles in Fig. 2 are examples of the connecting portions). The wave segment Ci · Co is constituted by a clip holding both ends in the width direction of the film.

2, the elongating direction D1 of the elongate film is different from the elongating direction D2 of the elongated oblong drawn film after elongating, and forms the elongating angle? I between the elongated elongated drawn film and the winding direction D2. The feed angle? I can be arbitrarily set to a desired angle in a range exceeding 0 ° and less than 90 °.

As described above, since the feeding direction D1 and the winding direction D2 are different from each other, the rail pattern of the tenter is asymmetrical in the lateral direction, and the conveying path of the film is curved in the middle. Then, the rail pattern can be manually or automatically adjusted in accordance with the orientation angle?, Stretching magnification factor, and the like applied to the long oblong stretched film to be produced. In the warp stretching machine used in the manufacturing method of the present embodiment, it is preferable that the positions of the rail portions and the rail connecting portions constituting the rails Ri and Ro are freely set and the rail pattern can be arbitrarily changed.

In this embodiment, the wave earth Ci · Co of the tenter is kept at a constant distance from the front and rear wave earths Ci · Co and travels at a constant velocity. The traveling speed of the wave earth Ci · Co can be appropriately selected, but is usually 1 to 150 m / min. In the present embodiment, as described later, it is preferable that the film is heated preferably in the width direction to change the temperature, and preferably 20 to 100 m / min in consideration of the productivity of the film. The difference in travel speed between the pair of left and right wave windings Ci · Co is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less of the traveling speed. This is because, if there is a difference in the traveling speed between the left and right sides of the film at the exit of the drawing process, wrinkles and warps occur at the exit of the drawing process, and therefore the speed difference between the left and right wave regions Ci · Co is required to be substantially the same . In a general tentering machine or the like, speed irregularities occur due to the order of seconds or less depending on the period of the teeth of the sprocket for driving the chain, the frequency of the drive motor, and the like. Often several percent of the irregularities occur. This does not apply to the speed difference described.

In the warp stretcher used in the production method of the present embodiment, a rail for regulating the trajectory of the crushing strip is often required to have a large bending rate, particularly at a position where the conveyance of the film is inclined. In order to avoid interference between waveguides due to abrupt bending, or local concentration of stress, it is desirable to make the locus of the waveguide curved at the bent portion.

As described above, the oblique stretching tenters used for imparting the oblique directional orientation to the long film can freely set the orientation angle of the film by variously changing the rail pattern, and the orientation axis (slow axis) Can be uniformly and horizontally aligned in the width direction of the film, and the film thickness and retardation can be controlled with high precision.

Next, the drawing operation in the stretching section 5 will be described. Both ends of the long film are gripped by the left and right wave regions Ci 占. O, and are transported in the heating zone Z in accordance with traveling of the waveguide Ci 占. Co. The left and right wave regions Ci 占 상대 r are opposed to each other in a direction substantially perpendicular to the traveling direction (feeding direction D1) of the film at the entrance portion (position A in the drawing) of the stretching portion 5, And runs on the rails Ri and Ro, respectively, and the film gripped at the exit portion (the position of B in the figure) at the end of drawing is opened. The film opened from the wave region Ci 占 은 co is wound on the winding core in the film winding section 8 described above. The pair of rails Ri and Ro each have an endless continuous track, and the wave segment Ci 占 한, which opens the grip of the film at the exit of the tenter, travels on the outer rail and is returned to the successive entrance portion.

At this time, since the rail Ri 占 is asymmetric in the left and right directions, the left and right waveguides Ci 占 상대 in the example of Fig. 2, which are located at the position A in Fig. 2, (On the in-course side) than the wave earth Co running on the rail Ro side (out-course side).

That is, when one waveguide Ci of the waveguide Ci 占 Co, which has been opposed in the direction substantially perpendicular to the feeding direction D1 of the film at the position A in the figure, first reaches the position B at the end of the film stretching, The straight line connecting the waveguide Ci · Co is inclined by an angle θL with respect to a direction substantially perpendicular to the winding direction D2 of the film. With the above operation, the long film is obliquely elongated at the angle of? L with respect to the width direction. Here, the term &quot; substantially perpendicular &quot;

Next, the heating zone Z will be described in detail. The heating zone Z of the stretching section 5 is composed of a preheating zone Z1, a stretching zone Z2 and a heat fixing zone Z3. In the stretching section 5, the film held by the waveguide Ci 占 폚 passes through the preheating zone Z1, the stretching zone Z2, and the heat fixing zone Z3 in this order. In the present embodiment, the preheating zone Z1 and the stretching zone Z2 are partitioned by partition walls, and the stretching zone Z2 and the heat fixing zone Z3 are partitioned by partition walls. Further, partition walls may be appropriately provided in the respective zones of the preheating zone Z1, the stretching zone Z2, and the heat fixing zone Z3 (the inside of each zone may be further divided into partitions).

The preheating zone Z1 indicates a section in which the waveguide Ci 占 한 peewith holding both ends of the film at the entrance of the heating zone Z travels with left and right spacing (in the film width direction).

The stretching zone Z2 indicates a section from the beginning of the interval between the wave regions Ci and Co holding the both ends of the film to a predetermined interval. At this time, oblique stretching is performed as described above, but may be stretched in the longitudinal direction or in the transverse direction before and after oblique stretching, if necessary. That is, in the stretching zone Z2, while holding both ends in the transverse direction of the film with the pair of wave cores Ci · Co, the film is conveyed by relatively delaying the one wave earth Ci and the other wave earth Co relatively Together, the film is bent in the middle of the conveying path to perform the warp stretching process of stretching the film in the oblique direction with respect to the width direction.

The heat fixing zone Z3 indicates a section for fixing the optical axis (slow axis) of the obliquely drawn film after the end of the oblique stretching step in the stretching zone Z2. That is, in the heat fixing zone Z3, a heat fixing step for fixing the optical axis of the obliquely drawn film is performed. In the heat fixing zone Z3, the wave cores Ci and Co at both ends run parallel to each other. Thereby, the optical axis of the obliquely-drawn film is fixed.

The stretched film may pass through a section (cooling zone) where the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg (占 폚) of the thermoplastic resin constituting the film after passing through the heat fixing zone Z3.

The temperature of the preheating zone Z1 is in the range of Tg to Tg + 60 占 폚, the temperature of the stretching zone Z2 is in the range of Tg to Tg + 50 占 폚, the temperature of the heat-fixing zone Z3 and the cooling zone is in the range of Tg-40 to Tg- Tg + 30 占 폚.

The length of the preheating zone Z1, the stretch zone Z2 and the heat-fixing zone Z3 can be appropriately selected. The length of the preheating zone Z1 is usually 50 to 200% of the length of the stretching zone Z2, 50 to 150%.

When the width of the film before stretching is W0 (mm) and the film width after stretching is W (mm), the stretching magnification R (W / W0) in the stretching step is preferably 1.1 to 3.0 Lt; / RTI &gt; When the stretching magnification falls within this range, thickness irregularity in the width direction of the film becomes small, which is preferable.

[Temperature control of film in oblique stretching process]

Next, the temperature control in the film width direction in the oblique stretching zone Z2 in which the oblique stretching process is performed will be described. In the present embodiment, in the oblique drawing step, the temperature of the film is changed in the width direction at the time when the curvature of the arc shape of the conveying path for drawing in the oblique direction starts at the earliest point in the width direction of the film . In the following description, the curvature of the conveying path means that the conveying path is curved in an arc shape, that is, the conveying path is smoothly curved.

Here, FIG. 3 schematically shows a state in which the conveying path of the film in the stretching section 5 (indicated by a thick solid line in the figure) is bent on the way. As described above, the transport path of the film can be changed by adjusting the position and the degree of bend (curvature) of the rails Ri and Ro on which the pair of waveguides Ci and Co that grip both ends in the width direction of the film are driven . The above-mentioned &quot; starting point of bending of the conveying path for drawing in the oblique direction &quot; means a point at the most upstream side of the curved portions Q1 and Q2 curved in an arc shape for performing oblique drawing, P2 indicate the point at which an arbitrary point of the film reaches the point on the line connecting the points P2 and P2.

Further, when the film reaches the line connecting the points P1 and P2, the conveying direction of the film begins to bend in an arc shape and changes in the film discharging direction after the oblique drawing. In this respect, the term &quot; starting point of curving of the conveying path for elongating in the oblique direction &quot; means that the direction of the vector representing the transport direction of the film starts to change from the direction before the oblique drawing to the discharging direction after the oblique drawing .

Further, on the upstream side of the line connecting the points P1 and P2 in the carrying direction, the film may be subjected to transverse stretching (preliminary stretching) or transverse stretching as shown in the drawing.

3 shows an example in which the curvature of the conveyance path is simultaneously started in the width direction of the film (with respect to all the points in the width direction). In this case, &quot; the point at which the curvature of the conveying path for oblique stretching starts the fastest in the width direction of the film &quot; refers to the point at which all the points in the width direction of the film Lt; / RTI &gt;

On the other hand, depending on the length and the degree of bending of the bent portions Q1 and Q2, the leading side in the transverse direction of the film (waveguide Ci preceding the oblique stretching) and the retarded side (the waveguide Co side delayed in oblique stretching) The timing at which the curvature of the conveyance path starts may differ. The specific example of this case will be described later. However, when the above timing is different, "the time at which the curvature of the conveyance path for oblique stretching is the fastest start in the width direction of the film" (The fastest) on the line connecting the points P1 and P2.

Fig. 4 shows another method of the stretching section 5 described above. As shown in the figure, in the stretching zone Z2, there is a case where the rails Ri and Ro are connected in a linear shape for convenience. However, in this case as well, in practice, the conveying path of the film is bent in an arc- . Therefore, in this drawing, the conveying path of the film in the stretching portion 5 is as shown by an arrow of a thick solid line, and at a position on the upstream side of the line connecting the points Q11 and Q12, The bending is started. The points Q11 and Q12 indicate points at which the curvatures of the curved portions Q1 and Q2 shown in Fig. 3 become the maximum, or the middle points of the curved portions Q1 and Q2 in the carrying direction. Accordingly, in the example of Fig. 4, the position (the line connecting the points P1 'and P2') at which the curvature of the conveying direction is started on the upstream side of the line connecting the points Q11 and Q12 is set to a point P1 · P2 The temperature control in the width direction of the film of the present embodiment can be applied.

(Method of Film Temperature Control)

Hereinafter, a specific method of temperature control in the transverse direction of the film in the warp stretching step will be described.

&Quot; When the leading-side winding timing is fast &quot;

5 shows an example of the detailed configuration of the stretching section 5 and shows a configuration of the stretching section 5 which is earlier in timing of starting the bending of the conveying path on the leading side than the retarding side in the width direction of the film, Respectively. In this configuration, at the time point when the curvature of the conveying path on the preceding side in the width direction of the film starts, that is, at the time point when the leading end first reaches the point P1 from the leading side end portion and the delayed side end portion in the width direction of the film , The film is heated by the heating unit 11 so that the temperature of the film becomes lower on the delay side than on the preceding side, thereby changing the temperature of the film in the width direction.

As a method of heating by the heating unit 11, a method of blowing hot air from the upper surface side or the lower surface side of the film and changing the temperature of the hot air in the width direction of the film, a method of heating the film with an infrared heater, A method of changing the heating temperature in the width direction of the film, or the like. The number of the heating units 11 may be either a single number or a plurality. 5, the heating temperature may be varied in the width direction of the film by a single heating unit 11, and a plurality of heating units 11 having different outputs (heating capability) may be arranged in the width direction, The temperature may be varied in the width direction.

As a means for changing the film temperature in the width direction, means for heating or cooling the opposite side of the retarded side or the preceding side may also be adopted. As the means, it is preferable to use a method in which a wind having a different temperature on the delay side and the preceding side is sprayed, or only the temperature of the wind is constant and only one of the delay side and the preceding side is heated by a heater, Heating, and the like, and is not particularly limited.

When the start of bending of the transport path of the film is faster on the leading side than on the delayed side, oblique stretching of the leading side of the delayed side of the film starts quickly. In this case, since the region ahead of the retardation side of the film is shrunk in the transport direction in the oblique stretching more rapidly, the region where the film thickness becomes relatively thick increases (in the film discharge direction) It is difficult to stretch the film at the time of oblique stretching by the increase of the area.

Thus, by heating the film as described above and changing the film temperature in the width direction, the leading side of the film becomes relatively soft due to the relatively higher temperature than the retarded side, and the film tends to stretch during oblique stretching. On the other hand, the delayed side of the film becomes harder because the temperature is relatively lower than that of the preceding side, and it becomes difficult to stretch the film at the time of oblique stretching. Therefore, by changing the film temperature in the width direction at the starting point of the bending of the conveyance path, that is, at the time of starting the oblique drawing, the film which is easy to elongate due to the high temperature on the leading side is increased by oblique stretching, Stretching a film that is difficult to stretch due to low elongation by stretching the stretched film by stretching the stretchable film so that stretching unevenness that occurs during oblique stretching does not occur and an increase in the thickness of the film on the leading side (due to contraction in the transport direction) It is possible to reduce the occurrence of unevenness in orientation in the width direction, and it is possible to reduce occurrence of unevenness in the orientation angle in the width direction. As a result, even when the film after the oblique stretching is applied to the circularly polarizing plate for preventing reflection of the external light of the OLED, the color unevenness caused by the unevenness of the orientation angle in the width direction of the film can be reduced.

When the film temperature on the delay side in the width direction of the film is T1 (占 폚) and the film temperature on the preceding side is T2 (占 폚) at the time when the curvature of the conveyance path of the film , From the viewpoint of reliably reducing the thickness irregularity in the width direction of the film,

-20 ° C? (T1-T2)? -1 ° C

It is preferable to change the temperature of the film in the width direction. If the value of T1-T2 becomes smaller than the lower limit, the film in the region where the temperature is relatively low becomes too hard, and the film thickness on the delay side becomes thick, making it difficult to make the film thickness uniform in the width direction. On the other hand, if the value of T1-T2 is larger than the upper limit, the effect of making the leading side easier to grow at the time of oblique stretching becomes smaller, and the effect of reducing the thickness unevenness in the width direction is reduced. A more preferable range of T1-T2 is,

-10 ° C? (T1-T2)? -2 ° C

to be.

The film temperature can be measured with a non-contact temperature sensor. Specifically, the temperature of the film during drawing can be measured using a heat-resistant type noncontact temperature sensor (IRtec Rayomatic 14, manufactured by Eurotron). The heating and cooling temperature ranges are not particularly limited, and heating or cooling may be performed in a temperature range where desired in-plane retardation can be ensured.

&Quot; When the warp timing of the delay side is fast &quot;

6 shows another example of the stretching portion 5 and schematically shows the configuration of the stretching portion 5 in which the timing of starting the bending of the conveying path is earlier at the delay side than the leading side in the width direction of the film have. In this configuration, at the time when the delay side end first reaches the point P2 out of the retard side end and the leading side end in the transverse direction of the film at the start of bending of the transport path on the retard side in the width direction of the film, The film is heated by the heating unit 11 so that the temperature of the film is higher on the delay side than on the preceding side, thereby changing the temperature of the film in the width direction.

When the start of bending of the conveying path of the film is faster on the retard side than on the preceding side, oblique stretching of the retarded side of the film is started earlier than on the preceding side of the film. In this case, since the retarded side of the film is increased in shrinkage in the carrying direction in the oblique stretching, the region where the film thickness becomes relatively thick increases (in the film discharging direction), and therefore, It is difficult to stretch the film at the time of oblique stretching by an amount corresponding to the increase of the area.

Thus, by heating the film as described above and changing the film temperature in the width direction, the retarded side of the film becomes relatively soft due to the relatively higher temperature than the preceding side, and the film tends to stretch during oblique stretching. On the other hand, the leading side of the film is harder than the retarded side because the temperature is relatively lower, and the film is hardly stretched at the time of oblique stretching. Therefore, by varying the film temperature in the width direction at the start of the bending of the conveyance path, that is, at the time of starting the oblique stretching, the film which is liable to increase due to the high temperature at the retarded side is increased by oblique stretching, Stretching a film which is difficult to stretch due to low elongation by stretching the film by stretching the stretched film to cause stretching unevenness to occur during warp stretching does not occur and it is possible to prevent the film thickness from increasing on the delay side (due to contraction in the conveying direction) Occurrence of uneven stretching can be reduced, and occurrence of unevenness of the orientation angle in the width direction can be reduced. As a result, in the same manner as described above, it is possible to reduce the color unevenness caused by the unevenness of the orientation angle in the width direction of the film in the OLED.

When the film temperature on the delay side in the width direction of the film is T1 (占 폚) and the film temperature on the preceding side is T2 (占 폚) at the time when the curvature of the conveying path of the film , From the viewpoint of reliably reducing the thickness irregularity in the width direction of the film,

1 ° C ≤ (T1-T2) ≤ 18 ° C

It is preferable to change the temperature of the film in the width direction. If the value of T1-T2 is larger than the upper limit, the film in the region where the temperature is relatively high becomes too soft, and the film thickness on the delay side becomes thin, making it difficult to make the film thickness uniform in the width direction. On the other hand, if the value of T1-T2 is smaller than the lower limit, the effect of making the retarded side easier to elongate at the time of oblique stretching becomes small, and the effect of reducing the thickness unevenness in the width direction is reduced. A more preferable range of T1-T2 is,

2 ° C? (T1-T2)? 9 ° C

to be.

&Quot; When the winding timing is the same throughout the width direction &quot;

Fig. 7 shows another example of the stretching portion 5, which schematically shows the configuration of the stretching portion 5 having the same timing at which bending of the transport path starts in the width direction of the film. In this configuration, when the point at which the bending of the transport path of the film starts, that is, the point located in the width direction of the film reaches the line segment connecting the points P1 and P2, The temperature of the film is changed in the width direction by heating the film by the heating section 11 so as to be higher on the delay side than on the film side.

When the start of bending of the conveying path of the film is the same throughout the width direction, as shown in the drawing, the degree of bending in the oblique stretching is larger on the retarded side than on the leading side of the film. As a result, the degree of shrinkage in the transport direction in oblique stretching becomes larger on the retard side than on the leading side of the film. As a result, the film thickness becomes thicker on the delay side than on the preceding side of the film.

Thus, by heating the film as described above and changing the film temperature in the width direction, the retarded side of the film becomes relatively soft due to the relatively higher temperature than the preceding side, and the film tends to stretch during oblique stretching. On the other hand, the leading side of the film is harder than the retarded side because the temperature is relatively lower, and the film is hardly stretched at the time of oblique stretching. Therefore, by changing the film temperature in the width direction at the start of the bending of the conveyance path, that is, at the time of starting the oblique stretching, the film which is liable to be elongated due to the high temperature at the delay side is increased by oblique stretching, By stretching the film which is difficult to be stretched due to low elongation by oblique stretching, stretching unevenness which occurs during oblique stretching is not generated, and the occurrence of stretch non-uniformity in the entire width direction of the film is suppressed while suppressing an increase in film thickness on the delay side And it is possible to reduce occurrence of unevenness of the orientation angle in the width direction. As a result, in the same manner as described above, it is possible to reduce the color unevenness caused by the unevenness of the orientation angle in the width direction of the film in the OLED.

When the film temperature on the delay side in the width direction of the film is T1 (占 폚) and the film temperature on the preceding side is T2 (占 폚) at the start of bending of the conveying path of the film, From the viewpoint of reliably reducing the thickness unevenness in the direction,

1 ° C ≤ (T1-T2) ≤ 18 ° C

It is preferable to change the temperature of the film in the width direction. The basis of the upper limit and the lower limit of T1-T2 is the same as the basis of the upper limit and the lower limit of T1-T2 in the case where the deflection timing on the delay side is fast. A more preferable range of T1-T2 is,

2 ° C? (T1-T2)? 9 ° C

to be.

As described above, in the oblique stretching process, at the time point when the oblique stretching starts, that is, when the arcuate curvature of the film transport path for stretching in the oblique direction starts at the earliest in the width direction of the film, By changing the temperature in the width direction, it is possible to reduce occurrence of stretch unevenness in the width direction due to shrinkage of the film in the transport direction which occurs during oblique stretching. As a result, it is possible to reduce the unevenness of the orientation angle in the width direction of the film, and to reduce occurrence of color unevenness in the OLED.

(Variation of film temperature control)

5 to 7, the heating unit 11 is used to change the temperature of the film in two steps in the width direction, but the temperature control in the width direction is not limited to the two steps described above.

8 shows another example of the stretching portion 5 and schematically shows another configuration of the heating portion 11 arranged in the stretching portion 5. As shown in Fig. The heating section 11 may be changed into four steps as shown in the drawing, or may be changed into three steps or five or more steps as long as the heating temperature of the film is changed stepwise in the width direction. In this case, the heating temperature of either the leading side or the retarded side in the width direction of the film should be set in accordance with the bending start timing of the conveyance path on the leading side and the delay side, as described above.

9 schematically shows another configuration of the heating unit 11 disposed in the extending portion 5. As shown in Fig. The heating section 11 may change the heating temperature of the film continuously in the width direction. The film temperature can be continuously changed in the width direction by continuously changing the temperature or air volume of the hot air blown out from the heating unit 11 in the width direction or continuously changing the irradiation amount of infrared rays in the width direction have.

By thus changing the temperature of the film stepwise or continuously in the width direction at the time when the curvature of the conveying path in the warp stretching process is the fastest start in the width direction of the film, It is possible to reduce irregularities and unevenness of orientation angles. Particularly, by varying the film temperature in four or more steps in the width direction, it is possible to surely reduce the thickness non-uniformity in the width direction and the unevenness of the orientation angle by the fine temperature control in the width direction.

(Other)

The film to be subjected to warp stretching in the present embodiment may be a film containing a cellulose resin (such as the above-mentioned cellulose ester resin). In this case, film-like unevenness in width direction and unevenness of orientation angle can be reduced by obliquely stretching a film containing a cellulose-based resin while performing the aforementioned temperature control in the width direction.

In the oblique stretching step, the film may be conveyed at a speed of 1 to 150 m / min. However, from the viewpoint of surely changing the temperature in the width direction by heating the film and improving the productivity of the film, Is preferably 5 to 120 m / min, and more preferably 20 to 100 m / min.

&Lt; Quality of long oblique stretched film >

In the long oblong stretched film obtained by the manufacturing method of the present embodiment, the orientation angle? Is inclined to a range of, for example, greater than 0 degrees and less than 90 degrees with respect to the winding direction. In a width of at least 1300 mm, Of the retardation Ro in the plane is 2 nm or less, and the variation of the orientation angle [theta] is less than 0.6 [deg.]. The in-plane retardation value Ro (550) of the long oblong stretched film measured at a wavelength of 550 nm is preferably in the range of 80 nm to 160 nm, more preferably in the range of 90 to 150 nm desirable.

That is, in the long oblong stretched film obtained by the production method of the present embodiment, the fluctuation of the in-plane retardation Ro is preferably 2 nm or less and 1 nm or less at 1300 mm in the width direction. When the fluctuation of the in-plane retardation Ro is in the above range, a long oblong stretched film is bonded to the polarizer to form a circularly polarizing plate. When this is applied to an organic EL image display apparatus, Can be suppressed. In addition, when a long oblong stretched film is used as a retardation film for a liquid crystal display device, for example, the display quality can be made good.

In the long oblong stretched film obtained by the production method of the present embodiment, the variation of the orientation angle? Is preferably less than 0.6 deg., Less than 0.4 deg., And less than 0.2 deg. Is most preferable. When a long oblong stretched film having a variation of the orientation angle? Of more than 0.6 is bonded to a polarizer to form a circularly polarizing plate and this film is provided in an image display apparatus such as an organic EL display device, light leakage occurs, .

The in-plane retardation Ro of the long oblong drawn film obtained by the production method of this embodiment is selected in accordance with the design of the display device to be used. (Ro = (nx-ny) x d) obtained by multiplying the difference between the refractive index nx in the in-plane slow axis direction and the refractive index ny in the plane perpendicular to the slow axis in the plane by the average thickness d of the film, to be.

The average thickness of the long oblong drawn film obtained by the production method of the present embodiment is preferably 1 to 400 占 퐉, preferably 10 to 200 占 퐉, more preferably 10 to 60 占 퐉, particularly preferably Lt; / RTI &gt; Further, the thickness unevenness in the width direction of the long oblong drawn film is preferably not more than 2 탆, more preferably not more than 1 탆, because it affects the winding ability of the winding.

The long oblong stretched film obtained by the production method of the present embodiment may have a functional layer on its surface. The functional layer may be an antireflection layer, a low refractive index layer, a hard coat layer, a light scattering layer, a light diffusion layer, an antistatic layer, a conductive layer, an electrode layer, a birefringent layer, a surface energy adjustment layer, a UV absorption layer, A heat resistant layer, a magnetic layer, an oxidation preventing layer, an overcoat layer, and the like.

<Circular Polarizer>

In the circular polarizer of this embodiment, a polarizing plate protective film, a polarizer and a lambda / 4 film are laminated in this order, and the angle formed by the slow axis of the lambda / 4 film and the absorption axis (or transmission axis) . When the circular polarizer of the present embodiment is used in an organic EL display device, the protective film 313, the polarizer 311, the? / 4 film 316, Respectively. In the present embodiment, it is preferable that a long polarizing plate protective film, a long polarizer, and a long? / 4 film (long obliquely stretched film) are laminated in this order.

When the circular polarizer of the present embodiment is used in a liquid crystal display, the polarizer protective film, the polarizer, and the? / 4 film are the same as the protective film 506, the polarizer 501, the? / 4 film 503 Respectively. A protective film 506 and a polarizer 501 are disposed outside (on the viewing side) of the display cell 401. A lambda / 4 film 503 is further provided on the viewer side (on the viewer side) The linearly polarized light emitted from the display cell 401 and transmitted through the polarizer 501 is converted into the circularly polarized light or the elliptically polarized light by the? / 4 film 503. Therefore, in the case where the observer observes the display image of the display device 400 by attaching the polarizing sunglasses, even when observing at an angle (the transmission axis of the polarizer 501 (perpendicular to the absorption axis) It is possible to induce a component of light parallel to the transmission axis of the polarizing sunglasses to the eye of the observer so as to observe the display image and to prevent the display image from becoming hard to be seen in accordance with the observation angle.

The circular polarizer of the present embodiment can be produced by using a polarizer obtained by stretching polyvinyl alcohol doped with iodine or a dichroic dye and bonding it with a constitution of? / 4 film / polarizer. The film thickness of the polarizer is 5 to 40 占 퐉, preferably 5 to 30 占 퐉, and particularly preferably 5 to 20 占 퐉.

The polarizing plate can be manufactured by a general method. The alkali saponified? / 4 film is preferably bonded to one side of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a fully saponified polyvinyl alcohol aqueous solution.

The polarizing plate may be constituted by bonding a peeling film to the opposite surface of the polarizing plate protective film of the polarizing plate. The protective film and the release film are used for the purpose of protecting the polarizing plate at the time of polarizing plate shipment, product inspection and the like.

<Organic EL Display Device>

10 is a cross-sectional view showing a schematic structure of an organic EL display device 100 as an OLED of the present embodiment. The configuration of the organic EL display device 100 is not limited to this.

The organic EL display device 100 is configured by forming a circularly polarizing plate 301 on an organic EL element 101 with an adhesive layer 201 interposed therebetween. The organic EL element 101 includes a metal electrode 112, a light emitting layer 113, a transparent electrode (such as ITO) 114, and a sealing layer 115 on a substrate 111 made of glass or polyimide Consists of. The metal electrode 112 may be composed of a reflective electrode and a transparent electrode.

The circularly polarizing plate 301 includes a quarter wave film 316, an adhesive layer 315, a polarizer 311, an adhesive layer 312, a protective film 313, and a cured layer 314 in this order from the organic EL element 101 side The polarizer 311 is sandwiched between the? / 4 film 316 and the protective film 313. By joining both of them so that the angle formed by the transmission axis of the polarizer 311 and the slow axis of the? / 4 film 316 including the long obliquely stretched film of the present embodiment is about 45 (or 135) (301).

The protective film 313 preferably has a cured layer 314 laminated thereon. The cured layer 314 not only prevents surface scratches of the organic EL display device 100 but also has an effect of preventing warping by the circularly polarizing plate 301. [ Further, an antireflection layer may be formed on the cured layer 314. The thickness of the organic EL element 101 itself is about 1 mu m.

When a voltage is applied to the metal electrode 112 and the transparent electrode 114 in the above configuration, electrons are injected into the light emitting layer 113 from the metal electrode 112 and the transparent electrode 114 as cathodes , Holes are injected from the electrode serving as the anode, and both are recombined in the light emitting layer 113, so that visible light corresponding to the light emitting property of the light emitting layer 113 is emitted. Light generated in the light emitting layer 113 is directly or reflected by the metal electrode 112 and then is taken out to the outside through the transparent electrode 114 and the circularly polarizing plate 301.

Generally, in an organic EL display device, a light emitting element (organic EL element) is formed by sequentially laminating a metal electrode, a light emitting layer, and a transparent electrode on a transparent substrate. Here, the light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer including a triphenylamine derivative and the like, and a light emitting layer containing a fluorescent organic solid such as anthracene, A multilayer body with an electron injecting layer including a hole injecting layer, a hole injecting layer, and a derivative, and a laminate of these hole injecting layers, a light emitting layer, and an electron injecting layer.

In the organic EL display device, holes and electrons are injected into the light emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by the recombination of the holes and the electrons excites the fluorescent substance, And emits light when it returns to the state. The mechanism of recombination in the middle is similar to that of a general diode, and as can be expected from this, the current and the light emission intensity exhibit strong nonlinearity accompanied by rectification with respect to the applied voltage.

In the organic EL display device, at least one of the electrodes must be transparent in order to extract light from the light emitting layer, and a transparent electrode formed of a transparent conductor such as indium tin oxide (ITO) is usually used as the anode. On the other hand, it is important to use a material having a small work function for the cathode in order to facilitate injection of electrons and increase the luminous efficiency, and metal electrodes such as Mg-Ag and Al-Li are generally used.

In the organic EL display device having such a structure, the light-emitting layer is formed of an extremely thin film having a thickness of about 10 nm. As a result, the light emitting layer almost completely transmits the light, like the transparent electrode. As a result, the light incident on the surface of the transparent substrate at the time of non-light emission, the light transmitted through the transparent electrode and the light emitting layer and reflected by the metal electrode is again directed to the surface side of the transparent substrate, The display surface looks like a mirror.

The circularly polarizing plate of the present embodiment is suitable for organic EL display devices in which such external light reflection is particularly problematic.

That is, half of the external light incident from the outside of the organic EL element 101 by room illumination or the like is absorbed by the polarizer 311 of the circularly polarizing plate 301 at the time of non-emission of the organic EL element 101, Half of the light is transmitted as linearly polarized light, and is incident on the? / 4 film 316. The light incident on the? / 4 film 316 is incident on the? / 4 film 316 because the transmission axis of the polarizer 311 and the slow axis of the? / 4 film 316 intersect at 45 degrees (or 135 degrees) And is converted into circularly polarized light by passing through the film 316.

The circularly polarized light emitted from the lambda / 4 film 316 is inverted in phase by 180 degrees when it is mirror-reflected by the metal electrode 112 of the organic EL element 101, and is reflected as circularly polarized light in the reverse rotation. This reflected light is incident on the lambda / 4 film 316 and is converted into linearly polarized light perpendicular to the transmission axis of the polarizer 311 (parallel to the absorption axis). Therefore, all of the reflected light is absorbed by the polarizer 311, . That is, by the circularly polarizing plate 301, reflection of external light in the organic EL element 101 can be reduced.

<Liquid Crystal Display Device>

11 is a cross-sectional view showing a schematic configuration of a display device 400 as a liquid crystal display device of the present embodiment. The display device 400 is constituted by disposing a polarizing plate 402 on one side of the display cell 401.

In the case of a liquid crystal display device, the display cell 401 can be a liquid crystal cell in which a liquid crystal layer is sandwiched between a pair of substrates. Although a polarizing plate 402 and a backlight for illuminating the liquid crystal cell are provided on the other side of the liquid crystal cell opposite to the polarizing plate 402 in a cross-Nicol state, they are not shown in Fig. 11 .

The display device 400 may have a front window 403 on the side opposite to the display cell 401 with respect to the polarizing plate 402. [ The front window 403 serves as an external cover of the display device 400, and is constituted by, for example, a cover glass. Between the front window 403 and the polarizing plate 402, a filler 404 containing, for example, an ultraviolet curable resin is filled. An air layer is formed between the front window 403 and the polarizing plate 402. When the front window 403 and the polarizing plate 402 are in contact with the air layer, The visibility of the image may be deteriorated. However, since the air layer is not formed between the front window 403 and the polarizing plate 402 by the filler 404, deterioration of the visibility of the display image due to reflection of light at the interface can be avoided.

The polarizing plate 402 has a polarizer 501 which transmits a predetermined linearly polarized light. The? / 4 film 503 and the cured layer 504 including the ultraviolet curable resin are bonded to one side (opposite to the display cell 401) of the polarizer 501 via the adhesive layer 502 in this order Respectively. A protective film 506 is bonded to the other surface side (the display cell 401 side) of the polarizer 501 with an adhesive layer 505 interposed therebetween.

The polarizer 501 is obtained, for example, by staining a polyvinyl alcohol film with a dichromatic dye and stretching it at a high magnification. After the polarizer 501 is subjected to an alkali treatment (also referred to as a saponification treatment), a lambda / 4 film 503 is bonded to one side via an adhesive layer 502 and a protective film 506 is bonded to the other side, (505).

Assuming that the thickness of the polarizer 501 is B 占 퐉, from the viewpoint of thinning of the polarizing plate 402,

1 mu m < B &lt;

, &Lt; / RTI &gt;

1 mu m < B &lt;

Is more preferable.

The adhesive layer 502 占 505 is, for example, a layer containing a polyvinyl alcohol adhesive (PVA adhesive, waterbath), but may be a layer containing an ultraviolet curable adhesive (UV adhesive). These adhesives are liquids in the state of being applied to the adhesive surface, and are cured by drying or ultraviolet irradiation after application, thereby adhering them. That is, the adhesive layer 502 · 505 adheres the polarizer 501 and the λ / 4 film 503, and the polarizer 501 and the protective film 506, respectively, due to the state change from the liquid phase. As described above, the adhesive layer 502 占 505 has a pressure-sensitive adhesive layer (a sheet-like pressure-sensitive adhesive layer having a pressure-sensitive adhesive agent on the substrate) for adhering the both without causing such a state change, .

The? / 4 film 503 is a layer which gives an in-plane retardation of about 1/4 of the wavelength of transmitted light. In the present embodiment, for example, the? / 4 film 503 contains a cellulose resin (cellulose polymer). The? / 4 film 503 may contain a polycarbonate resin (polycarbonate-based polymer) instead of the cellulose-based polymer, or may include a cycloolefin-based resin (cycloolefin-based polymer) . However, from the viewpoint of chemical resistance, it is preferable that the? / 4 film 503 contains a cellulose polymer or a polycarbonate polymer.

The? / 4 film 503 is a? / 4 film of a thin film having a thickness of 10 mu m to 70 mu m. The angle (angle of intersection) between the slow axis of the? / 4 film 503 and the absorption axis of the polarizer 501 is 30 to 60 degrees so that the linearly polarized light from the polarizer 501 becomes? / 4 film 503 into circularly polarized light or elliptically polarized light.

The cured layer 504 (also referred to as a hard coat layer) is composed of an active energy ray curable resin (for example, an ultraviolet curable resin).

The protective film 506 is composed of an optical film including, for example, a cellulose-based resin (a cellulose-based polymer), an acrylic resin, a cyclic polyolefin (COP), and a polycarbonate (PC). Although the protective film 506 is provided as a film for simply protecting the back surface of the polarizer 501, it may be provided as an optical film serving as a retardation film having a desired optical compensation function.

In the case of a liquid crystal display device, a separate polarizing plate disposed on the side opposite to the polarizing plate 402 with respect to the display cell 401 (liquid crystal cell) is constituted by sandwiching the surface of the polarizing plate with two optical films, And the optical film may be the same as the polarizer 501 and the protective film 506 of the polarizing plate 402.

Here, the polarizer 501 and the? / 4 film 503 may be each long. In this case, it is preferable that the slow axis of the? / 4 film 503 is inclined by 30 to 60 degrees with respect to the longitudinal direction of the? / 4 film 503. In this case, the elongated lambda / 4 film 503 is formed by oblique stretching to form a roll-shaped film, which is then joined to the roll polarizer 501 by so-called roll- Of the polarizing plate 402 can be manufactured. Therefore, as compared with the case where the polarizing plate 402 is manufactured by a batch process in which the film pieces are bonded one by one, the productivity is remarkably improved and the yield can be greatly improved.

Further, an easy adhesion layer for improving the adhesiveness of the? / 4 film 503 may be provided on the adhesive layer 502 side of the? / 4 film 503. The adhesion facilitating layer is formed by performing an adhesion facilitating treatment on the adhesive layer 502 side of the? / 4 film 503. As the adhesion facilitating treatment, there are corona (discharge) treatment, plasma treatment, frame treatment, etch treatment, glow treatment, ozone treatment, primer coating treatment, and the like. Among these adhesion facilitating treatments, from the viewpoint of productivity, the corona treatment and the plasma treatment are preferable as the adhesion facilitating treatment.

<Examples>

Hereinafter, examples which are specific examples of the production of the warp stretched film in the present embodiment will be described with reference to comparative examples. The present invention is not limited to the following examples. In the following description, the notation &quot; part &quot; or &quot;% &quot; is used, but unless otherwise stated, they are expressed as &quot; part by mass &quot;

<Fabrication of Fabric Film>

Long films 1 to 2 as a raw film were produced by the following method.

(Long film 1)

The long film 1 is a cellulose ester resin film and was produced by the following production method.

&Quot; Fine particle dispersion liquid &

Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by mass

Ethanol 89 parts by mass

The mixture was stirred with a dissolver for 50 minutes, and then dispersed with mannitol. Thus, a fine particle dispersion 1 was prepared.

&Lt; Particulate additive liquid &

On the basis of the following composition, the fine particle dispersion was added slowly while stirring well in a dissolution tank containing methylene chloride. And dispersed by an attritor so that the particle diameter of the secondary particles became a predetermined value. This was filtered with Finetmet NF (manufactured by Nippon Seisen Co., Ltd.) to prepare a fine particle addition liquid 1.

 99 parts by mass of methylene chloride

 Fine particle dispersion 1 5 parts by mass

«Juodope»

To prepare a main dope liquid having the following composition. First, methylene chloride and ethanol were added to the pressure-melting tank. Cellulose acetate was added to the pressurized dissolution tank containing the solvent while stirring. This was heated and dissolved completely with stirring, and this was dissolved in Azumi filter paper No. 1 manufactured by Azumi Co., Ltd. 244 was used for filtration to prepare a main dope solution. As the sugar ester compound and the ester compound, the compound synthesized by the following synthesis examples was used.

&Quot; Composition of the main doping solution &quot;

Methylene chloride 340 parts by mass

64 parts by mass of ethanol

Cellulose acetate propionate (acetyl group degree of substitution: 1.50, propionyl group degree of substitution: 0.90, total degree of substitution: 2.40) 100 parts by weight

5.0 parts by mass of a sugar ester compound

Ester compound 5.0 parts by mass

1.5 parts by mass of ultraviolet absorber

Fine particle addition liquid 1 1 part by mass

&Lt; Synthesis of sugar ester compound &

A sugar ester compound was synthesized by the following process.

34.2 g (0.1 mol) of sucrose, 180.8 g (0.6 mol) of anhydrous benzoic acid, and 379.7 g (4.8 mol) of pyridine were fed into 4-necked colbins equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas introducing tube, The temperature was raised while bubbling nitrogen gas through a nitrogen gas introducing tube, and the esterification reaction was carried out at 70 DEG C for 5 hours.

Subsequently, the internal pressure of the colb inside was reduced to 4 × 10 ² Pa or less, excess pyridine was distilled off at 60 ° C., the internal pressure of the colb inside was reduced to 1.3 × 10 Pa or less, and the temperature was raised to 120 ° C. to obtain an anhydrous benzoic acid Was distilled off.

Finally, 100 g of water was added to the separated toluene layer, and the mixture was washed with water at room temperature for 30 minutes. Then, the toluene layer was collected, and toluene was distilled off at 60 캜 under reduced pressure (4 × 10 ² Pa or less) 1, A-2, A-3, A-4 and A-5 (sugar ester compound).

The obtained mixture was analyzed by HPLC and LC-MASS to find that the content of A-1 was 1.3 mass%, that of A-2 was 13.4 mass%, that of A-3 was 13.1 mass%, that of A-4 was 31.7 mass%, that of A- %. The average degree of substitution was 5.5.

&Quot; Measurement conditions of HPLC-MS &

1) LC section

(JASCO CO-965), detector (JASCO UV-970-240 nm), pump (JASCO PU-980), degasser (JASCO DG-980-50) manufactured by Nippon Bunko Co.,

Column: Inertsil ODS-3 Particle diameter 5 mu m 4.6 x 250 mm (manufactured by GL Sciences Inc.)

Column temperature: 40 DEG C

Flow rate: 1 ml / min

Mobile phase: THF (1% acetic acid): H ₂ O (50:50)

Injection volume: 3μl

2) MS Department

Apparatus: LCQ DECA (Thermo Quest Co., Ltd.)

Ionization method: Electrospray ionization (ESI) method

Spray Voltage: 5 kV

Capillary temperature: 180 DEG C

Vaporizer temperature: 450 DEG C

&Lt; Synthesis of ester compound &

An ester compound was synthesized by the following steps.

251 g of 1,2-propylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were put into a 2 L four-necked flask equipped with a thermometer, And the temperature is gradually raised while stirring in a nitrogen stream until the temperature becomes 230 캜. After dehydration condensation reaction for 15 hours, unreacted 1,2-propylene glycol was removed by distillation under reduced pressure at 200 占 폚 to obtain an ester compound. The ester compound has an ester of benzoic acid at the end of the polyester chain formed by condensing 1,2-propylene glycol, phthalic anhydride and adipic acid. The acid value of the ester compound was 0.10, and the number average molecular weight was 450.

Subsequently, using an endless belt flexing device, it was uniformly pliable on the stainless steel belt support.

In the endless belt flexing apparatus, the main dope liquid was uniformly softened on the stainless steel belt support. On the stainless steel belt support, the solvent was evaporated until the amount of the residual solvent in the long film (cast) was 75%, peeled from the top of the stainless steel belt support, dried and transferred to a plurality of rolls, Of long film 1 was obtained. At this time, the film thickness of the long film 1 was 67 탆.

(Long film 2)

The long film 2 is a cycloolefin resin film (COP) and was produced by the following production method.

1.2 parts by mass of 1-hexene, 0.15 parts by mass of dibutyl ether and 0.30 parts by mass of triisobutylaluminum were put into a reactor at room temperature and mixed in 500 parts by mass of dehydrated cyclohexane in a nitrogen atmosphere. 20 parts by mass of cyclo [4.3.0.12,5] deca-3,7-diene (dicyclopentadiene, hereinafter abbreviated as DCP), 1,4-methano-1,4,4a, 9a-tetrahydrofluoreene And 40 parts by mass of 8-methyl-tetracyclo [4.4.0.12,5.17,10] -dodeca-3-ene (hereinafter abbreviated as MTD) were mixed with a norbornene monomer mixture And 40 parts by mass of tungsten hexachloride (0.7% toluene solution) were continuously added over 2 hours to polymerize. 1.06 parts by mass of butyl glycidyl ether and 0.52 parts by mass of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst to terminate the polymerization reaction.

Subsequently, 270 parts by mass of cyclohexane was added to 100 parts by mass of the reaction solution containing the obtained ring-opening polymer, and 5 parts by mass of a nickel-alumina catalyst (manufactured by Nikkiso Co., Ltd.) was added as a hydrogenation catalyst. And the mixture was heated to 200 DEG C while stirring and then reacted for 4 hours to obtain a reaction solution containing 20% of a hydrogenated polymer of DCP / MTF / MTD ring opening polymer.

After the hydrogenation catalyst was removed by filtration, a soft polymer (Septon 2002, manufactured by Kuraray Co., Ltd.) and an antioxidant (Irganox 1010, manufactured by Ciba Specialty Chemicals) were added and dissolved respectively in the obtained solution 0.1 part by mass per 100 parts by mass of the polymer). Subsequently, cyclohexane and other volatile components as a solvent were removed from the solution by using a cylindrical condenser dryer (manufactured by Hitachi, Ltd.), and the hydrogenated polymer was extruded from the extruder in the form of a strand in a molten state, And then recovered by pelletizing. The copolymerization ratio of the respective norbornene monomers in the polymer was calculated by the composition of residual norbornenes in the solution after the polymerization (by gas chromatography), and it was found that DCP / MTF / MTD = 10/70/20 Respectively. The ring opening polymer hydrogenation product had a weight average molecular weight (Mw) of 31,000, a molecular weight distribution (Mw / Mn) of 2.5, a hydrogenation rate of 99.9%, and a Tg of 134 캜.

The resulting pellets of the ring opening polymerized hydrogenation product were dried at 70 DEG C for 2 hours using a hot-air drier through which air was circulated to remove moisture. Subsequently, the pellets were cut using a single-screw extruder (manufactured by Mitsubishi Kagaku Kogyo Co., Ltd., screw diameter 90 mm, T-die lip portion material was tungsten carbide, peel strength with molten resin 44 N) having a coat hanger type T die Followed by melt extrusion molding to produce a cycloolefin polymer film having a thickness of 75 탆. In the extrusion molding, a long film 2 having a width of 1500 mm was obtained in a clean room of class 10,000 or less under the molding conditions of a molten resin temperature of 240 캜 and a T-die temperature of 240 캜.

[Production of warp stretched film]

Using the long film 1 containing the cellulose-based resin prepared above, oblique stretching was carried out in the following manner. That is, the long film 1 (raw film) of the cellulose resin thus obtained was subjected to a temperature change in the film width direction at the start of oblique stretching using the stretching portion 5 shown in each of Figs. 5 to 8 , Thereby obtaining a long warp stretched film (see Examples 1 to 10 in Table 1). The temperature of the preheating zone Z1 was set to 200 占 폚, the temperature of the stretching zone Z2 was set to 200 占 폚, the temperature of the heat-set zone Z3 was set to 160 占 폚, the stretching magnification was set to 1.16 times And the thickness was 58 탆, and the final film width after the trimming treatment was 1300 mm. As a comparison, oblique stretching was performed without heating by the heating section 11 in the stretching section 5 shown in Figs. 5 to 7 to obtain a long oblong stretched film (refer to Comparative Examples 1 to 5 in Table 1) ).

In addition, for the raw material film (long film 2) containing COP, oblique stretching was performed in the same manner as described above. First, both ends of the unstretched film A fed from the film feeder 2 are moved in the vicinity of the front of the heating zone Z by the first clip as the leading waveguide Ci and the second clip as the waveguide Co on the delay side, Respectively. Further, when gripping the unstretched film A, the clip lever of the first and second clips is moved by the clip closure to grip the unstretched film A. When the clip is gripped, both ends of the unstretched film A are grasped by first and second clips at the same time, and a line connecting the grasping positions at both ends is parallel to an axis parallel to the film width direction. do.

Subsequently, using the stretching section 5 shown in Fig. 5 and Fig. 7, oblique stretching was performed while giving a temperature change in the film width direction at the start of oblique stretching to obtain a long obliquely stretched film (see See Examples 11 to 12). That is, the untuned film A gripped and held is transported while being grasped by the first and second clips and is heated by passing through the preheating zone Z1, the stretching zone Z2 and the heat fixing zone Z3 in the heating zone Z, To obtain a stretched film A 'that was stretched in an oblique direction. 5 and 7, the oblique stretching was performed without heating by the heating section 11 to obtain a long warped stretched film (refer to Comparative Examples 6 to 7 in Table 1) ).

The film moving speed at the time of heating and stretching was 40 m / min. The temperature of the preheating zone Z1 was 147 占 폚, the temperature of the stretching zone Z2 was 147 占 폚, and the temperature of the heat-fixing zone Z3 was 140 占 폚. The stretching magnification of the film before and after stretching was 1.16 times, and the film thickness after stretching was 58 占 퐉.

In addition, oblique stretching was performed under the same stretching condition (width temperature control) as in Example 7 except that the film moving speed at the time of oblique stretching was changed to 5 m / min to obtain a long warped stretched film (Example 13 Reference).

Further, when stretched under the same stretching conditions as in Example 7, a fabric film (cellulose ester resin film) having a film thickness of 40 mu m after stretching was produced by the same manufacturing method as that of the long film 1 , And this fabric film was obliquely stretched under the same stretching conditions as in Example 7 (except that the temperature in the preheating zone and the stretching zone were set at 198 占 폚) and the film moving speed (15 m / min) To obtain an oblique stretched film (see Example 14 of Table 1). Further, except that the same fabric film as used in Example 14 was used and the film moving speed at the time of oblique stretching was changed to 5 m / min, oblique stretching was performed under the same stretching conditions as in Examples 7 and 14, A film was obtained (see Example 15 of Table 1).

In addition, the temperature described in each of the above embodiments is the temperature of the zone, not the film temperature.

[Production of circularly polarizing plates 1 to 15]

Using the long oblique stretched film obliquely stretched under the same conditions as above, circular polarizers 1 to 15 were produced as follows.

That is, a polyvinyl alcohol film having a thickness of 120 占 퐉 was uniaxially stretched (temperature 110 占 폚, stretching magnification 5 times), immersed in an aqueous solution containing 0.075g of iodine, 5g of potassium iodide and 100g of water for 60 seconds, 6 g of potassium, 7.5 g of boric acid, and 100 g of water. The immersed film was washed with water and dried to obtain a polarizer.

Subsequently, the long oblique stretched films of Examples 1 to 15 produced were bonded to one surface of the polarizer using a 5% aqueous solution of polyvinyl alcohol as a pressure-sensitive adhesive. At that time, the polarizing element was bonded so that the transmission axis of the polarizer and the slow axis of the warp stretched film were in a direction of 45 degrees. Then, the other side of the polarizer was similarly joined with Konica Minolta Tact Film KC4UAH (Konica Minolta Co., Ltd.) subjected to alkali saponification treatment to prepare circularly polarizing plates 1 to 15.

[Production of circularly polarizing plates 16 to 30]

Using the long warp stretched film obliquely stretched under the same conditions as above, circular polarizers 16 to 30 were produced as follows.

That is, a polyvinyl alcohol film having a thickness of 120 占 퐉 was uniaxially stretched (temperature 110 占 폚, stretching magnification 5 times), immersed in an aqueous solution containing 0.075g of iodine, 5g of potassium iodide and 100g of water for 60 seconds, 6 g of potassium, 7.5 g of boric acid, and 100 g of water. The immersed film was washed with water and dried to obtain a polarizer.

Subsequently, the long oblique stretched films of Examples 1 to 15 produced were bonded to one surface of the polarizer using a 5% aqueous solution of polyvinyl alcohol as a pressure-sensitive adhesive. At this time, the transmission axis of the polarizer and the slow axis of the warp stretched film were bonded so as to be in a direction of 45 degrees. Then, Konica Minolta Tact Film KC2CT1 (manufactured by Konica Minolta Co., Ltd.) subjected to alkali saponification treatment was similarly bonded to the other side of the polarizer to prepare circularly polarizing plates 16 to 30.

[Production of organic EL display devices 1 to 15]

A reflective electrode containing chromium of 80 nm thickness was formed on the glass substrate by sputtering. Subsequently, ITO (indium tin oxide) was formed as a positive electrode on the reflective electrode to a thickness of 40 nm by sputtering. Subsequently, poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate (PEDOT: PSS) was formed as a hole transporting layer on the anode at a thickness of 80 nm by sputtering. Thereafter, using a shadow mask on the hole transporting layer, each light emitting layer of RGB was formed to a thickness of 100 nm.

In addition, calcium was deposited to a thickness of 4 nm by vacuum evaporation as a first cathode having a low work function capable of efficiently injecting electrons onto the light emitting layer. Thereafter, aluminum was formed to a thickness of 2 nm as a second cathode on the first cathode. The aluminum used as the second cathode has a role of preventing the chemical change of the calcium serving as the first anode when the transparent electrode formed thereon is formed by the sputtering method. Thus, an organic light emitting layer was obtained.

Next, a transparent conductive film was formed to a thickness of 80 nm on the cathode by a sputtering method. ITO was used as the transparent conductive film. Further, 200 nm of silicon nitride was formed on the transparent conductive film by a CVD method (chemical vapor deposition method) to form an insulating film. Thus, an organic EL device was fabricated. The size of the prepared organic EL device was 1296 mm x 784 mm.

The circular polarizers 1 to 15 prepared as described above were fixed with an adhesive so that the surface of the obliquely drawn film was directed to the insulating film surface of the organic EL element on the insulating film of the organic EL element thus fabricated. Thus, the organic EL display devices 1 to 15 were produced.

[Production of liquid crystal display devices 1 to 15]

&Quot; Fabrication of liquid crystal display device &quot;

The polarizing plate on the viewing side of the commercially available 10-inch liquid crystal display device was peeled off and bonded to the substrate surface of the liquid crystal cell to produce a liquid crystal display device. At that time, bonding of the polarizing plate was performed so that the absorption axis was directed in the same direction as that of the polarizing plate previously bonded. Then, the circular polarizers 16 to 30 produced above were bonded with a pressure-sensitive adhesive so that the side of the Konica Minolta Tact Film KC2CT1 faced the surface of the liquid crystal cell, thereby producing liquid crystal display devices 1 to 15.

〔evaluation〕

In order to investigate the variation of the orientation angle in the width direction of the produced film, the obliquely drawn film produced in the same manner as in Examples 1 to 15 and Comparative Examples 1 to 7 in Table 1 was subjected to measurement of the orientation angle in the width direction and the longitudinal direction Was measured by the following method to determine the variation of the orientation angle. That is, a rectangular film having a length of 10 cm was cut out at intervals of 1 m from the long obliquely stretched film in the width direction, and the width of the film at the time of manufacture was left as it was for 24 hours in a room at 23 캜 and 55% RH (KOBRA-WXK manufactured by Oji Keisoku Co., Ltd.) was used to measure the orientation angle at an interval of 25 mm in the width direction of the long oblong drawn film, and the difference between the maximum value and the minimum value was determined as the orientation angle (°). Then, on the basis of the following evaluation criteria, the unevenness of the orientation angle in the width direction was quantitatively evaluated.

"Evaluation standard"

AA: Variation of the orientation angle in the width direction is less than 0.3 degrees.

A: The variation of the orientation angle in the width direction is 0.3 DEG or more and less than 0.4 DEG.

B: Variation of the orientation angle in the width direction is 0.4 DEG or more and less than 0.6 DEG.

C: Variation of the orientation angle in the width direction is 0.6 DEG or more and less than 0.8 DEG.

D: Variation of the orientation angle in the width direction is 0.8 degrees or more.

Table 1 shows the results of evaluation of the uneven orientation angles performed on the warp stretched films of Examples 1 to 15 and Comparative Examples 1 to 7. In Table 1, the stretching methods 1 to 3 correspond to the stretching methods of Figs. 5 to 7, respectively. That is, the stretching method 1 refers to the oblique stretching method with a faster leading-edge bending timing than the retarding side with respect to the film. The stretching method 2 refers to the oblique stretching method with a faster bending timing on the delay side than the leading side of the film, Reference numeral 3 denotes a warp stretching method in which the warp timing is the same throughout the entire width direction of the film. The width temperature difference indicates a difference between the temperature at the most delayed position and the temperature at the most preceding position in the film width direction and the temperature indicates the temperature in the hot air blowing portion of the heating portion . The width temperature difference was measured using the above-mentioned heat-resistant type noncontact temperature sensor (IRtec Rayomatic 14, manufactured by Eurotron Co., Ltd.). The width temperature difference shown in Table 1 is the temperature difference of the film measured by the above method and is not the temperature difference of each zone of the stretching portion.

In the temperature distribution in the width direction in Table 1, the temperature difference adjustment pattern (pattern 1) indicates the temperature distribution when the film is not heated in the width direction and no temperature change is applied (see FIG. 12). The retarded side low temperature (pattern 2) indicates the temperature distribution when the film is heated by changing the heating temperature in two steps in the width direction so that the retarded side becomes lower than the preceding side (see a solid line graph in FIG. 13). The leading low temperature (pattern 3) indicates the temperature distribution when the film is heated by changing the heating temperature in two steps in the width direction so that the leading side becomes lower than the delay side (see the dashed line graph in FIG. 13). The retarded low temperature (pattern 4) indicates the temperature distribution when the film is heated by varying the heating temperature in four steps in the width direction so that the delayed side is lower in temperature than the preceding side (see the solid line graph in FIG. 14). The leading low temperature (pattern 5) indicates the temperature distribution when the film is heated by varying the heating temperature in four steps in the width direction so that the leading side becomes lower than the delay side (see the broken line graph in Fig. 14).

From the results of Examples 1 to 15 and Comparative Examples 1 to 7, it was found that by changing the film temperature in the width direction at the start of oblique stretching (at the time when the curvature of the arc shape for oblique stretching is started) It can be seen that the unevenness of orientation is reduced.

In particular, from the results of Example 1 and Example 4, it was found that in the stretching method 1, the temperature difference in the width direction was -3.3 DEG C or less (-10 DEG C lower than -0.9 DEG C in Example 1) It is preferable that the unevenness of the orientation angle in the width direction can be further reduced. From the results of Example 2 and Example 5, it is understood that in the stretching method 2, the temperature difference in the width direction is 1 ° C or more (the delay side is higher than the leading side), which is larger than 0.8 ° C in Example 2, It is possible to further reduce the unevenness of orientation of the liquid crystal display device. Likewise, from the results of Examples 3 and 6, it is understood that even in the stretching method 3, the temperature difference in the width direction is 1 ° C or more (the delay side is higher than the preceding side), which is larger than 0.7 ° C in Example 3, It is possible to further reduce the unevenness of orientation of the liquid crystal display device.

From the results of Examples 4 to 5 and Examples 7 to 8, even if the temperature difference in the width direction is substantially the same, if the number of steps for controlling the temperature in the width direction stepwise is increased from 2 to 4, And it is possible to reduce the unevenness of the orientation angle in the width direction.

From the results of Comparative Examples 1 to 2 and Comparative Examples 4 to 5, it can be seen that when the transporting speed of the film is increased, the unevenness of the orientation angle in the width direction is worsened. However, as in the case of Examples 9 to 10, even when the conveying speed is fast, by giving a temperature change in the width direction of the film at the start of oblique drawing (by heating the leading side or the delaying side), the unevenness of the orientation angle in the width direction is reduced Can be seen.

Furthermore, from the results of Comparative Examples 6 to 7 and Examples 11 to 12, regardless of the material used for the film (whether it is a cellulose resin or a COP resin), a temperature change is imparted in the width direction of the film at the start of oblique stretching , It can be seen that the unevenness of the orientation angle in the width direction can be reduced.

It is also understood from the results of Examples 7 and 13 that even when the film moving speed at the time of oblique stretching is further reduced from 15 m / min to 5 m / min, a temperature change is applied in the width direction of the film at the start of oblique stretching, It is possible to sufficiently reduce the unevenness of the orientation angles.

From the results of Examples 7 and 14, it is also possible to sufficiently reduce the unevenness of the orientation angle in the width direction by applying a temperature change in the film width direction at the time of start of oblique stretching even in a thin film. From the results of Example 15, it can be seen that the unevenness of the orientation angle in the width direction can be sufficiently reduced by imparting a temperature change in the width direction of the film at the time of start of oblique stretching even in a thin film, have.

In the organic EL display devices 1 to 15 in which the circular polarizers 1 to 15 were fabricated using the obliquely drawn films prepared in Examples 1 to 15 and the circular polarizers 1 to 15 thus prepared were used for preventing reflection of external light, It was confirmed that the color unevenness was reduced.

In addition, in the liquid crystal display devices 1 to 15 produced by using the obliquely drawn films produced in Examples 1 to 15 and the circularly polarizing plates 16 to 30 using the circularly polarizing plates 16 to 30, a black screen was displayed, It was confirmed that even when the polarized sunglasses were mounted, even when the display screen was visually observed, the screen was uniformly displayed in black, and the color unevenness due to the unevenness of the reflected light quantity was not observed.

The above-described method of producing the warp stretched film of this embodiment can be expressed as follows.

1. The film is gripped by a pair of gripping portions on both ends in the width direction of the film to relatively advance the one waveguide and relatively delay the other waveguide, And a warp stretching step of stretching the film in an oblique direction with respect to the width direction,

In the warp stretching step, the temperature of the film is changed in the width direction at the time when the arcuate curvature of the conveying path for stretching in the oblique direction is started at the earliest in the width direction of the film By weight based on the total weight of the composition.

2. The method of claim 1, wherein, when the leading edge of the film on the leading side of the widthwise delayed side is early in the bending of the conveying path, And the temperature of the film is changed in the width direction so as to be lower on the retarded side than on the side of the film.

3. When the film temperature on the retarded side is T1 (占 폚) and the film temperature on the preceding side is T2 (占 폚) in the width direction of the film,

-20 ° C? (T1-T2)? -1 ° C

, And the temperature of the film is changed in the width direction so that the temperature of the obliquely-drawn film becomes equal to or less than the thickness of the film.

4. The method of claim 1, wherein, in the case where the timing at which the bending of the conveyance path starts is earlier at the retarded side than the preceding side in the width direction of the film, at the time when the bending of the retarded- And the temperature of the film is changed in the width direction so as to be higher on the delay side than on the preceding side.

5. A method for producing a film according to any one of claims 1 to 4, wherein, at the start of bending of the conveyance path, the temperature of the film is delayed from the leading side in the width direction of the film And the temperature of the film is changed in the width direction so as to be higher at the side of the film.

6. When the film temperature on the delay side is T1 (占 폚) and the film temperature on the preceding side is T2 (占 폚) in the width direction of the film,

1 ° C ≤ (T1-T2) ≤ 18 ° C

, Wherein the temperature of the film is changed in the width direction so that the temperature of the film is changed.

7. The method according to any one of 1 to 6 above, characterized in that the temperature of the film is changed stepwise or continuously in the width direction at the time when the curvature of the conveying path starts at the earliest point in the width direction of the film By weight based on the total weight of the composition.

8. The method of producing an obliquely-drawn film according to 7 above, wherein the temperature of the film is changed in four or more steps in the width direction.

9. The method of producing an obliquely-drawn film according to any one of 1 to 8 above, wherein the film comprises a cellulose-based resin.

10. The method of producing an obliquely-drawn film according to any one of 1 to 9 above, wherein the film has a conveying speed of 20 to 100 m / min.

INDUSTRIAL APPLICABILITY The present invention can be used for manufacturing a circularly polarizing plate for preventing reflection of external light of an organic EL image display apparatus, for example.

Ci: Pe district
Co: Far East

Claims (10)

delete delete delete The film is transported in such a manner that both ends in the transverse direction of the film are gripped by a pair of gripping portions and one of the wave earths is relatively advanced and the other wave earth is relatively delayed, Stretching the film in an oblique direction with respect to a transverse direction of the film,
In the warp stretching step, the temperature of the film is changed in the width direction at the time when the arcuate curvature of the conveyance path for stretching in the oblique direction is the fastest start in the width direction of the film,
When the timing at which the bending of the conveyance path starts is faster at the delay side than the preceding side in the width direction of the film, at the time when the bending of the conveyance path on the delay side is started, Wherein the temperature of the film is changed in the width direction so as to be higher on the retarded side than on the retarded side. The film is transported in such a manner that both ends in the transverse direction of the film are gripped by a pair of gripping portions and one of the wave earths is relatively advanced and the other wave earth is relatively delayed, Stretching the film in an oblique direction with respect to a transverse direction of the film,
In the warp stretching step, the temperature of the film is changed in the width direction at the time when the arcuate curvature of the conveyance path for stretching in the oblique direction is the fastest start in the width direction of the film,
Wherein when the temperature at which the film starts to bend is smaller than the temperature at which the temperature of the film is lower than the temperature at the front side in the width direction of the film, Wherein the temperature of the film is changed in the width direction so as to increase the film thickness of the film. The film according to claim 4 or 5, wherein, in the width direction of the film, the film temperature on the delay side is T1 (占 폚) and the film temperature on the preceding side is T2 (占 폚)
1 ° C ≤ (T1-T2) ≤ 18 ° C
, Wherein the temperature of the film is changed in the width direction so that the temperature of the film is changed. The method according to claim 4 or 5, characterized in that the temperature of the film is changed stepwise or continuously in the width direction at a time point when the curvature of the conveyance path starts the earliest in the width direction of the film A method for producing an oblique stretched film. The method of producing an obliquely-drawn film according to claim 7, wherein the temperature of the film is changed in four or more steps in the width direction. The method according to claim 4 or 5, wherein the film comprises a cellulose-based resin. The method of producing an obliquely-drawn film according to claim 4 or 5, wherein the transporting speed of the film is 20 to 100 m / min.

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