KR100831192B1 - Method for producing birefringent film, optical film and image display device using the same - Google Patents

Abstract

Provided is a birefringent film having excellent in-plane retardation, thickness direction retardation, and uniformity of alignment axes. In the process of extending | stretching a polymer film, when extending | stretching the said polymer film in the width direction, and shrink | contracting in the longitudinal direction, when making the length of the width direction and the length direction of the polymer film before extending | stretching 1 respectively, And the birefringence film is manufactured by the relationship between the change ratio STD of the length direction of the width direction by the said extending | stretching, and the change ratio SMD of the length direction of the longitudinal direction by the said contraction satisfying following formula (1).

SMD<1 … (1) (1 / STD) ^1/2

SMD <1... (One)

Birefringence film, polarizing film, optical film, image display device

Description

The manufacturing method of a birefringent film, the optical film and the image display apparatus using the same {METHOD FOR PRODUCING BIREFRINGENT FILM, OPTICAL FILM AND IMAGE DISPLAY DEVICE USING THE SAME}

This invention relates to the manufacturing method of a birefringent film, the optical film using the same, and various image display apparatuses.

In various image display apparatuses, such as a liquid crystal display device, in order to improve display characteristics, a birefringent film is normally used for the purpose of eliminating coloring, expanding a viewing angle, etc., for example. Generally, such a birefringent film is produced by adjusting the birefringence and the phase difference by performing uniaxial stretching or biaxial stretching on a polymer film.

When using such a birefringent film together with a polarizing film for a liquid crystal display device, it is usually necessary to arrange | position the said film so that the slow axis of the said birefringent film and the transmission axis of a polarizing film may become parallel. In general, the slow axis of the birefringent film coincides with the stretching direction, and the transmission axis of the polarizing film coincides with the vertical direction with respect to the stretching direction.

However, disposing a birefringent film and a polarizing film in this way has the following problems in manufacturing. That is, when extending | stretching a polymer film industrially, it is common to carry out an extending | stretching process to a film, and to move a film in a longitudinal direction and to wind it with a roll simultaneously. And when attaching the birefringent film wound by the roll and the polarizing film wound by the roll in this way, if it winds again with a roll, attaching both in the state which made the longitudinal direction of each film constant, continuous adhesion can be implement | achieved. For this reason, in order to continuously adhere | attach the said both films, arrange | positioning the said transmission axis and the said slow axis in parallel, while extending | stretching the said polarizing film in the longitudinal direction, it is necessary to extend | stretch the said birefringent film in the width direction. In other words, in order to set the direction of the transmission axis (the direction perpendicular to the stretching direction) of the polarizing film and the direction of the slow axis (the stretching direction) of the birefringent film to the width direction of each film, it is necessary to stretch the birefringent film in the width direction. Is there. However, in the production of the birefringent film, when the polymer film is continuously stretched in the width direction, for example, an in-plane orientation axis becomes a fan shape, that is, a bowing phenomenon occurs. Thus, the stretching direction in the width direction is uniform. It was difficult to generate birefringence and phase difference.

Therefore, as a method of stretching the polymer film in the width direction, a method of improving the uniformity of the slow axis in the width direction (stretching direction) by performing a relaxation treatment that is once stretched in the width direction and then returns to the original width position It is adopted. In general, however, since the polymer film is directly formed on the substrate and then stretched together with the substrate, the method may be affected by variations in the physical properties of the substrate, or may have a small relaxation effect depending on the polymer film. This makes it difficult to produce industrially stable and uniform birefringent films. Moreover, although there exists an attempt to reduce the bowing phenomenon by cooling after extending | stretching, it is impossible to avoid the said bowing phenomenon completely (for example, nonpatent literature 1). Moreover, although the method of thermally contracting the said base material by loosening the base material with a polymer film between the chucks of a tenter stretching machine is also disclosed (for example, patent document 1), it is limited to the base material which has a heat shrinkability, If the thickness of the base material is too thick, wrinkles may occur when the base material is loosened, so that it is difficult to stably loosen the base material. Moreover, besides these, the method of setting extending | stretching conditions, for example, the method of making the width | variety of a stretched film into the square root of a draw ratio (for example, patent document 2), and the method of defining the width | variety of shrinkage accompanying longitudinal stretch Although patent method 3 (for example, patent document 3) and the method of heat relaxation after extending | stretching (for example, patent document 4) etc. are disclosed, stable production is difficult from an industrial standpoint.

Non-Patent Document 1: T. Yamada et al. Intn. Polym. Process., Vo.X, Issue 4, 334-340 (1995)

Patent Document 1: Japanese Unexamined Patent Publication No. Hei 6-51116

Patent Document 2: Japanese Patent Application Laid-Open No. 3-23405

Patent Document 3: Japanese Patent Application Laid-Open No. 2-191904

Patent Document 4: Japanese Patent Application Laid-Open No. 5-249316

Therefore, the objective of this invention is the birefringence film which is excellent in external appearance, and excellent in the uniformity of the optical characteristic by which the birefringence, retardation, and the deviation of the orientation axis angle were suppressed when extending | stretching a polymer film in the width direction, and manufacturing a birefringence film. It is to provide a method for producing.

In order to achieve the above object, the birefringent film production method of the present invention, in the stretching step, while stretching the polymer film in the width direction, and shrink in the longitudinal direction (vertical direction with respect to the width direction), The relationship between the change ratio (STD) of the length in the width direction by the stretching and the change ratio (SMD) of the length in the longitudinal direction due to the shrinkage based on the length in the width direction and the length in the longitudinal direction of the polymer film before stretching. It is characterized by satisfy | filling following formula (1). Moreover, in this invention, the change ratio (STD) of the length of the width direction by the said extending | stretching, and the change ratio (SMD) of the length direction of the longitudinal direction by the said shrinkage are the length and length of the width direction of the polymer film before extending | stretching. It may be based on the case where the length of a direction is set to 1, respectively.

SMD<1 … (1) (1 / STD) ^1/2

SMD <1... (One)

As described above, the birefringent film production method of the present invention, in the stretching step, stretches the polymer film in the width direction, shrinks it in the longitudinal direction, and length and length in the width direction of the polymer film before stretching. In the case where the length in the direction is set to 1, the change ratio STD of the length in the width direction due to the stretching and the change ratio SMD of the length in the longitudinal direction due to the shrinkage satisfy the following expression (1). It is characterized by. In addition, in this invention, when a polymer film is rectangular, a longitudinal direction shows the direction where the distance of both ends is long, and the width direction shows the direction perpendicular | vertical to the said longitudinal direction. In addition, when a polymer film is square, what is necessary is just the direction which becomes a perpendicular | vertical direction.

SMD<1 …(1) (1 / STD) ^1/2

SMD <1... (One)

When "SMD = 1", i.e., the dimension in the longitudinal direction does not change, the problem of occurrence of the bowing phenomenon cannot be solved, and when "(1 / STD) ^1/2 >SMD", wrinkles occur in the width direction. There is a cosmetic problem.

In said Formula (1), SMD = (1 / STD) ^1/2 is preferable. In addition, the SMD is preferably less than 0.99, more preferably 0.85 to 0.95, and particularly preferably 0.88 to 0.93. In formula (1), (1 / STD) ^1/2 is preferably less than 0.99, more preferably 0.85-0.95, particularly preferably 0.88-0.93, that is, STD is less than 1.5. It is preferable, More preferably, it is 1.01 or more and less than 1.5, Especially preferably, it is 1.1-1.3. Specifically, when STD is 1.2, it is preferable that SMD is 0.9-0.92, and when STD is 1.3, it is preferable that SMD is 0.86-0.90. As a preferred condition of the present invention, SMD = (1 / STD) 1/2 In the case of, changing the magnification of the three-dimensional polymeric film, such as the longitudinal direction SMD = (1 / STD) in the above formula (1) ^It is estimated that ^1/2 , the width direction becomes STD, and the thickness direction becomes (1 / STD) ^1/2 .

As mentioned above, the extending | stretching process and shrinkage | contraction process performed simultaneously can be performed directly to the said polymer film. In addition, the polymer film may be disposed on a substrate, and the substrate may be subjected to an stretching treatment and a shrinkage treatment at the same time, indirectly to the polymer film, or to the laminate of the substrate and the polymer film.

There is no restriction | limiting in particular as said polymer film, The conventionally well-known polymer film used as a formation material of a birefringent film can be used. As said polymer, For example, Polycarbonate; Polyallylates; Polysulfones; Polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; Polyether sulfone; Polyvinyl alcohol; Polyolefins such as polyethylene and polypropylene; Cellulose polymers; Polystyrene, polymethacrylate; Polyvinyl chloride; Polyvinylidene chloride; Polyamides; Norbornene-based polymers; The mixture containing the alternating copolymer which consists of isobutene and N-methyl maleimide, and an acrylonitrile styrene copolymer, etc. are mentioned.

It is preferable that the said polymer film is light transmissive, for example, It is preferable that the light transmittance is 85% or more, for example, More preferably, it is 90%. Moreover, it is preferable that there is little orientation nonuniformity.

When forming a polymer film directly on a base material, it is also preferable to use the non-liquid crystalline polymer shown below, for example. When the non-liquid crystalline polymer is used, for example, the film shows optically negative uniaxiality (nx> nz) or (ny> nz) by its own properties only by coating regardless of the orientation of the substrate. A birefringent polymer film can be formed, and by extending | stretching, an optical characteristic can be changed to negative biaxiality (nx> ny> nz). For this reason, it is easy to adjust birefringence and phase difference further, and the said base material is not limited to an orientation base material. In addition, nx, ny, and nz represent the refractive index of the X-axis (ground axis), Y-axis, and Z-axis direction of the said polymer film, respectively, and the said X-axis direction is the axial direction which shows the largest refractive index in the surface of the said polymer film. Y axis direction is the axial direction perpendicular to the X axis in the plane, Z axis represents the thickness direction perpendicular to the X axis and Y axis.

Examples of the non-liquid crystalline polymers include polyamide, polyimide, polyester, polyether ketone, polyaryl ether ketone, polyamideimide, and polyamide because they are excellent in heat resistance, chemical resistance and transparency, and are also rich in rigidity. Polymers, such as esterimide, are preferable. These polymers may be used individually by 1 type, and may be used as 2 or more types of mixtures which have a different functional group like the mixture of polyaryl ether ketone and a polyamide, for example. Among these polymers, polyimide and the like are preferred in that high birefringence is obtained.

Although the molecular weight of the said polymer is not specifically limited, For example, it is preferable that weight average molecular weights (Mw) are the range of 1,000-1,000,000, More preferably, it is the range of 2,000-500,000.

As said polyimide, the in-plane orientation is high, for example, and the polyimide soluble in an organic solvent is preferable. Specifically, the condensation polymerization product of 9,9-bis (aminoaryl) fluorene and aromatic tetracarboxylic dianhydride disclosed in, for example, Japanese Patent Publication No. 2000-511296, specifically, the following formula (1) The polymer containing one or more repeating units shown to can be used.

[Formula 1]

The formula (1) of, R ³ is ~R ^6, from hydrogen, halogen, phenyl, the group consisting of a phenyl group, and C ₁ ~C ₁₀ alkyl group substituted by 1 to 4 halogen atoms or C ₁ ~C ₁₀ alkyl group One or more types of substituents selected independently. Preferably, R ³ to R ⁶ are each independently selected from the group consisting of a halogen, a phenyl group, a phenyl group substituted with _{1 to} 4 halogen atoms or a C _{1 to} C ₁₀ alkyl group, and a C _{1 to} C ₁₀ alkyl group. It is a substituent more than a kind.

In the formula (1), Z is, for example, a group of four C ₆ ~C ₂₀ aromatic, preferably, pyromellitic dawn, the polycyclic aromatic group, and derivatives thereof, or the formula of a cyclic aromatic group (2 ).

[Formula 2]

In the formula (2), Z 'is, for example, a covalent bond, C (R ⁷⁾ ₂ group, a CO group, an O atom, S atom, SO ₂ group, a Si (C ₂ H _{5) 2} group, or NR ⁸ groups, and in some cases, it is the same or different. In addition, w represents the integer of 1-10. R ^{7 's} are each independently hydrogen or C (R ⁹ ) ₃ . R ⁸ is hydrogen, an alkyl group having 1 to about 20 carbon atoms, or a C ₆ -C ₂₀ aryl group, and in the case of a plurality, they are the same or different. R ^{9 's} are each independently hydrogen, fluorine, or chlorine.

As said polycyclic aromatic group, the tetravalent group derived from naphthalene, fluorene, benzofluorene, or anthracene is mentioned, for example. Further, it is a derivative of the polycyclic aromatic group, such as C ₁ ~C ₁₀ alkyl group, and fluorinated derivatives thereof, and F and Cl as halogen, such as the above substituted with one or more groups selected from the group consisting of polycyclic aromatic group of the Can be mentioned.

In addition, the homopolymer in which the repeating unit described in Unexamined-Japanese-Patent No. 8-511812 is represented by following General formula (3) or (4), for example, and the polyimide in which a repeating unit is represented by the following General formula (5) Etc. can be mentioned. In addition, the polyimide of following formula (5) is a preferable form of the homopolymer of following formula (3).

[Formula 3]

[Formula 4]

[Formula 5]

In the above general formula (3) ~ (5), G and G 'is, for example, a covalent bond, CH ₂ group, C (CH _{3) 2} group, C (CF _{3) 2} group, C (CX _{3) 2} Group (where X is halogen), CO group, O atom, S atom, SO ₂ group, Si (CH ₂ CH ₃ ) ₂ group and N (CH ₃ ) group , May be the same or different, respectively.

In said Formula (3) and Formula (5), L is a substituent and d and e represent the number of substitutions. L is, for example, halogen, C ₁ ~C ₃ alkyl group, C ₁ ~C ₃ halogenated alkyl group, a phenyl group, or a substituted phenyl group, in the case of a plurality, are each the same or different. In the tooth ring a phenyl group is, for example, there may be mentioned a phenyl group substituted with a halogen, C ₁ ~C ₃ alkyl group, and C ₁ ~C ₃ halogenated alkyl group one or more kinds of substituents selected from the group consisting of. Moreover, as said halogen, fluorine, chlorine, bromine, or iodine is mentioned, for example. d is an integer of 0-2 and e is an integer of 0-3.

In said formula (3)-(5), Q is a substituent and f shows the number of substitution. Q is, for example, an atom selected from the group consisting of hydrogen, a halogen, an alkyl group, a substituted alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, an aryl group, a substituted aryl group, an alkylester group, and a substituted alkylester group, or Group, and when there are a plurality of Q's, they are the same or different. As said halogen, a fluorine, chlorine, bromine, and iodine are mentioned, for example. As said substituted alkyl group, a halogenated alkyl group is mentioned, for example. Moreover, a halogenated aryl group is mentioned as said substituted aryl group, for example. f is an integer from 0 to 4, and g and h are integers from 0 to 3 and 1 to 3, respectively. In addition, g and h are preferably larger than one.

In said formula (4), R <^10> and R <^11> is group selected independently from the group which consists of hydrogen, a halogen, a phenyl group, a substituted phenyl group, an alkyl group, and a substituted alkyl group, respectively. Especially, it is preferable that R <^10> and R <^11> is a halogenated alkyl group each independently.

The formula (5) of, M ¹ and M ² are the same or different and, for example, halogen, C ₁ ~C ₃ alkyl group, C ₁ ~C ₃ halogenated alkyl group, a phenyl group, or a substituted phenyl group. As said halogen, a fluorine, chlorine, bromine, and iodine are mentioned, for example. Further, in the substituted phenyl group is, for example, there may be mentioned a phenyl group substituted with a halogen, C ₁ ~C ₃ alkyl group, and one or more kinds of substituents selected from the group consisting of a C ₁ ~C ₃ halogenated alkyl group.

As a specific example of the polyimide represented by said Formula (3), what is represented by following formula (6), etc. are mentioned, for example.

[Formula 6]

Moreover, as said polyimide, the copolymer which suitably copolymerized acid dianhydride and diamine other than frame | skeleton (repeating unit) as mentioned above is mentioned, for example.

As said acid dianhydride, aromatic tetracarboxylic dianhydride is mentioned, for example. As said aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride, a benzophenone tetracarboxylic dianhydride, a naphthalene tetracarboxylic dianhydride, a heterocyclic aromatic tetracarboxylic dianhydride, 2,2'-substituted biphenyl tetracarboxylic acid 2, for example Anhydrides etc. are mentioned.

As said pyromellitic dianhydride, a pyromellitic dianhydride, 3, 6- diphenyl pyromellitic dianhydride, 3, 6-bis (trifluoromethyl) pyromellitic dianhydride, 3, 6, for example -Dibromo pyromellitic dianhydride, 3, 6- dichloro pyromellitic dianhydride, etc. are mentioned. As said benzophenone tetracarboxylic acid dianhydride, For example, 3,3 ', 4,4'- benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'- benzophenone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic acid dianhydride and the like. As said naphthalene tetracarboxylic acid dianhydride, it is 2,3,6,7-naphthalene- tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene- tetracarboxylic acid dianhydride, 2,6- dichloronaphthalene-1, for example. And 4,5,8-tetracarboxylic dianhydride. Examples of the heterocyclic aromatic tetracarboxylic dianhydride include thiophene-2,3,4,5-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride and pyridine-2,3 And 5, 6-tetracarboxylic dianhydride. As said 2,2'-substituted biphenyl tetracarboxylic acid dianhydride, it is 2,2'- dibromo-4,4 ', 5,5'-biphenyl tetracarboxylic acid dianhydride, 2,2'-, for example. Dichloro-4,4 ', 5,5'-biphenyltetracarboxylic acid dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetracarboxylic acid dianhydride, and the like. Can be mentioned.

Other examples of the aromatic tetracarboxylic dianhydride include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (2,5 , 6-trifluoro-3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane 2 anhydride, 4,4'-bis (3,4-dicarboxyphenyl) -2,2-diphenylpropane 2 anhydride, bis (3,4-dicarboxyphenyl) ether 2 anhydride, 4,4'-oxydi Phthalic anhydride, bis (3,4-dicarboxyphenyl) sulfonic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 4,4'-[4,4'-isopropylidene -Di (p-phenyleneoxy)] bis (phthalic anhydride), N, N- (3,4-dicarboxyphenyl) -N-methylamine dianhydride, bis (3,4-dicarboxyphenyl) diethylsilane 2 anhydride etc. are mentioned.

Among these, as said aromatic tetracarboxylic dianhydride, 2,2'-substituted biphenyltetracarboxylic dianhydride is preferable, More preferably, 2,2'-bis (trihalomethyl) -4,4 ' And 5,5'-biphenyltetracarboxylic acid dianhydride, more preferably 2,2'-bis (trifluoromethyl) -4,4 ', 5,5'-biphenyltetracarboxylic acid dianhydride.

As said diamine, aromatic diamine is mentioned, for example, A benzenediamine, a diamino benzophenone, naphthalenediamine, a heterocyclic aromatic diamine, and other aromatic diamine are mentioned as a specific example.

Examples of the benzenediamine include o-, m- and p-phenylenediamine, 2,4-diaminotoluene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2 And diamines selected from the group consisting of benzenediamines such as -phenylbenzene and 1,3-diamino-4-chlorobenzene. 2,2'- diamino benzophenone, 3,3'- diamino benzophenone, etc. are mentioned as an example of the said diamino benzophenone. As said naphthalenediamine, 1, 8- diamino naphthalene, 1, 5- diamino naphthalene, etc. are mentioned, for example. Examples of the heterocyclic aromatic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-S-triazine and the like.

Moreover, as said aromatic diamine, besides these, 4,4'- diamino biphenyl, 4,4'- diamino diphenylmethane, 4,4'- (9-fluorenylidene)-dianiline, 2 , 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2'-dichloro-4,4 '-Diaminobiphenyl, 2,2', 5,5'-tetrachlorobenzidine, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2 , 2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4 -Aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4 -(4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4'-diaminodiphenylthioether, 4,4'- And the like amino-diphenyl sulfone.

As said polyether ketone which is a formation material of the said birefringent film, the polyaryl ether ketone represented by following General formula (7) described, for example in Unexamined-Japanese-Patent No. 2001-49110 is mentioned.

[Formula 7]

In said formula (7), X represents a substituent and q represents the number of substitution. X is a halogen atom, a lower alkyl group, a halogenated alkyl group, a lower alkoxy group, or a halogenated alkoxy group, for example, and when X is multiple, each is the same or different.

As said halogen atom, a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom are mentioned, for example, A fluorine atom is preferable among these. As the lower alkyl group is, for example, it is a lower alkyl group having a straight-chain or branched-chain C ₁ ~C _6, more preferably an alkyl group of a straight-chain or branched-chain C ₁ ~C _4. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group are preferable, and methyl and ethyl group are particularly preferable. As said halogenated alkyl group, the halide of the said lower alkyl group, such as a trifluoromethyl group, is mentioned, for example. The lower alkoxy group includes, for example, it is a linear or branched-chain C ₁ ~C ₆ alkoxy group, more preferably an alkoxy group of a straight-chain or branched-chain C ₁ ~C _4. Specifically, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group are more preferable, and particularly preferably methoxy group and ethoxy group to be. As said halogenated alkoxy group, the halide of the said lower alkoxy group, such as a trifluoro methoxy group, is mentioned, for example.

In said formula (7), q is an integer of 0-4. In Formula (7), it is preferable that q = 0 and the carbonyl group couple | bonded at the both ends of a benzene ring, and the oxygen atom of an ether exist in para position mutually.

In addition, in said Formula (7), R <^1> is group represented by following formula (8), m is an integer of 0 or 1.

[Formula 8]

In said formula (8), X 'represents a substituent and is the same as X in the said Formula (7), for example. In said Formula (8), when there are multiple X ', they are the same or different, respectively. q 'represents the number of substitution of said X', is an integer of 0-4, and q '= 0 is preferable. In addition, p is an integer of 0 or 1.

In said formula (8), R <^2> represents a bivalent aromatic group. As this bivalent aromatic group, it is o-, m- or p-phenylene group, or naphthalene, biphenyl, anthracene, o-, m- or p-terphenyl, phenanthrene, dibenzofuran, biphenyl ether, for example. Or a divalent group derived from biphenyl sulfone. In these bivalent aromatic groups, hydrogen directly bonded to the aromatic group may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group. Among these, as said R <^2> , the aromatic group chosen from the group which consists of following formula (9)-(15) is preferable.

[Formula 9]

In said formula (7), as said R <^1> , group represented by following formula (16) is preferable, and in following formula (16), R <^2> and p are synonymous with said formula (8).

[Formula 10]

In addition, in said formula (7), n represents a polymerization degree, For example, it is the range of 2-5000, Preferably it is the range of 5-500. In addition, the superposition | polymerization may consist of repeating units of the same structure, and may consist of repeating units of a different structure. In the latter case, block polymerization may be sufficient as the superposition | polymerization form of a repeating unit, and random polymerization may be sufficient as it.

Moreover, it is preferable that the terminal of the polyaryl ether ketone represented by said Formula (7) is a fluorine on the p- tetrafluoro benzoylene group side, and a hydrogen atom on the oxyalkylene group side, and such polyaryl ether ketone is the following general It can be represented by Formula (17). In addition, in following formula, n shows the polymerization degree similar to said Formula (7).

[Formula 11]

As a specific example of the polyaryl ether ketone represented by said Formula (7), what is represented by following formula (18)-(21), etc. are mentioned, In each following formula, n is the same as said Formula (7) The degree of polymerization is shown.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

Moreover, besides these, as said polyamide or polyester which is a formation material of the said birefringent film, the polyamide and polyester of Unexamined-Japanese-Patent No. 10-508048 are mentioned, for example, These repeating units Can be represented by following General formula (22), for example.

[Formula 16]

In said formula (22), Y is O or NH. In addition, E is, for example, a covalent bond, a C ₂ alkylene group, a halogenated C ₂ alkylene group, a CH ₂ group, a C (CX ₃ ) ₂ group (where X is a halogen or hydrogen), a CO group, an O atom, S atom, SO ₂ group, and also Si (R) ₂ group, and N (R) the same group is a group the one or more kind selected from the group consisting, respectively, or be different. In the E, R is in the meta position or para position with respect to groups is at least one kind of C ₁ ~C ₃ alkyl group and a C ₁ ~C ₃ halogenated alkyl group, a carbonyl functional group or a Y.

In addition, in said (22), A and A 'are substituents, t and z represent each substitution number. In addition, p is an integer of 0-3, q is an integer of 1-3, and r is an integer of 0-3.

A is substituted aryl by an alkoxy group, an aryl group, halogenation or the like represented by, for example, hydrogen, a halogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ halogenated alkyl group or OR (where R is defined above). group, C ₁ ~C ₉ alkoxycarbonyl group, C ₁ ~C ₉ alkylcarbonyloxy group, C ₁ ~C ₁₂ aryloxycarbonyl group, C ₁ ~C ₁₂ aryl carbonyloxy group and a substituted derivative thereof, C ₁ ~C ₁₂ aryl-carbamoyl group, and a C ₁ ~C ₁₂ aryl selected from the group consisting of carboxylic carbonyl group and its substituted derivatives, in the case of a plurality, are each the same or different. Wherein A 'is, for example, halogen, C ₁ ~C ₃ alkyl group, is selected from the group consisting of a C ₁ ~C ₃ halogenated alkyl group, a phenyl group and a substituted phenyl group, in the case of a plurality, they are each the same or different. As the substituent on the phenyl ring of the substituted phenyl group may be, for example, a halogen, C ₁ ~C ₃ alkyl group, C ₁ ~C ₃ halogenated alkyl group, and combinations thereof. T is an integer from 0 to 4, and z is an integer from 0 to 3.

It is preferable to represent with the following general formula (23) also in the repeating unit of the polyamide or polyester represented by said Formula (22).

[Formula 17]

In said Formula (23), A, A ', and Y are what was defined by the said Formula (22), v is an integer of 0-3, Preferably it is an integer of 0-2. x and y are each 0 or 1, but are not 0 together.

On the other hand, as said base material, the translucent polymer film which can be extended | stretched and shrunk is preferable, and it is preferable that phase difference does not generate | occur | produce also by extending | stretching especially in practical use. Especially if it is a polymer film excellent in transparency, since the base material and the birefringent film formed on the said base material can also be used as an optical film as a laminated body, it is preferable. Moreover, in order to perform the contraction of the longitudinal direction mentioned above smoothly, the base material is preferably previously stretched, a heat shrinkable film, or the like. As the material for forming the base material, for example, a thermoplastic resin is preferable.

Specifically as a forming material of the said base material, For example, polyolefin, polyimide, polyamideimide, polyamide, polyetherimide, polyether ether, such as polyethylene, a polypropylene, poly (4-methylpentine-1), etc. Ketone, polyketone sulfide, polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyallylate, acrylic resin , Polyvinyl alcohol, polypropylene, cellulose-based plastics, epoxy resins, phenol resins, and the like, acetate resins such as triacetyl cellulose (TAC), polyester resins, acrylic resins, polynorbornene resins, cellulose resins, polystyrene resins, Polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic resin And these mixtures, and the like and liquid crystal polymers can also be used. Among these, polypropylene, polyethylene terephthalate, polyethylene naphthalate, etc. are preferable at the point of solvent resistance and heat resistance, for example. Moreover, the thermoplastic resin which has a substituted imide group or an unsubstituted imide group in a side chain, as described in Unexamined-Japanese-Patent No. 2001-343529 (WO 01/37007), and a substituted phenyl group or unsubstituted in a side chain, for example. The mixture etc. of the thermoplastic resin which has a phenyl group and a nitrile group can also be used. Specifically, it is a resin composition etc. which have the alternating copolymer which consists of isobutene and N-methyl maleimide, and an acrylonitrile styrene copolymer, for example. Among these forming materials, for example, a mixture of a thermoplastic resin having a substituted imide group or an unsubstituted imide group in the side chain and a thermoplastic resin having a substituted phenyl group or an unsubstituted phenyl group and a nitrile group in the side chain are preferable.

Next, an example of the manufacturing method of the birefringent film of this invention is demonstrated.

First, a polymer film to be stretched and contracted is prepared. The thickness of the polymer film is not particularly limited and can be appropriately determined according to the desired phase difference of the birefringent film to be produced, the material of the polymer film, and the like. Generally, it is the range of 5-500 micrometers, for example, Preferably it is the range of 10-350 micrometers, More preferably, it is the range of 20-200 micrometers. If it is the said range, in an extending | stretching / shrinkage process, sufficient strength will be shown, for example, without being cut | disconnected. In addition, the length of the longitudinal direction and the width direction is not specifically limited, For example, it can determine suitably according to the magnitude | size of the stretching machine etc. to be used.

Stretching treatment in the width direction and shrinkage treatment in the longitudinal direction are simultaneously performed on the polymer film so as to satisfy the condition of the above formula (1). In this manner, the stretching in the width direction and the contraction in the longitudinal direction can be performed using, for example, a biaxial stretching machine, and specifically, a high-performance thin film device manufactured by Ichinkin Industries Co., Ltd., which can automatically perform the stretching and contraction ( Trade name FITZ) and the like. This apparatus can arbitrarily set the draw ratio in the longitudinal direction (length direction of the film = the advancing direction of the film) and the draw ratio in the transverse direction (width direction = the advancing direction of the film and the vertical direction). Since the shrinkage magnification can be arbitrarily set, stretching and shrinkage can be simultaneously performed under predetermined conditions. For example, by appropriately combining a generally known rail width control method, a panda graph method, a method of controlling the traveling speed by a linear motor, and the like, the draw ratio in the width direction is controlled and the film end is sandwiched. It is also possible to use a biaxial stretching machine for controlling the length in the longitudinal direction by changing the distance between the clips.

The temperature in the stretching and shrinkage treatment is not particularly limited and can be appropriately determined according to the type of the polymer film. However, the temperature is preferably set in accordance with the glass transition temperature of the polymer film. For example, it is preferable that it is the range of glass transition temperature +/- 30 degreeC, More preferably, it is the range of glass transition temperature +/- 20 degreeC, Especially preferably, it is the range of the said glass transition temperature +/- 10 degreeC.

By such a production method, the birefringent film of the present invention can be obtained from the polymer film, and the birefringent film becomes a film excellent in the properties such as birefringence, retardation, orientation axis, in particular, uniformity of these properties in the width direction. . In addition, although the value of birefringence and retardation of a birefringent film changes with the material, the draw ratio, etc. of the polymer film to be used, for example, if it manufactures according to the conditions shown by said Formula (1), regardless of the magnitude | size of a birefringence and a phase difference, The uniformity becomes excellent.

As for the said birefringent film, the precision of in-plane phase difference value "(nx-ny) * d", ie, the deviation of a phase difference, for example, -9 to + 9% of the range is preferable, More preferably, -8 to + 8% More preferably -7 to + 7%. In addition, the accuracy of the phase difference value "(nx-nz) .d" in the thickness direction is preferably in the range of -7 to + 7%, more preferably -6 to + 6%, and more preferably- 5 to + 5%. In addition, the precision of each phase difference can be measured as follows. First, when it is the intermediate point of the longitudinal direction of a birefringent film, and divided into 8 equally at equal intervals in the width direction, the in-plane phase difference and the phase difference of thickness direction are measured at seven points except a terminal. And when these average values are made into 100%, the difference of each measured value and an average value is computed as the precision (%) of in-plane phase difference and thickness direction phase difference.

In the birefringent film of the present invention, the deviation of the orientation axis angle in the X axis direction (ground axis direction) is preferably 5 ° or less, and more preferably 4 ° or less. According to the above-described method, since the deviation of the axial angle can be controlled in such a range, the uniformity of the refractive index can be improved. The angle of the orientation axis means the deviation of the slow axis, and can be automatically calculated using, for example, an automatic birefringence meter (trade name KOBRA-21ADH; manufactured by Oji Instrument Co., Ltd.), and is equal to the deviation, for example, the above-described phase difference. When the orientation axis angle is measured at multiple points (seven points), it can be represented by the difference between the maximum value and the minimum value. Moreover, in this invention, the width direction with a large change ratio becomes a slow axis direction.

Although the thickness of the birefringent film obtained differs according to the thickness, the draw ratio, etc. of the polymer film to be used, it is generally the range of 5-500 micrometers, Preferably it is the range of 10-350 micrometers, More preferably, it is 20-200 micrometers Range.

Moreover, it is not limited to such a manufacturing method, For example, you may form the polymer film which consists of the above-mentioned non-liquid crystalline polymer on a base material, and may perform extending | stretching / shrink-processing to this laminated body simultaneously. In this case, as described later, the substrate and the polymer film may be stretched and shrunk together, or the polymer film may be indirectly processed by stretching and shrinking only the substrate in the laminate. Moreover, after peeling a polymer film from a base material, you may process only to the said polymer film.

Thus, an example in the case of directly forming a polymer film on a base material is shown below. First, the forming material of a polymer film is disperse | distributed or melt | dissolved in a solvent, and a coating liquid is prepared. Although the density | concentration of the formation material in the said coating liquid is not specifically limited, For example, since it becomes the viscosity which is easy to apply | coat, it is preferable that it is 0.5-50 weight% of said formation materials, More preferably, it is 1-40 Wt%, particularly preferably 2-30 wt%. Specifically, in the case where the forming material is a non-liquid crystalline polymer, the amount of the polymer added is preferably 5 to 50 parts by weight of the forming material, more preferably 10 to 40 parts by weight based on 100 parts by weight of the solvent. It is wealth.

Although the said solvent is not specifically limited, Although it can select suitably according to a formation material, For example, it is preferable that the formation material can be melt | dissolved and a base material does not erode well. Specifically, for example, halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene and orthodichlorobenzene, phenol, parachlorophenol and the like Aromatic hydrocarbons such as phenols, benzene, toluene, xylene, methoxybenzene, 1,2-dimethoxybenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrroli Don, ketone solvents such as N-methyl-2-pyrrolidone, ester solvents such as ethyl acetate and butyl acetate, t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene Alcohol solvents such as glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, and amide solvents such as dimethylformamide and dimethylacetamide Nitrile solvents such as acetonitrile, butyronitrile, diethyl ether, dibutyl ether, ether solvents such as tetrahydrofuran, carbon disulfide, ethyl cellosolve, butyl cellosolve, sulfuric acid and the like can be used. . In addition, these solvents may be used independently and may be used in mixture of 2 or more types.

You may mix | blend various additives, such as surfactant, a stabilizer, a plasticizer, metals, with the said coating liquid as needed, for example.

In addition, the said coating liquid may contain other different resin, for example in the range which the orientation or the like of the said forming material does not fall remarkably. As said other resin, various general purpose resins, engineering plastics, a thermoplastic resin, a thermosetting resin, etc. are mentioned, for example.

As said general-purpose resin, polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMMA), ABS resin, AS resin, etc. are mentioned, for example. Examples of the engineering plastics include polyacetate (POM), polycarbonate (PC), polyamide (PA: nylon), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like. . As said thermoplastic resin, for example, polyphenylene sulfide (PPS), polyether sulfone (PES), polyketone (PK), polyimide (PI), polycyclohexanedimethanol terephthalate (PCT), polyallylate (PAR), a liquid crystal polymer (LCP), etc. are mentioned. As said thermosetting resin, an epoxy resin, a phenol novolak resin, etc. are mentioned, for example. Thus, when mix | blending said other resin etc. with the said coating liquid, the compounding quantity is 0-50 weight% with respect to the said forming material, for example, Preferably it is 0-30 weight%.

Then, the prepared said coating liquid is apply | coated to the base material surface, and the coating film of the said forming material is formed. As a coating method of the said application | coating, a spin coating method, the roll coating method, the printing method, the dipping impression method, the curtain coating method, the wire bar coating method, the doctor blade method, the knife coating method, the die coating method, for example , Gravure coating method, microgravure coating method, offset gravure coating method, lip coating method, spray coating method and the like. Moreover, in application | coating, the superimposition method of a polymer layer can also be employ | adopted as needed.

Although the thickness in particular of the said base material is not restrict | limited, Usually, it is 10 micrometers or more, The range of 10-200 micrometers is preferable, More preferably, it is the range of 20-150 micrometers, Especially preferably, it is the range of 30-100 micrometers. When it is 10 micrometers or more, since sufficient intensity | strength is shown in the extending | stretching / shrinkage process mentioned later, generation | occurrence | production of the nonuniformity in an extending | stretching / shrinkage process, etc. can be fully suppressed. Moreover, if it is 200 micrometers or less, since an extending | stretching process is possible at an appropriate tension, it is preferable.

And the coating film formed on the said base material is dried. By this drying, the forming material can be fixed on the substrate to form a polymer film directly on the substrate.

There is no restriction | limiting in particular as said drying method, For example, natural drying and heat drying are mentioned. Although the conditions can also be suitably determined according to the kind of the said formation material, the kind of the said solvent, etc., for example, temperature is 40 degreeC-250 degreeC, Preferably it is 50 degreeC-200 degreeC. In addition, drying of a coating film may be performed, for example at constant temperature, and you may carry out, raising or decreasing temperature in steps. The drying time is not particularly limited, for example, 10 seconds to 60 minutes, preferably 30 seconds to 30 minutes.

After the drying treatment, the solvent of the polymer liquid remaining in the polymer film may change the optical properties over time in proportion to the amount thereof, so that the remaining amount is, for example, 5% or less. It is preferable, More preferably, it is 2% or less, More preferably, it is 0.2% or less.

Although the thickness in particular of the polymer film formed on the said base material is not restrict | limited, For example, it is preferable to set normally to 0.5-10 micrometers, More preferably, it is 1-8 micrometers, Especially preferably, it is 1-7 micrometers.

Subsequently, the polymer film formed on the substrate is subjected to stretching and shrinkage treatment simultaneously under the conditions described above. In this case, for example, only the polymer film may be directly stretched and shrunk, or the laminate of the base material and the polymer film may be stretched and shrunk together. In particular, it is preferable to treat only the substrate for the following reasons. That is, when only the said base material is extended | stretched and contracted, the polymer film on the said base material is extended | stretched and contracted indirectly with extending | stretching and shrinkage | contraction of the said base material. Usually, it is easier to process a monolayer more uniformly than to process a laminated body. Therefore, when only a base material is processed as mentioned above, the said base material can be extended | stretched and contracted uniformly, and accordingly, the said polymer film on the said base material can also be extended | stretched and contracted uniformly. In addition, after peeling a polymer film from the said base material, only the said polymer film may be processed as mentioned above.

When formed on a base material as mentioned above, the birefringent film of this invention may be used, for example as a laminated body with the said base material, and can also be used as a monolayer peeled from the said base material. In addition, after peeling from the said base material (henceforth "the 1st base material"), for example, the base material which does not disturb the optical characteristic (henceforth "the 2nd base material") is interposed between the adhesive layers. It can also be laminated | stacked (transferred) and used.

As said 2nd base material, if it has a suitable planarity, it will not specifically limit, For example, glass, a polymer film which has transparent and optical isotropy, etc. are preferable. As said polymer film, for example, polymethacrylate, polyallylate, polycarbonate, polyether sulfone, polyphenylene sulfide, polyallylate, amorphous polyolefin, TAC, epoxy resin, isobutene / N as described above The film formed from the resin composition of -methyl maleimide copolymer and an acrylonitrile / styrene copolymer, etc. are mentioned. Among these, polymethyl methacrylate, polycarbonate, polyallylate, TAC, polyether sulfone, isobutene / N-methylmaleimide copolymer and a resin composition of acrylonitrile / styrene copolymer are preferable. Moreover, even the base material which shows optically anisotropy can be used according to the objective. As such an optically anisotropic base material, the retardation film, polarizing film, etc. which extended | stretched polymer films, such as polycarbonate polystyrene and norbornene-type resin, are mentioned, for example.

As an adhesive layer in the transfer as mentioned above, what is necessary is just to be usable for optical uses, For example, adhesives and adhesives, such as an acryl type, an epoxy type, and a urethane type, can be used.

Next, the optical film of this invention should just contain the birefringent film of this invention as mentioned above, For example, the structure is not restrict | limited, such as having a base material as mentioned above.

It is preferable that the optical film of this invention has an adhesive layer further to an outermost layer. This is because, for example, the optical film of the present invention can be easily bonded to other optical layers, other members such as a liquid crystal cell, and the peeling of the optical film of the present invention can be prevented. In addition, the said adhesive layer may be arrange | positioned only to one surface of the optical film of this invention, and may be arrange | positioned to both surfaces.

Although it does not restrict | limit especially as a material of the said adhesion layer, For example, adhesives, such as an acryl type, silicone type, polyester type, a rubber type, can be used. Moreover, it is good also as a layer which shows light-diffusion property by containing microparticles | fine-particles in these materials. Among these, the material excellent in hygroscopicity and heat resistance, for example is preferable. With such a property, for example, when used in a liquid crystal display device, it is possible to prevent a decrease in optical characteristics due to foaming, peeling due to moisture absorption, a difference in thermal expansion, warping of a liquid crystal cell, etc., and a display device having excellent durability and high quality. Becomes

As above-mentioned, the birefringent film of this invention may be sufficient as the optical film of this invention, or the laminated body combined with another optical member as needed may be sufficient. There is no restriction | limiting in particular as said other optical member, For example, another birefringent film, another retardation film, a liquid crystal film, a light scattering film, a lens sheet, a diffraction film, a polarizing plate, etc. are mentioned.

When the optical film of this invention contains the said polarizing plate, the polarizing plate may be only a polarizer, and a transparent protective layer may be laminated | stacked on one side or both surfaces of the said polarizer.

It is preferable to use the optical film of this invention for formation of various apparatuses, such as a liquid crystal display device, for example, it can arrange | position to one side or both sides of a liquid crystal cell, and can use it for a liquid crystal display device as a liquid crystal panel. In addition, the arrangement | positioning method of an optical film is not specifically limited, It is the same as that of the optical film containing a conventional birefringent film.

The type of liquid crystal cell forming the liquid crystal display device can be arbitrarily selected, for example, active matrix drive type, IPS drive type, plasma addressing drive type, twist nematic type or super twisted type type such as thin film transistor or MIM. Various types of liquid crystal cells, such as the typical simple matrix drive type, can be used. Specifically, for example, Super Twisted Nematic (STN) cells, Twisted Nematic (TN) cells, In-Plane Switching (IPS) cells, Vertical Nematic (VA) cells, Optimal Controlled Birefringence (OCB) cells, Hybrid Aligned (HAN) Nematic cells, ASM (Axially Symmetric Aligned Microcell) cells, ferroelectric and antiferroelectric cells, and regular orientation division to these, random orientation division, and the like.

As a liquid crystal display device provided with such an optical film of this invention, the form of a transmissive type with a backlight system, the reflective type with a reflecting plate, a projection type, etc. may be sufficient, for example.

In addition, the optical film of this invention is not limited to the liquid crystal display device mentioned above, For example, it can be used also for self-luminous display devices, such as organic electroluminescent (EL) display, PDP, FED. In this case, the structure is not limited except using the optical film of the present invention instead of the conventional optical film.

Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example. In addition, about the various characteristics, it measured by the following method.

(Measurement of birefringence, phase difference, and axial angle distribution)

The value at the wavelength of 590 nm was measured using the automatic birefringence meter (brand name KOBRA-21ADH; the product made by Oji Instrument Co., Ltd.).

(Measurement of film thickness)

The film thickness of the birefringence layer was measured using an instantaneous multi-photometric system (trade name MCPD-2000; manufactured by Otsuka Electronics Co., Ltd.).

Example 1

Using a high-performance thin film device (trade name FITZ: manufactured by Ichikin Industries Co., Ltd.), an unstretched polycarbonate film (manufactured by Kaneka Fuchi Chemical Co., Ltd.) having a thickness of 68 µm and a width of 330 mm was continuously stretched in the width direction and simultaneously in the longitudinal direction. Shrinkage formed a birefringent film. In addition, the process temperature made the STD of the width direction 1.2 times 160 degreeC, and the SMD of the said longitudinal direction 0.93 times. Since (1 / STD) ^1/2 is 0.913, the condition of the above formula (1) is satisfied. Regarding this birefringent film, the deviation of the orientation axis angle in the width direction, the in-plane retardation (Δnd = (nx-ny) · d) and its deviation, the thickness direction retardation (Rth = (nx−nz) · d) and the deviation thereof Measurement was made by the above-described method, and the occurrence of wrinkles and cracks was visually observed. These results are shown in Table 2 below. The deviation of the orientation axis angle in Table 2 represents the difference between the maximum measured value and the minimum measured value during the seven-point measurement. In addition, nx, ny, and nz represent the refractive index of the X-axis (ground axis), Y-axis, and Z-axis direction of the said birefringent film, respectively, and the said X-axis direction is the axial direction which shows the largest refractive index in the plane of the said birefringent film. And Y axis direction is the axial direction perpendicular to the X axis in the plane, Z axis represents the thickness direction perpendicular to the X axis and Y axis, and d represents the thickness of the birefringent film.

(Comparative Example 1)

A birefringent film was produced in the same manner as in Example 1 except that the STD in the width direction was uniaxially stretched to 1.2 times and the longitudinal direction was not shrunk, and the characteristics thereof were examined. These results are shown in Table 2 below. Moreover, SMD = 1.

(Comparative Example 2)

1.2 times the STD in the width direction, except that for the SMD in the longitudinal direction of 0.9 times ^{and, (1 / STD) 1/} 2 to 0.913, by preparing a birefringent film in the same manner as in Example 1, the same and the characteristics It was investigated. These results are shown in Table 2 below. Moreover, it was (1 / STD) ^1/2 > SMD.

Example 2

As a material for forming the polymer film, 2,2'-bis (3,4-dicarboxyphenyl) hexafluoro propanoic anhydride (6 FDA) and 2,2'-bis (trifluoromethyl) -4,4 The polyimide (Mw = 120000) comprised from the repeating unit represented by following General formula (6) was synthesize | combined using '-diaminobiphenyl (PFMB). This polyimide was dissolved in MIBK so as to be 20% by weight, to prepare a polyimide solution, and was continuously applied to a TAC film (trade name TF80UL; manufactured by Fuji Photo Film Co., Ltd.) (width 400 mm, thickness 40 μm) by a blade coat method. It was. By drying this coating film at 120 degreeC for 2 minutes, the polyimide film of 6.0 micrometers in thickness was formed. This polyimide film showed optical uniaxial birefringence (nx = ny> nz), and was in-plane retardation of 0.4 nm and thickness direction retardation of 248 nm. And the laminated body of a base material and a polyimide film was continuously extended in the width direction, and simultaneously contracted in the longitudinal direction, and the birefringent film was formed. The treatment temperature was set at 160 ° C., 1.1 times the STD in the width direction, and 0.97 times the SMD in the longitudinal direction. Since (1 / STD) ^1/2 is 0.953, the condition of the above formula (1) is satisfied. In addition, the said base material did not generate substantial phase difference by extending | stretching of the width direction, and shrinkage | contraction of the longitudinal direction. About this birefringence film, each characteristic was investigated similarly to the said Example 1. These results are shown together in Table 2 below.

[Formula 18]

(Comparative Example 3)

A birefringent film was produced in the same manner as in Example 2 except that the STD in the width direction was uniaxially stretched to 1.1 times, and the longitudinal direction was not shrunk, and the characteristics thereof were examined in the same manner. These results are shown in Table 2 below. Moreover, SMD = 1.

(Comparative Example 4)

STD 1.1 times in the transverse direction, except that for the SMD in the longitudinal direction of 0.9 times ^{and, (1 / STD) 1/} 2 to 0.913 in the same manner as Example 2 to prepare a birefringent film, the same and the characteristics It was investigated. These results are shown in Table 2 below. Moreover, it was (1 / STD) ^1/2 > SMD.

Orientation axis angle deviation (°) Δnd (nm) Δnd deviation (%) Rth (nm) Rth deviation (%) Exterior Example 1 3.6 218.6 ± 10.5 284.8 ± 12.1 clear Comparative Example 1 20.6 173.7 ± 18.2 394.1 ± 22.5 clear Comparative Example 2 8.1 235.1 ± 15.3 301.4 ± 17.2 Wrinkles Example 2 2.3 49.7 ± 3.2 250.7 ± 3.0 clear Comparative Example 3 11.3 50.9 ± 10.4 309.2 ± 25.5 clear Comparative Example 4 4.3 63.0 ± 10.1 261.4 ± 8.5 Wrinkles

As shown in Table 2 above, Example 1 performed stretching and contraction satisfying the condition of the above formula (1), so that each of the orientation axis angles, Δnd, and Rth was lower than that of Comparative Example 1, which was drawn only in the width direction. The deviation of was extremely suppressed. In addition, in the comparative example 2 in which extending | stretching and shrinkage | contraction are performed simultaneously, but the conditions do not satisfy | fill the said Formula (1), while wrinkles generate | occur | produced in the width direction, Example 1 is each of orientation axis angle, (DELTA) nd, and Rth, respectively. Was not only able to suppress the variation of but also excellent in appearance. In addition, also in Example 2 using the laminated body of a base material and a polyimide film, since extending | stretching and shrinkage which satisfy | filled the conditions of said Formula (1) were performed, compared with the comparative example 3 which extended | stretched only the width direction, The variation of each of the orientation axes, Δnd, and Rth was extremely suppressed. In Comparative Example 4 in which stretching and shrinkage were performed at the same time, but the condition did not satisfy the above formula (1), whereas wrinkles occurred in the width direction, Example 2 was each of the orientation axis angles Δnd and Rth. Was not only able to suppress the variation of but also excellent in appearance. From these results, if the birefringent film produced by the manufacturing method of the present invention is not only excellent in appearance but also excellent in uniformity of optical properties in which variations in orientation axes, in-plane retardation, thickness direction retardation, etc. are suppressed, the liquid crystal display device is excellent. It can be said that it can contribute to the improvement of the display characteristic of various image display apparatuses including these. Moreover, even if it extends in the width direction in this way, since it is excellent in an external appearance and an optical characteristic, it is especially useful when the slow axis of a birefringent film and the transmission axis of a polarizing film are attached continuously in parallel, for example as mentioned above.

Industrial availability

As described above, by performing the stretching in the width direction and the contraction in the longitudinal direction under the conditions of the above formula (1), the appearance is excellent, the birefringence, the phase difference in the in-plane direction and the thickness direction is uniform, and the birefringence is excellent in the optical characteristics. A film can be obtained. Thus, the birefringent film which is excellent in an optical characteristic is useful for various optical films, for example, and when it applies to various image display apparatuses, such as a liquid crystal display device, excellent display characteristics can be implement | achieved.

As described above, the polymer film is stretched in the width direction and simultaneously contracted in the longitudinal direction, and the stretching degree in the width direction and the shrinkage degree in the longitudinal direction are set under the conditions of the above formula (1), so that the appearance is excellent and in-plane. And a refractive index in the thickness direction can be highly controlled, and a birefringent film having excellent optical characteristics with uniform birefringence, retardation, and orientation axes, particularly in the width direction, can be efficiently obtained. The birefringent film obtained by such a manufacturing method can realize the improvement of the display characteristic of various image display apparatuses, such as a liquid crystal display device, etc. from the characteristic, and also the continuous adhesion with the polarizing film as mentioned above is It is very useful industrially in that it is possible.

As mentioned above, extending | stretching of the width direction and contraction of a longitudinal direction simultaneously and setting the conditions to said Formula (1) is the first thing that the present inventors discovered after earnestly researching. That is, the present inventors compared the deformation | transformation of the polymer film by the conventional longitudinal direction with the deformation | transformation of the polymer film by the conventional longitudinal direction, and noticed that these deformation | transformation showed the behavior as shown in following Table 1. In addition, following Table 1 is a table | surface which shows the change magnification in the three-dimensional (length direction, width direction, thickness direction) of a polymer film, The said change magnification shows the width, length, and thickness of an unstretched polymer film, respectively. Is a magnification in the case of &quot;, and the magnification in the width direction is STD and the magnification in the longitudinal direction is SMD. That is, as shown in Table 1 below, in the conventional widthwise drawing, since deformation does not occur in the longitudinal direction, this is considered to be one cause and the bowing phenomenon occurs, while in the conventional longitudinal drawing, the width is generally wide. It is noted that it is easy to deform the direction and the thickness direction freely. And as a result of earnest research, the present invention was reached.

Longitudinal deformation Widthwise deformation Thickness deformation Conventional: Width direction drawing One STD 1 / STD Conventional: Longitudinal stretching SMD STD = (1 / SMD) ^1/2 (1 / SMD) ^1/2 The present invention: stretching + shrinkage

SMD(1 / STD) ^1/2

SMD STD (1 / STD) ^1/2

Claims (22)

As a manufacturing method of a birefringent film including the process of extending | stretching a polymer film, In the stretching step, the polymer film is stretched in the width direction and simultaneously shrunk in the longitudinal direction, Based on the length in the width direction and the length in the longitudinal direction of the polymer film before stretching, the relationship between the change ratio (STD) of the length in the width direction by the stretching and the change ratio (SMD) of the length in the longitudinal direction by the shrinkage are , The following formula (1), (1 / STD) ^1/2 ≦ SMD <1... (One) Method for producing a birefringent film, characterized in that to satisfy. The method of claim 1, SMD is less than 0.99, The manufacturing method of a birefringent film. The method of claim 1, (1 / STD) ^1/2 is a method for producing a birefringent film, which is less than 0.99. The method of claim 1, The process for producing a birefringent film, wherein when the STD is 1.2, the SMD is in the range of 0.9 to 0.92. The method of claim 1, The process for producing a birefringent film, wherein when the STD is 1.3, the SMD is in the range of 0.86-0.90. delete delete delete delete delete delete delete delete delete The method of claim 1, And the polymer film is a film containing polycarbonate or polyimide. The birefringent film obtained by the manufacturing method according to any one of claims 1 to 5 or 15. The optical film containing the birefringent film of Claim 16. The method of claim 17, An optical film further comprising a polarizer. The method of claim 18, An optical film, further comprising a transparent protective film, wherein the transparent protective film is disposed on at least one surface of the polarizer. The liquid crystal panel in which the optical film of Claim 17 is arrange | positioned on the at least one surface of a liquid crystal cell. The liquid crystal display device containing the liquid crystal panel of Claim 20. The image display apparatus containing the optical film of Claim 17.