JP2005195984A - Method of manufacturing polarizing plate with optical compensation layer, polarizing plate with optical compensation layer and image displaying device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To adopt a polarizing film protection film with an optical compensation layer without drastically reforming the conventional process of manufacturing a polarizing plate and manufacture the polarizing plate with the optical compensation layer without damaging the optical compensation function of the optical compensation layer. <P>SOLUTION: A polarizing film protection film 5 with an optical compensation layer prepared by sequentially laminating a optical compensation layer 2 and an optical compensation layer protection film 3 on a polarizing film protection film 1 is saponified. The polarizing film protection film 5 with the optical compensation layer is stuck to the polarizing film 4 by using the surface 1a of the saponified polarizing film protection film. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a polarizing plate with an optical compensation layer, a polarizing plate with an optical compensation layer obtained thereby, and an image display device including the polarizing plate with an optical compensation layer.

  Conventionally, a polarizing plate with an optical compensation layer in which an optical compensation layer and a polarizing film are integrated is known. Such a polarizing plate with an optical compensation layer can improve the viewing angle and the visibility of a liquid crystal display device by being stacked on a liquid crystal cell.

And as such a polarizing plate with an optical compensation layer, for example, a thin film of polyvinyl alcohol (PVA) is immersed in an aqueous potassium iodide solution to adsorb iodine, and then 3 in one direction in an aqueous boric acid solution. After creating a polarizing film by stretching in the range of 10 times, creating a polarizing plate by laminating a polarizing film protective film having high optical transparency on both sides of the polarizing film, It is disclosed that it can be obtained by attaching an optical compensation layer separately prepared via an adhesive or the like (Patent Documents 1 and 2).
JP 2000-321992 A JP 2000-32426 A

  However, since such a conventional manufacturing method requires a step of attaching an optical compensation layer separately after creating a polarizing plate, the conventional manufacturing equipment for attaching a polarizing film and a polarizing film protective film greatly increases. It becomes necessary to modify, and the manufacturing process becomes complicated. As a result, there is a problem that the manufacturing cost of the polarizing plate with an optical compensation layer increases.

  Further, in order not to significantly modify the conventional manufacturing equipment, a polarizing film protective film with an optical compensation layer in which the optical compensation layer is bonded in advance to the polarizing film protective film is adopted, and the optical compensation layer is attached. A method of attaching the polarizing film protective film to the polarizing film is also conceivable.

However, when the polarizing film and the polarizing film protective film are bonded together, the polarizing film protective film is used as a saponification bath such as an inorganic alkaline aqueous solution in order to enhance the adhesiveness between the polarizing film and the polarizing film protective film by an adhesive. It is said that the surface is preferably saponified by immersing in water.
Then, when the polarizing film protective film with the optical compensation layer is adopted, the optical compensation layer is eroded by the saponification bath, and the optical compensation function is impaired. Therefore, the polarizing film protective film with the optical compensation layer Has a problem that it cannot be adopted in the conventional manufacturing process.

  Therefore, the present invention employs a polarizing film protective film with an optical compensation layer without significantly modifying the conventional polarizing plate manufacturing process, and with an optical compensation layer without impairing the optical compensation function of the optical compensation layer. It is an object to produce a polarizing plate.

  In order to solve the above-described problems, the present invention provides a saponification treatment for a polarizing film protective film with an optical compensation layer in which an optical compensation layer and an optical compensation layer protective film are sequentially laminated on the polarizing film protective film. A polarizing plate with an optical compensation layer is produced by bonding the polarizing film protective film with an optical compensation layer to the polarizing film on the surface of the polarizing film protective film thus manufactured. Provide a method.

  According to such a manufacturing method, since the polarizing film protective film is saponified in a state where the optical compensation layer protective film is laminated on the optical compensation layer, the optical compensation function of the optical compensation layer is impaired by the saponification process. It will not be. And since it is not necessary to change the manufacturing process of the conventional polarizing plate significantly except laminated | stacking an optical compensation layer protective film, it becomes possible to manufacture a polarizing plate with an optical compensation layer at low cost.

Hereinafter, the manufacturing method of the polarizing plate with an optical compensation layer according to the present invention will be described in detail.
In the method for producing a polarizing plate with an optical compensation layer of the present invention, a polarizing film protective film with an optical compensation layer in which an optical compensation layer and an optical compensation layer protective film are sequentially laminated on the polarizing film protective film is saponified. The polarizing film with an optical compensation layer is manufactured by bonding the polarizing film protective film to the polarizing film on the surface of the saponified polarizing film protective film.

  FIG. 1 is a flowchart showing an embodiment of the present invention. In this embodiment, first, the optical compensation layer 2 is laminated on the polarizing film protective film 1, and further the optical compensation layer protective film 3 is laminated on the optical compensation layer 2, followed by saponification treatment. The polarizing film protective film with an optical compensation layer 5 and the polarizing film 4 are bonded to each other on the saponified polarizing film protective film surface 1a. Also, the polarizing film protective film 1 ′ is saponified on the opposite surface of the polarizing film 4, and then bonded to the polarizing film protective film 1 ′ on the surface of the saponified polarizing film protective film. Thus, a polarizing plate with an optical compensation layer as one embodiment can be produced.

The polarizing film protective film 1 is not particularly limited as long as it is conventionally used by being laminated on the polarizing film in order to protect the polarizing film 4, and is transparent, mechanical strength, thermal stability, moisture shielding property. From the viewpoint of isotropicity, an appropriate one can be used.
Examples of the polarizing film protective film 1 include a film made of a cellulose-based polymer such as diacetyl cellulose or triacetyl cellulose.

  The thickness of the polarizing film protective film 1 is generally 500 μm or less, preferably 1 to 100 μm, and more preferably 30 to 50 μm.

  The optical compensation layer 2 is not particularly limited, and depending on the use of the polarizing plate with the optical compensation layer, a film containing various liquid crystal polymers, a birefringent film obtained by stretching a polymer film, or the like Can be used as appropriate.

  As a film comprising a liquid crystal polymer, for example, a film formed by polymerizing or crosslinking a liquid crystal monomer in a state of having a cholesteric structure and being oriented can be preferably used. In such a film, the liquid crystal polymer has a cholesteric structure such as a cholesteric liquid crystal phase and is oriented, but the liquid crystal molecule changes into a liquid crystal phase, a glass phase, and a crystal phase due to a temperature change like a liquid crystal molecule. I don't get up. Therefore, the film comprising the liquid crystal polymer can be used as an extremely stable optical compensation layer that is not affected by temperature changes.

  Specifically, the film containing the liquid crystal polymer forms a spread layer by spreading a coating liquid containing a liquid crystal monomer, a chiral agent, and at least one of a polymerization agent and a crosslinking agent on an alignment substrate. The development layer can be heated so that the liquid crystal monomer has a cholesteric structure, and the liquid crystal monomer can be polymerized or crosslinked to fix the cholesteric structure of the liquid crystal monomer.

  As said liquid crystal monomer, a nematic liquid crystal monomer can be used, for example, and the monomer illustrated by following formula (1) can be used more suitably. In addition, these liquid crystal monomers may be used independently and may use 2 or more types together.

In the formula (1), A ¹ and A ² each represent a polymerizable group, and may be the same or different. One of A ¹ and A ² may be hydrogen. X represents a single bond, —O—, —S—, —C═N—, —O—CO—, —CO—O—, —O—CO—O—, —CO—NR—, —NR—, respectively. CO -, - NR -, - O-CO-NR -, - NR-CO-O -, - CH 2 -O- or an -NR-CO-NR-. Further, in the X, R represents H or C ₁ -C ₄ alkyl, M represents a mesogenic group.

  In the formula (1), Xs may be the same or different, but are preferably the same.

Among the monomers represented by the formula (1), each A ² is preferably located in the ortho position with respect to A ¹ .

A ¹ and A ² are each independently represented by the following formula (2):
Z-X- (Sp) n (2)
And A ¹ and A ² are preferably the same group.

In the above formula (2), Z represents a crosslinkable group, X is the same as in the above formula (1), and Sp consists of a linear or branched alkyl group having 1 to 30 C atoms. Represents a spacer, and n represents 0 or 1. Carbon chain in the Sp, for example, oxygen in ether functional group, sulfur in a thioether functional group, may be interrupted by such alkylimino group nonadjacent imino or C ₁ -C _4.

  In the formula (2), Z is preferably any one of atomic groups represented by the following formula. In the following formula, examples of R include groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl.

In the formula (2), Sp is preferably any one of the atomic groups represented by the following formula. In the following formula, m is preferably 1 to 3, and p is preferably 1 to 12.

In the formula (1), M is preferably represented by the following formula (3). In the following (3), X is the same as X in the formula (1). Q represents, for example, a substituted or unsubstituted alkylene or aromatic hydrocarbon group, and may be, for example, a substituted or unsubstituted linear or branched C _{1 to} C ₁₂ alkylene.

When Q is the aromatic hydrocarbon atomic group, for example, an atomic group represented by the following formula or a substituted analog thereof is preferable.

The substituted analog of the aromatic hydrocarbon group represented by the above formula may have, for example, 1 to 4 substituents per aromatic ring, and may include one aromatic ring or one group. Each may have 1 or 2 substituents. The substituents may be the same or different. Examples of the substituent include C _{1 to} C ₄ alkyl groups, nitro groups, halogens such as F, Cl, Br, and I, phenyl groups, C _{1 to} C ₄ alkoxy groups, and the like.

Specific examples of the liquid crystal monomer include monomers represented by the following formulas (4) to (19).

  The temperature range in which the liquid crystal monomer exhibits liquid crystallinity varies depending on the type, but is preferably in the range of 40 to 120 ° C., more preferably in the range of 50 to 100 ° C., and particularly preferably 60. It is the range of -90 degreeC.

  The chiral agent is not particularly limited as long as it imparts a twist to the liquid crystal monomer so that the liquid crystal monomer is aligned to have a cholesteric structure, but a polymerizable chiral agent is preferable. A chiral agent may be used individually by 1 type, and may use 2 or more types together.

Specifically, as the polymerizable chiral agent, for example, chiral compounds represented by the following general formulas (20) to (23) can be used.
(Z−X ⁵ ) _n Ch (20)
^{(Z-X 2 -Sp-X} 5) n Ch ··· (21)
(P ¹ −X ⁵ ) _n Ch (22)
^{(Z-X 2 -Sp-X} 3 -M-X 4) n Ch ··· (23)

In the above formulas, Z and Sp are the same as those in the formula (2), and X ² , X ³ and X ⁴ are each independently a chemical single bond, —O—, —S—, —O. —CO—, —CO—O—, —O—CO—O—, —CO—NR—, —NR—CO—, —O—CO—NR—, —NR—CO—O— or —NR—CO. It represents -NR-, wherein R represents H, a C ₁ -C ₄ alkyl. X ⁵ represents a chemical single bond, —O—, —S—, —O—CO—, —CO—O—, —O—CO—O—, —CO—NR—, —NR—CO—. , —O—CO—NR—, —NR—CO—O—, —NR—CO—NR—, —CH ₂ O—, —O—CH ₂ —, —CH═N—, —N═CH— or —N≡N— is represented. R is the same manner as described above, represents H, C ₁ -C ₄ alkyl. M represents a mesogen group as described above, and P ¹ represents hydrogen, a C _{1 to} C ₃₀ alkyl group substituted with _{1 to} 3 C _{1 to} C ₆ alkyls, a C _{1 to} C ₃₀ acyl group, or C 1 It represents ₃ -C ₈ cycloalkyl radical, n is an integer from 1 to 6. Ch represents an n-valent chiral group. In the formula (23), at least one of X ³ and X ⁴ is —O—CO—O—, —O—CO—NR—, —NR—CO—O—, or —NR—CO—NR—. It is preferable that In the formula (22), when P ¹ is an alkyl group, an acyl group or a cycloalkyl group, for example, the carbon chain is oxygen in the ether functional group, sulfur in the thioether functional group, non-adjacent imino group or it may be interrupted by C ₁ -C ₄ alkylimino groups.

Examples of the chiral agent for Ch include an atomic group represented by the following formula.

In the atomic group, L is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, COOR, OCOR, CONHR or NHCOR, and R represents a C ₁ -C ₄ alkyl group. In addition, the terminal in the atomic group represented by the above formula represents a bond with an adjacent group.

Among the atomic groups, an atomic group represented by the following formula is particularly preferable.

The chiral compound represented by the formula (21) or (23) is, for example, an atomic group in which n is 2, Z represents H ₂ C═CH—, and Ch is represented by the following formula. preferable.

Specific examples of the chiral compound include compounds represented by the following formulas (24) to (44). These chiral compounds have a twisting force of 1 × 10 ⁻⁶ nm ⁻¹ · (wt%) ⁻¹ or more.

  In addition to the above-mentioned chiral compounds, for example, chiral compounds listed in RE-A 4342280 and German Patent Applications 19520660.6 and 195207041 can be preferably used.

  Although it does not restrict | limit especially as said polymerizer and a crosslinking agent, For example, the following can be used. That is, as the polymerization agent, for example, benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), etc. can be used, and as the crosslinking agent, for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a metal chelate crosslinking agent, etc. Can be used. Any of these may be used alone or in combination of two or more.

Further, the liquid crystal monomer is not limited to the nematic liquid crystal as described above, and a discotic liquid crystal can also be used.
The type of discotic liquid crystal is also not particularly limited, and can be appropriately selected from known ones.

The non-liquid crystalline polymer film constituting the optical compensation layer 2 is excellent in heat resistance, chemical resistance, transparency, and rigidity, so that, for example, polyamide, polyimide, polyester, polyetherketone, polyamideimide, A polymer film such as polyesterimide can be preferably used.
Any one of these polymers may be used alone, or a mixture of two or more having different functional groups such as a mixture of polyaryletherketone and polyamide may be used. . Among such polymers, polyimide is particularly preferable because of its high transparency, high orientation, and high stretchability.

  The molecular weight of the polymer is not particularly limited, but for example, the weight average molecular weight (Mw) is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 2,000 to 500,000. .

As the polyimide, for example, a polyimide that has high in-plane orientation and is soluble in an organic solvent is preferable. Specifically, for example, it includes a condensation polymerization product of 9,9-bis (aminoaryl) fluorene and an aromatic tetracarboxylic dianhydride disclosed in JP 2000-511296 A, and has the following formula ( A polymer containing one or more repeating units shown in 45) can be used.

In the formula (45), R ³ ~R ⁶ is hydrogen, halogen, a phenyl group, 1-4 halogen atoms, or C ₁ ~ ₁₀ alkyl-substituted phenyl, and C ₁ ~ ₁₀ alkyl group And at least one substituent selected independently from the group. Preferably, R ³ to R ⁶ is a halogen, a phenyl group, each independently from the group consisting of one to four halogen atoms or C ₁ ~ ₁₀ alkyl-substituted phenyl, and C ₁ ~ ₁₀ alkyl group It is at least one type of substituent selected.

In the formula (45), Z is, for example, a tetravalent aromatic group having C ₆ ~ _20, preferably a pyromellitic group, a polycyclic aromatic group, a derivative of a polycyclic aromatic group, or, It is group represented by following formula (46).

In the formula (46), Z ′ represents, for example, a covalent bond, C (R ⁷ ) ₂ group, CO group, O atom, S atom, SO ₂ group, Si (C ₂ H ₅ ) ₂ group, or NR ^{There are 8} groups, and when there are multiple groups, they are the same or different. W represents an integer from 1 to 10.
Each R ⁷ is independently hydrogen or C (R ⁹ ) ₃ . R ⁸ is hydrogen, an alkyl group having 1 to about 20 carbon atoms, or an aryl group having ₆ to ₂₀ carbon atoms, and in a plurality of cases, they are the same or different. Each R ⁹ is independently hydrogen, fluorine, or chlorine.

Examples of the polycyclic aromatic group include a tetravalent group derived from naphthalene, fluorene, benzofluorene or anthracene. The substitution Examples of the substituted derivatives of polycyclic aromatic group, for example, an alkyl group of C ₁ ~ _10, at least one group selected from the group consisting of fluorinated derivatives, and F or a halogen such as Cl And the above-mentioned polycyclic aromatic group.

  In addition to this, for example, the homopolymer represented by the following general formula (47) or (48) described in JP-A-8-511812, or the repeating unit represented by the following general formula (49) The polyimide etc. which are shown are mention | raise | lifted. In addition, the polyimide of following formula (49) is a preferable form of the homopolymer of following formula (47).

In the general formulas (47) to (49), G and G ′ are, for example, a covalent bond, a CH ₂ group, a C (CH ₃ ) ₂ group, a C (CF ₃ ) ₂ group, or a C (CX ₃ ) ₂ group. (Where X is halogen), from the group consisting of CO, O, S, SO ₂ , Si (CH ₂ CH ₃ ) ₂ and N (CH ₃ ) groups, respectively It represents independently selected groups, and may be the same or different.

In Formula (47) and Formula (49), L is a substituent, and d and e represent the number of substitutions. L is, for example, halogen, C ₁ ~ ₃ alkyl group, C ₁ ~ ₃ halogenated alkyl group, a phenyl group, or a substituted phenyl group, in the case of multiple or different are each identical. Examples of the substituted phenyl group, for example, halogen, a substituted phenyl group having at least one substituent selected from C ₁ ~ ₃ alkyl group, and C ₁ ~ ₃ the group consisting of halogenated alkyl groups. Examples of the halogen include fluorine, chlorine, bromine and iodine. d is an integer from 0 to 2, and e is an integer from 0 to 3.

  In the formulas (47) to (49), Q is a substituent, and f represents the number of substitutions. Q is, for example, selected from the group consisting of hydrogen, halogen, alkyl group, substituted alkyl group, nitro group, cyano group, thioalkyl group, alkoxy group, aryl group, substituted aryl group, alkyl ester group, and substituted alkyl ester group And when Q is plural, they are the same or different. Examples of the halogen include fluorine, chlorine, bromine and iodine. Examples of the substituted alkyl group include a halogenated alkyl group. Examples of the substituted aryl group include a halogenated aryl group. f is an integer from 0 to 4, and g and h are integers from 0 to 3 and 1 to 3, respectively. Further, g and h are preferably larger than 1.

In the formula (48), R ¹⁰ and R ¹¹ are groups independently selected from the group consisting of hydrogen, halogen, phenyl group, substituted phenyl group, alkyl group, and substituted alkyl group. Among these, R ¹⁰ and R ¹¹ are preferably each independently a halogenated alkyl group.

In the formula (49), M ¹ and M ² are identical or different, for example, halogen, C ₁ ~ ₃ alkyl group, C ₁ ~ ₃ halogenated alkyl group, a phenyl group or a substituted phenyl group is there. Examples of the halogen include fluorine, chlorine, bromine and iodine. The above-mentioned substituted phenyl group, for example, halogen, a substituted phenyl group having at least one substituent selected from the group consisting of C ₁ ~ ₃ alkyl group, and C ₁ ~ ₃ halogenated alkyl group and the like .

Specific examples of the polyimide represented by the formula (47) include those represented by the following formula (50).

  Furthermore, examples of the polyimide include a copolymer obtained by appropriately copolymerizing an acid dianhydride other than the skeleton (repeating unit) as described above and a diamine.

  Examples of the acid dianhydride include aromatic tetracarboxylic dianhydrides. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, heterocyclic aromatic tetracarboxylic dianhydride, 2, And 2'-substituted biphenyltetracarboxylic dianhydride.

  Examples of the pyromellitic dianhydride include pyromellitic dianhydride, 3,6-diphenylpyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, and 3,6-dibromo. Examples include pyromellitic dianhydride and 3,6-dichloropyromellitic dianhydride. Examples of the benzophenone tetracarboxylic dianhydride include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2 , 2 ′, 3,3′-benzophenone tetracarboxylic dianhydride and the like. Examples of the naphthalenetetracarboxylic dianhydride include 2,3,6,7-naphthalene-tetracarboxylic dianhydride, 1,2,5,6-naphthalene-tetracarboxylic dianhydride, 2,6 -Dichloro-naphthalene-1,4,5,8-tetracarboxylic dianhydride and the like. Examples of the heterocyclic aromatic tetracarboxylic dianhydride include thiophene-2,3,4,5-tetracarboxylic dianhydride and pyrazine-2,3,5,6-tetracarboxylic dianhydride. Pyridine-2,3,5,6-tetracarboxylic dianhydride and the like. Examples of the 2,2′-substituted biphenyltetracarboxylic dianhydride include 2,2′-dibromo-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride and 2,2′-dichloro. -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetracarboxylic dianhydride, etc. can give.

  Other examples of the aromatic tetracarboxylic dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 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 dianhydride, 4,4 ′-(3,4-dicarboxyphenyl) -2,2-diphenylpropane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4 , 4′-oxydiphthalic dianhydride, bis (3,4-dicarboxyphenyl) sulfonic dianhydride (3,3 ′, 4,4′-diphenylsulfonetetracarboxylic 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 dianhydride, etc. Is given.

  Among these, the aromatic tetracarboxylic dianhydride is preferably 2,2′-substituted biphenyltetracarboxylic dianhydride, more preferably 2,2′-bis (trihalomethyl) -4,4. ', 5,5'-biphenyltetracarboxylic dianhydride, more preferably 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetracarboxylic dianhydride It is.

  Examples of the diamine include aromatic diamines, and specific examples include benzene diamine, diaminobenzophenone, naphthalene diamine, heterocyclic aromatic diamine, and other aromatic diamines.

  Examples of the benzenediamine include o-, m- and p-phenylenediamine, 2,4-diaminotoluene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-phenylbenzene, and 1, Examples include diamines selected from the group consisting of benzenediamines such as 3-diamino-4-chlorobenzene. Examples of the diaminobenzophenone include 2,2'-diaminobenzophenone and 3,3'-diaminobenzophenone. Examples of the naphthalene diamine include 1,8-diaminonaphthalene and 1,5-diaminonaphthalene. Examples of the heterocyclic aromatic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, and 2,4-diamino-S-triazine.

  In addition to these, the aromatic diamine includes 4,4′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 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′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 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-amino Phenoxy) 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'-diaminodiphenyl thioether, 4,4'-diaminodiphenyl sulfone and the like.

  Examples of the polyether ketone used as the material of the optical compensation layer include polyaryl ether ketones represented by the following general formula (51) described in JP-A No. 2001-49110.

  In the formula (51), X represents a substituent, and q represents the number of substitutions. X is, for example, a halogen atom, a lower alkyl group, a halogenated alkyl group, a lower alkoxy group, or a halogenated alkoxy group, and when there are a plurality of Xs, they are the same or different.

Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and among these, a fluorine atom is preferable. Examples of the lower alkyl group, for example, preferably a lower alkyl group having a straight-chain or branched C ₁ ~ _6, more preferably a straight-chain or branched alkyl group of C ₁ ~ _4. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are preferable, and a methyl group and an ethyl group are particularly preferable. Examples of the halogenated alkyl group include halides of the lower alkyl group such as a trifluoromethyl group. Examples of the lower alkoxy group, for example, preferably a straight chain or branched chain alkoxy group of C ₁ ~ _6, more preferably a straight chain or branched chain alkoxy group of C ₁ ~ _4. Specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group are more preferable, and a methoxy group and an ethoxy group are particularly preferable. . Examples of the halogenated alkoxy group include halides of the lower alkoxy group such as a trifluoromethoxy group.

  In the formula (51), q is an integer from 0 to 4. In the formula (51), it is preferable that q = 0, and the carbonyl group bonded to both ends of the benzene ring and the oxygen atom of the ether are present in the para position.

In the formula (51), R ¹ is a group represented by the following formula (52), and m is an integer of 0 or 1.

  In the formula (52), X ′ represents a substituent, and is the same as X in the formula (51), for example. In Formula (52), when there are a plurality of X ′, they are the same or different. q ′ represents the number of substitutions of X ′ and is an integer from 0 to 4, preferably q ′ = 0. P is an integer of 0 or 1.

In the formula (52), R ² represents a divalent aromatic group. Examples of the divalent aromatic group include an o-, m- or p-phenylene group, or naphthalene, biphenyl, anthracene, o-, m- or p-terphenyl, phenanthrene, dibenzofuran, biphenyl ether, or And divalent groups derived from biphenylsulfone. In these divalent 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, R ² is preferably an aromatic group selected from the group consisting of the following formulas (53) to (59).

In the formula (51), the R ¹ is preferably a group represented by the following formula (60). In the following formula (60), R ² and p have the same meanings as the formula (52).

  Furthermore, in said Formula (51), n represents a polymerization degree, for example, is the range of 2-5000, Preferably, it is the range of 5-500. The polymerization may be composed of repeating units having the same structure, or may be composed of repeating units having different structures. In the latter case, the polymerization mode of the repeating unit may be block polymerization or random polymerization.

  Furthermore, it is preferable that the end of the polyaryl ether ketone represented by the formula (51) is fluorine on the p-tetrafluorobenzoylene group side and a hydrogen atom on the oxyalkylene group side. For example, it can be represented by the following general formula (61). In the formula below, n represents the same degree of polymerization as in formula (51).

  Specific examples of the polyaryletherketone represented by the formula (51) include those represented by the following formulas (62) to (65). In each formula below, n represents the formula (51). Represents the same degree of polymerization.

  In addition to these, examples of the polyamide or polyester as the material of the optical compensation layer include polyamides and polyesters described in JP-T-10-508048, and the repeating units thereof are, for example, Can be represented by the following general formula (66).

In the formula (66), Y is O or NH. 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, It is at least one kind of group selected from the group consisting of O atom, S atom, SO ₂ group, Si (R) ₂ group, and N (R) group, and may be the same or different. In the E, R is at least one of C ₁ ~ ₃ alkyl group and C ₁ ~ ₃ halogenated alkyl group, in the meta or para position relative to the carbonyl functional group or a Y group.

  Moreover, in said (66), A and A 'are substituents and t and z represent the number of each substitution. P is an integer from 0 to 3, q is an integer from 1 to 3, and r is an integer from 0 to 3.

Wherein A is selected from hydrogen, a halogen, C ₁ ~ ₃ alkyl group, C ₁ ~ ₃ halogenated alkyl group, OR (wherein, R represents those defined above.) The alkoxy group represented by aryl group, a substituted aryl group by a halogen, etc., C ₁ ~ ₉ alkoxycarbonyl group, C ₁ ~ ₉ alkylcarbonyloxy group, C ₁ ~ ₁₂ aryloxycarbonyl group, C ₁ ~ ₁₂ arylcarbonyloxy group and a substituted derivative thereof, C _1-12 arylcarbamoyl group, and is selected from the group consisting of C _1-12 arylcarbonylamino group and a substituted derivative thereof, in the case of a plurality, they may be the same or different. Wherein A 'is, for example, halogen, C ₁ ~ ₃ alkyl group, C ₁ ~ ₃ halogenated alkyl group, selected from the group consisting of phenyl group and a substituted phenyl group and when there are plural, they may be the same or different. Examples of the substituent on the phenyl ring of the substituted phenyl group include halogen, C _1-3 alkyl group, C _1-3 halogenated alkyl group, and combinations thereof. The t is an integer from 0 to 4, and the z is an integer from 0 to 3.

  Among the repeating units of polyamide or polyester represented by the formula (66), those represented by the following general formula (67) are preferable.

  In the formula (67), A, A ′ and Y are as defined in the formula (66), and v is an integer of 0 to 3, preferably an integer of 0 to 2. x and y are each 0 or 1, but are not 0 at the same time.

  In order to laminate the optical compensation layer 2 having such a configuration on the polarizing film protective film 1, a pressure-sensitive adhesive or an adhesive can be used. Especially, it is preferable to use an adhesive from a viewpoint that thickness reduction of a polarizing plate with an optical compensation layer can be achieved.

  As the pressure-sensitive adhesive, those having excellent transparency and exhibiting appropriate wettability, cohesion and adhesive properties are preferable. For example, rubber-based, acrylic-based and silicone-based pressure-sensitive adhesives can be used. .

Moreover, as said adhesive agent, an epoxy type, an acrylic type, an acrylic urethane type adhesive agent, etc. can be used.
When a polarizing film protective film and an optical compensation layer are laminated by an adhesive, the produced polarizing plate with an optical compensation layer is excellent in thin and lightweight properties, and is suitable for an image display device used for mobile applications. It becomes a polarizing plate with a compensation layer.

The optical compensation layer protective film 3 is not particularly limited as long as it has alkali resistance to the extent that the surface of the optical compensation layer 2 is not adversely affected in the subsequent saponification treatment and can be peeled off after the saponification treatment.
As the optical compensation layer protective film 3, for example, polyolefin-based or polyester-based polymers can be widely used. Among them, polyethylene or polyethylene terephthalate is preferable from the viewpoint of excellent alkali resistance.
The optical compensation layer protective film 3 may be peeled off immediately after the saponification treatment, may be peeled off before lamination with the polarizing film 4, or may be peeled off after lamination with the polarizing film 4.
However, when passing through the process heated to high temperature in the process after a saponification process, it is preferable to set it as the optical compensation layer protective film excellent in heat resistance.

  The method for bonding the optical compensation layer protective film to the optical compensation layer is not particularly limited. For example, the optical compensation layer protective film is not peeled off during the saponification treatment, and can be easily peeled off after the saponification treatment. Such a thing can be used conveniently. Examples of such a method include a method of attaching via a rubber-based, acrylic-based, or silicone-based pressure-sensitive adhesive.

  The saponification treatment method of the polarizing film protective film is not particularly limited, and it is optimal from known methods as appropriate depending on the adhesive used for bonding the polarizing film protective film and the polarizing film and the type of the polarizing film protective film. The conditions (immersion time in alkali, temperature of alkali solution, concentration of alkali solution, etc.) may be selected.

  Next, the polarizing film protective film with an optical compensation layer and the polarizing film are bonded via the surface of the polarizing film protective film saponified by the saponification treatment. As the adhesive, for example, an aqueous solution containing polyvinyl alcohol and its crosslinking agent, an isocyanate-based adhesive, or the like can be used.

  The liquid crystal display device of the present invention includes the polarizing plate with an optical compensation layer of the present invention as described above. The type of the liquid crystal display device is not particularly limited, and for example, an STN (Super Twisted Nematic) cell, a TN (Twisted Nematic) cell, a VA (Vertical Aligned Birefringence) cell, an OCB (Optically Controlled Birefringence) cell, an HN cell, an HN cell, an HN cell, an HN cell, an HN cell, an HN cell, an HN cell, an HN cell, a HN These cells can include various types of cells such as those subjected to regular alignment division and those subjected to random alignment division, and also include a simple matrix type, TFT (Thin Film Transistor) electrode, MIM (Metal Insulator Metal). ) Active matrix system using electrodes, etc., IPS (In− Various driving methods such as a plane switching method and a plasma addressing method can be adopted. Further, it can be of a transmissive type provided with a backlight system, a reflective type provided with a reflecting plate, or a projection type.

  In the liquid crystal display device of the present invention, the aspect including the polarizing plate with the optical compensation layer is not particularly limited, but usually, the upper side of the driving cell and the optical compensation layer are positioned between the polarizing film and the driving cell. There may be mentioned an embodiment in which one or a plurality of the polarizing plates with optical compensation layers are arranged at the lower position. Moreover, it can also be set as the aspect combined with another optical film, for example, the phase difference film which has a refractive index structure different from the optical film of this invention, a scattering film, a lens sheet, etc.

The polarizing plate with an optical compensation layer of the present invention can also be used in other image display devices such as an organic electroluminescence device.
An organic electroluminescent device includes, for example, a transparent electrode on the surface side of an organic light emitting layer that emits light when a voltage is applied, and a metal electrode on the back surface side of the organic light emitting layer. In the organic electroluminescence device having such a configuration, for example, the polarizing plate with an optical compensation layer of the present invention can be provided on the surface side of the transparent electrode, and preferably, optical compensation is performed between the transparent electrode and the polarizing film. It can be provided that the layer is located.

  Hereinafter, the present invention will be described in more detail by giving examples.

Example 1
(1) Using a triacetyl cellulose film (LC film) manufactured by Nippon Oil Corporation with an optical compensation layer having a thickness of 56 μm, an optical compensation layer protective film (manufactured by Sanei Kaken Co., Ltd.) is attached to the optical compensation layer. Then, the laminated film was immersed in a saponification bath, and the surface of the triacetylcellulose film was saponified to produce a polarizing film protective film 5 with an optical compensation layer.
(2) A polyvinyl alcohol film (manufactured by Kuraray Co., Ltd.) was stretched 2.7 times while immersed in pure water at 30 ° C. for 1 minute. Next, the film was stretched 1.4 times while immersed in an aqueous solution having an iodine concentration of 3% at 30 ° C. for 1 minute. Next, the film was stretched 1.7 times while immersed in a mixed aqueous solution of boric acid and iodine having a boric acid concentration of 4% and an iodine concentration of 3% at 55 ° C. for 2 minutes. Further, it was immersed in an aqueous solution having an iodine concentration of 3.4% at 30 ° C. for 5 seconds. Thereafter, the polarizing film 4 was produced by drying in air at 27 ° C. for 7 minutes.
(3) Furthermore, a saponified triacetyl cellulose film (Fuji Film, Fujitac) was separately prepared as the polarizing film protective film 1 ′.
A polarizing plate with an optical compensation layer of Example 1 was produced by laminating these 5, 4, 1 ′ films and films in that order.

  When the polarizing plate with an optical compensation layer of Example 1 was examined, the total thickness was 121 μm, and no erosion of the optical compensation layer was observed.

Comparative Example 1
The optical compensation layer of Comparative Example 1 was the same as Example 1 except that the polarizing film protective film 5 with the optical compensation layer was subjected to saponification treatment without bonding the optical compensation layer protective film to the optical compensation layer. An attached polarizing plate was produced.
When the polarizing plate with an optical compensation layer of Comparative Example 1 was examined, the total thickness was 121 μm, but the optical compensation layer was eluted by saponification.

Comparative Example 2
A polarizing plate was prepared by pasting the polarizing film protective film 1 ′ on both sides of the polarizing film 4. The polarizing plate protective film 5 with an optical compensation layer is coated with a pressure-sensitive adhesive (acrylic, 20 μm) applied to the opposite side of the polarizing film protective film 5 with the optical compensation layer, and the optical compensation layer of Comparative Example 2 is attached. A polarizing plate was produced.
When the polarizing plate with an optical compensation layer of Comparative Example 2 was examined, the total thickness was 181 μm.

Comparative Example 3
A polarizing plate was prepared by pasting the polarizing film protective film 1 ′ on both sides of the polarizing film 4. Next, an optical compensation layer is formed by applying a liquid crystal polymer on a polyethylene terephthalate film to a thickness of 16 μm, and further bonding an adhesive (acrylic) applied to a thickness of 20 μm, and then peeling the polyethylene terephthalate film. Was transferred to a polarizing plate to produce a polarizing plate with an optical compensation layer of Comparative Example 3.
When the polarizing plate with an optical compensation layer of Comparative Example 3 was examined, the total thickness was 141 μm.

The flowchart which showed one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 1 'Polarizing film protective film 1a Saponified polarizing film protective film surface 2 Optical compensation layer 3 Optical compensation layer protective film 4 Polarizing film 5 Polarizing film protective film with an optical compensation layer

Claims (7)

  A polarizing film protective film with an optical compensation layer in which an optical compensation layer and an optical compensation layer protective film are sequentially laminated on the polarizing film protective film is saponified, and the optical film is formed on the surface of the saponified polarizing film protective film. A method for producing a polarizing plate with an optical compensation layer, comprising producing a polarizing plate with an optical compensation layer by attaching a polarizing film protective film with a compensation layer to the polarizing film.   The method for producing a polarizing plate with an optical compensation layer according to claim 1, wherein the optical compensation layer is laminated on a polarizing film protective film via an adhesive.   The method for producing a polarizing plate with an optical compensation layer according to claim 1, wherein the optical compensation layer comprises a liquid crystal polymer.   The said polarizing film protective film is a triacetyl cellulose film, The manufacturing method of the polarizing plate with an optical compensation layer in any one of Claims 1-3 characterized by the above-mentioned.   The thickness of the said polarizing film protective film is 30-50 micrometers, The manufacturing method of the polarizing plate with an optical compensation layer in any one of Claims 1-4 characterized by the above-mentioned.   The polarizing plate with an optical compensation layer obtained by the manufacturing method in any one of Claims 1-5.   An image display device comprising the polarizing plate with an optical compensation layer according to claim 6.