TW200540001A - Laminated film and process for producing the same - Google Patents

Abstract

A laminated film that excels in environment-resistant dimensional stability, and that having a phase-contrast property as an optical compensation function, excels in the stability of the phase-contrast property, and that is useful as a polarizer protection film having excellent adherence to polarizers. This laminated film comprises a transparent film of thermoplastic synthetic polymer and, superimposed on one major surface thereof, a thin film of hydrophilic polymer, between which there is interposed a layer of crosslinking resin cured. The transparent film is a birefringent film satisfying the formulae: (1) 0 ≤ (Nx-ny)xd ≤ 300 nm, and (2) -150 ≤ {(Nx+ny)/2-nz}xd ≤ 400 nm.

Description

200540001 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a laminated film and a method for manufacturing the same. More specifically, it relates to chemical resistance, environmental resistance, and the like having excellent durability and optical compensation. Functional laminated film and manufacturing method thereof. [Prior art] Although the prior art has been using cellulose triacetate resin films as protective films for polarizers, in recent years, polarizers have been used in various applications and in various environments. A polarizer that has never been used under severe conditions. At present, a protective film for polarizers made of cellulose triacetate resin is still used, but it causes dimensional shrinkage in environmental tests under high temperature and high humidity, the function of polarizers deteriorates, and stress caused by shrinkage. The influence of the image quality of the liquid crystal display element used as a polarizing plate has become a great problem. Furthermore, a retardation film has been bonded to a polarizing plate with an adhesive to produce a polarizing plate with an optical compensation function. However, in order to further reduce the cost of the liquid crystal display element, it is desirable to reduce the number of members and the number of processing steps, and to work to make the function of the protective film as a polarizer exhibit a retardation function. In addition, the use of stretched cellulose triacetate Resin film is used to make it a retardation film, and materials are developed to make the protective film of polarizers have optical compensation function (refer to JP 7-2 1 8 724 and JP 2003-279729). 200540001 (2) However, because the cellulose triacetate resin film is used as the material, the optical characteristics of the environmental resistance test are significantly reduced, and the problem of dimensional stability still exists, so it has not been obtained so far. Polarization protective film with excellent dimensional stability for environmental resistance and retardation characteristics as an optical compensation function. [Summary of the Invention] φ The object of the present invention is to provide a layer that is excellent in dimensional stability in terms of environmental resistance and has phase difference characteristics as an optical compensation function. This phase difference has excellent stability and excellent adhesion to polarizers.合 Film. Another object of the present invention is to provide a method for manufacturing the laminated film of the present invention, which is suitable for industrial use. Other objects and advantages of the present invention will be understood from the following description. In order to achieve the above-mentioned object, the present inventor focused on the adhesion between a polarizer having a polarizing function φ and a film having a retardation characteristic and the film having a retardation characteristic, and learned the adhesion between the polarizer and the above-mentioned related film. • It is important to use a hydrophilic material and a cross-linkable resin, and to form the layers in a specific order to achieve the invention. According to the present invention, the above-mentioned objects and advantages of the present invention are achieved firstly by a laminated film, which is characterized by (A) a transparent film of a thermoplastic synthetic polymer, (B) a transparent film (a) At least one hardened layer of a crosslinkable resin on one side and a layer of a hydrophilic polymer on the hardened layer (b) of -6-200540001 (3) (C), The thin film system satisfies the following formulae (1) and (2) (0 〇 < (nx — ny) xd < 3 OOnm (2) · 150 < {(nx + ny) / 2-nz} xd < 400nm this Where nx is the maximum refractive index in the film plane, ny is the refractive index perpendicular to the film plane in the direction of ηχ, nz is the refractive index in the positive g direction of the film plane, and d is the thickness of the film ( nm), and is used for manufacturing polarizing plates by adhering with polarizers. According to the present invention, the above-mentioned objects and advantages of the present invention are secondly achieved by a manufacturing method of a laminated film, and the manufacturing method of the laminated film is characterized by A solution of a cross-linkable resin coated on at least one side of a transparent film made of a thermoplastic synthetic polymer It is formed by hardening to form a hardened layer of a cross-linkable resin. Then, a hydrophilic polymer solution is coated on the hardened layer, and a layer of the hydrophilic polymer is formed after the heat φ is fixed. The transparent film satisfies the following formula (1) and (2) • (1) 0 < (nx — ny) xd < 3 OOnm • (2) -1 5 Ο < {(nx + ny) / 2 — nz} xd < 400nm here nx is the maximum refractive index in the film plane, ny is the refractive index in the nx direction that is perpendicular to the film plane, ~ is the refractive index in the positive direction of the film plane, and d is the thickness (nm) of the film. 200540001 (4) [The best form of the present invention] «T Thermoplastic Synthetic Polymer Transparent Film 'The thermoplastic synthesis used in the present invention can be used as a protective film for polarizers with high strength, thermal stability, moisture shielding, Examples of thermoplastic synthetic polymers such as polyethylene terephthalate (polyethylene φ such as polymethyl methacrylate, acrylic polyacrylonitrile · styrene copolymer (AS resin) carbonate, polyethylene, poly Copolymerization of propylene, cycloolefins, and ethylene / propylene Polyolefin polymers, such as compounds of nylon and aromatic polyamines, fluorene polymers, polyether fluorene polymers, vinyl alcohol, vinylidene chloride polymers, vinyl ester polymers, polyoxymethylene φ, etc. Among them, polycarbonate, ice-reducing, and polyhedral are particularly suitable as materials for the protection of polarizers. Among them, polycarbonate is particularly suitable for the thermoplastic carbonic acid and ethylene glycol used in the present invention. Or a polyester of a 2-membered phenol 'selected from 1,1-bis (4-acrylphenyl) -cholylcyclohydroxyphenyl) -alkylcycloalkane, 1, bis (2) -alkylcycloalkane, As long as the transparent film having a homogeneous molecular weight of a dihydric phenol of a group consisting of 9,9-bis (4-hydroxyphenyl group) as a monomer component is acceptable, it is preferably one having excellent transparency and mechanical directionality. Polyesters and compounds of polyethylene terephthalate and polynaphthal at e), such as polystyrene and acrylic styrene-based polymers, poly- or norbornene-structured polymers, vinyl chloride-based Ammonium polymer, ammonium polyetheretherketone, polyphenylene sulfide, butyral-based polymer, aromatic and blended film of the above-mentioned polymer film and give sufficient sintered polymer, polyaromatic Esters are particularly good. Examples of the synthetic polymer polycarbonate include at least one alkane, 1,1-bis (3-substituted-4-i, 5-disubstituted-4-hydroxyphenyl) fluorene, and other bisphenols. Carbonate, copolycarbonate-8-200540001 (5), such as copolycarbonates of the above-mentioned dihydric phenols and bisphenol A as monomer components other than bisphenol A, and mixtures of such polycarbonates, such as Mixture of polycarbonate with other acids as bisacid A. Specific examples of 1,1_bis (4-hydroxyphenyl) -alkylcycloalkane include 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1- Bis (4-hydroxyphenyl) -3,3-dimethyl-5,5-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl-5 -Methylcyclopentane and the like. φ 1,1-bis (3-substituted hydroxyphenyl) -alkylcycloalkanes, such as i, b bis (4, where 3-position of 4-hydroxyphenyl is replaced by an alkyl or halo group having 1 to 12 carbon atoms -Hydroxyphenyl) -alkylcycloalkanes include, for example, 1,1-bis (3-methyl-4 · hydroxyphenyl) -3,3,5-trimethylcyclohexane, and 1,1-bis (3-ethyl-4-hydroxyphenyl) -3,3-dimethyl-5,5-dimethylcyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) -3, 3-dimethyl-4-methylcyclohexane, 1J-bis (3-bromo-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclopentane, and the like. 1,1-bis (3,5-di-substituted-4 -controlylphenyl) -ring base ring, for example, the 3- and 5-positions of Lu 4-hydroxyphenyl are respectively Examples of 1,1-bis (4-hydroxyphenyl) _alkylcycloalkanes substituted by halogen groups, such as M • bis (3,5-dimethyl-4-hydroxyphenyl) -3,3 , 5-trimethylcyclohexane •, bis (3,5-dichloro-4-hydroxyphenyl) -3,3_dimethyl-5-methylcyclohexane, 1,1-bis (3 -Ethyl-5-methyl-4-hydroxyphenyl) · 3,3,5-5methylcyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl)- 3,3,5-trimethylcyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) _3,3-dimethyl_5-methylcyclopentane, etc. 9,9-Double (4_ via the basic group) Do not pass the compound shown by the following formula (I) -9-200540001

φ (where R1 and R2 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.) Examples of the aforementioned related compounds include 9,9-bis (4-hydroxyphenyl) fluorene, 9 , 9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene and the like. Other bisphenols include, for example, 2,2'-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A), 4,4 '-(α-methylbenzylidene) bisphenol, and bis (4- Hydroxyphenyl) methane, 2,2'-bis (4-hydroxyphenyl) butane, 3,3'-bis® (4-hydroxyphenyl) pentane, 4,4'-bis (4-hydroxybenzene Group) heptane, 4,4'-bis (4-hydroxyphenyl) 2,5-dimethylheptane, bis (4-hydroxyphenyl) methylphenylmethane, bis (4-hydroxyphenyl) Diphenylmethane, 2,2'-bisMim hydroxyphenyl) octane, bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) 4-fluorophenylmethane, 2,2'- Bis (3-fluoro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2'-bis (3,5-dimethyl-4-hydroxy Phenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) phenylethane, bis (3-methyl-4-hydroxyphenyl) diphenylmethane, etc., these 2-valent phenols Can be used alone or mixed for shake. • 10- 200540001 (7) In addition to the above-mentioned dihydric phenols, the polycarbonates described above include a polymer of aliphatic, aromatic and aromatic dicarboxylic acids using a part of the dihydric phenols as a comonomer. For the ester carbonate, the ratio of the above-mentioned related comonomers is preferably 30 mol% or less relative to the total of the divalent phenol. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, p-xylene glycol, bis (4-hydroxyphenyl) -methane, and 1,1'-bis (4 · hydroxyphenyl)- Ethane, 1,1'-bis (4-hydroxyphenyl) -butane, 2,2'-bis (4-hydroxyphenyl)-^ butane, etc., among which terephthalic acid and isophthalic acid Better. The viscosity average molecular weight of the polycarbonate used is preferably 2,000 to 100,000, preferably 5,000 to 70,000, and more preferably 7,000 to 50,000. This is a dichloromethane solution with a concentration of 0.7 g / dl at 20 ° C. The measured specific viscosity is approximately equivalent to 0.07 ~ 2/70, preferably 0.15 ~ 1.80, and more preferably 0.20 ~ 1.30. If the viscosity average molecular weight is less than 2,000, the resulting film is liable to become brittle and unfavorable, and more than 100,000 is not suitable because it is difficult to process the film. The polycarbonate used in the present invention is particularly preferably a polycarbonate formed from a repeating unit represented by the following formula (II) and a repeating unit represented by the following formula (III). Is a copolymer or mixture.

In the above formula (II), R3 to R1G are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 6 carbon atoms, and X is a group represented by the following formula, -11-200540001 (8)

R19 and R20 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.

(III) In the above formula (in), Ru to R18 are each a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 22 carbon atoms, and Y is the following formula,

Ari ~ Ar3 are each independently aryl groups having 6 to 10 carbon atoms, and R21 to R23, R2 5 and R2 6 are each independently hydrogen atom, halogen atom or hydrocarbon group having 1 to 22 carbon atoms, and R24 and R27 are carbon atoms Hydrocarbyl groups of 1 to 20. R3 ~ Rl °, & 19 and R2 in the above formula (1 丨). Examples of the hydroxyl group having 1 to 6 carbon atoms include methyl, ethyl alkyl, and -12-200540001 (9) aryl groups such as phenyl. Examples of the hydrocarbon group represented by Rii to Ri8 in the above formula (III) include, for example, a methyl group, an alkyl group such as an ethyl group, and an aryl group such as a phenyl group. In addition, a hydroxyl group having 1 to 22 carbon atoms represented by R21 to R23, R25, and r26 and a hydrocarbon group having 1 to 20 carbon atoms represented by R24 and R27 can be exemplified by methyl and ethyl alkyl groups such as phenyl Of aryl. Examples of the aryl group represented by An to Alm * 3 include a phenyl group and a naphthalene Φ group. The content of (II) in the polycarbonate formed from the repeating units represented by the above formulae (II) and (III) is preferably 5 to 95 mol% of the total amount of the repeating units. When the content of the ester (II) is less than 5 mol%, it is difficult to obtain a uniform retardation film in the plane because the birefringence of the polymer film becomes large. On the other hand, if the content of '(II) exceeds 95 mol%, the film becomes brittle and easily breakable, and it is not suitable as a film having a retardation. For a better effect, the content of (11) is 20 to 80 mole%, and for a better effect, the content of (11) is 30 to 70 mole%. Especially for applications that require shorter wavelengths, the larger the phase difference, the content of (Π) ranges from 30 to 55. • Molar% is more suitable, while shorter wavelengths have shorter phase differences and smaller characteristics. The content of (II) is preferably 55 to 70 mole%. Wherein the repeating unit represented by the above formula (III) is derived from bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane or 2,2,- Bis (4- (phenyl) phenyl) · Bingyuan, and the repeating unit represented by the above formula (π) comes from a total of 9,9-bis (4-hydroxyphenyl) fluorene (also known as biscresol hydrazone) Polymerized polycarbonate has excellent heat resistance, dimensional stability, and transparency. -13- 200540001 (10) In addition, the transparent film of the thermoplastic synthetic polymer used in the present invention may also contain heat-resistant stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, transparent core agents, permanent antistatic agents, fluorescent Polymer modifiers such as light whiteners. This transparent film is excellent in transparency, and the haze is preferably 5% or less, and the total light transmittance is preferably 85% or more. The glass transition point temperature of the transparent film is preferably 150 to 260 ° C, more preferably 160 to 250 ° C, particularly preferably 170 to 240 ° C, and a temperature lower than 150 ° C, because the dimensional stability is variable. Poor, making the manufacture of transparent films difficult. The transparent film of the present invention is a birefringent film having a retardation. The birefringence of this optical characteristic is represented by retardation (値), and is particularly divided into an in-plane retardation (R 値) and a retardation in the thickness direction (K 値). ), These R 値 and K 値 are each defined by the following formulae (a) and (b). R = Anxd = (nx — ny) xd (a) K = ((nx + ny) / 2- nz) xd (b) The unit of R 値, K 値 is nm, d is the thickness of the film (nm), nx , Ny, nz are defined here as follows. nx: the maximum refractive index in the film plane ny: the refractive index in the direction of the maximum refractive index (nx) and the vertical orientation in the film plane nz: the refractive index in the positive direction of the film plane transparent used in the present invention The thin film 'is that R 所示 shown in the above formula (a) is in the range of 0 to 300 nm' and K 所 not shown in the above formula (b) is -14.

200540001 (11) 1 In a range of 50 to +400 nm, R 値 is preferably in a range of 150 to +300. The above-mentioned transparent film used in the present invention may be manufactured by a manufacturing method, and may be a film manufactured by any method such as an extrusion method, or a method, or any of the above-mentioned stretch film or biaxially stretched film. It is better to learn isotropic and small anisotropy, so it is more suitable to borrow a film. The thickness of the transparent film is preferably 500 μm. 3 0 0 μτη »particularly preferably 5 to 200 μm. The laminated film of the present invention is the hardened layer of the transparent thin film crosslinkable resin described above, and the child layer of the hardened layer can be implemented even if it is only transparent and thin. One side of the film has the other side without the hardened layer, and can be implemented. In order to prevent the abrasion of the polarizing plate, the anti-glare treatment with anti-adhesion and non-diffusion is used as the hard coating treatment. For example, acrylic and polysiloxane-based greases can be used to form hard and slippery hard materials. In order to prevent external light reflection on the surface of the polarizing plate, an anti-adhesion treatment such as forming an anti-reflection film according to the prior art may be used to prevent adhesion treatment with an adjacent layer. The anti-glare treatment is a treatment performed to prevent the surface of the polarizer from obstructing the visual recognition. For example, in the range of -200nm, κ is made by its own conventional liquid casting method or calendering method. The light having an excellent degree of U obtained by the solution casting method, more preferably 1 to 1, has a hydrophilic high component on at least one side and has the above-mentioned hardened layer, a hard coating treatment, and a treatment for anti-reflection purposes. UV-curable dendritic coatings used for other purposes, anti-reflection treatment, etc. can be achieved. In addition, anti-reflection of light on the surface and outside can be prevented by sandblasting. -15-

200540001 (12) The roughening method of the processing method and the embossing processing method. The formation of a fine uneven structure on the above surface to form a fine uneven structure, such as silicon dioxide, zirconium oxide, Transparent fine particles such as tin oxide, indium oxide, cadmium oxide, oxide-based fine particles, and crosslinked or uncrosslinked polymer particles. Formation of fine surface recesses The amount used is about 50 parts by weight based on 100 parts by weight of the thermoplastic, more preferably 5 to 25 parts by weight. It is used to diffuse polarized light and expand the viewing angle and the field angle function. Hardened layer of crosslinkable resin In the present invention, the hardened layer obtained by curing at least the resin of the above-mentioned transparent film further improves the adhesiveness of the polymer layer. The hardened crosslinked resin obtained by hardening the crosslinkable resin crosslinks the reaction layer by external excitation energy. Examples of the crosslinkable resin include an active-wire-curable resin and a thermally-crosslinkable resin which are hardened by irradiating the active wire. Examples of the active-ray-curable resin include ultraviolet rays, and examples thereof include the addition of ultraviolet-curable polyester acryl propylene urethane resin, ultraviolet-curable ultraviolet-curable polyester acrylate resin, and purple transparent particles. For example, when an organic fine particle convex structure made of an average particle size, titanium dioxide, antimony oxide, or an inorganic material having conductivity can be used, the polymer of the fine particles is preferably 2 parts by weight, and the anti-glare layer can also serve as a degree of diffusion. Layer (transparent film with a transparent film and a hydrophilic layer on one side of the enlarged viewing surface) are formed by curing the cross-linking reaction with heat, such as ultraviolet rays and electron beams, and curing the resin by heat. Representative ester resins, UV hard methacrylate resins, exterior hardenable polyalcohol propylene-16-200540001 (13) acid ester resins, etc. Particularly preferred is UV hardenable polyalcohol acrylic vinegar *, and preferred examples thereof include Trimethylolpropane triacrylate, * methylpropane tetraacrylate, pentaerythritol triacrylate, pentaerythracrylate, dipentaerythritol Alcohol pentaacrylate, dipentaerythritol hexaester, alkyl-modified dipentaerythritol pentaerythritol photopolymerizable monomer polymer, these polyalcohol acrylate resins have high hardening hardness, low hardening shrinkage due to high crosslinkability, and because of low Odorless, low toxicity, high 0. Those with acrylic functional groups are preferred, and polyester resins, polyether resins, acrylic resins, moon resins, urethane resins, Alkyd resins, spiro-formaldehyde resins, polybutadiene, polythiol-polyene resins, etc. Examples of heat-crosslinkable resins include epoxy resins, phenoxyphenoxy ether resins, phenoxy ester resins, Acrylic resin, trimer, phenol resin, and urethane resin. Among them, epoxy resin, phenoxy, and phenoxy ether resin are preferable, and phenoxy ester resin, φ ether resin, and phenoxy ester are more preferable. Resin (hereinafter these three are collectively referred to as phenoxylipids) 'These phenoxy-based resins and polyfunctional isocyanate compounds are suitable for use.. Phenoxy-based resins are represented by the following formula (IV) Repeat order

Here, R28 ~ R33 may be the same or different. The resin is hydrogen atom or carbon. The resin is ditrihydroxy; tetraol tetraacrylic acid and its oligocity are large. Therefore, for example, epoxy resin and cyanamide resin are safe. (IV) alkyl groups of 1 to -17- 200540001 (14) 3 formed by phenoxy-based dendrimers, UN is an alkylene group having 2 to 5 carbon atoms, χ is an ether group or an ester group, m is an integer of 0 to 3, and η is an integer of 20 to 300. 'Among them, those in which R28 and RW are methyl, R3Q, R31, r32, and R33 are hydrogen, and 1134 is pentyl are preferable because they are easy to synthesize and can be produced at low cost. Or a polyfunctional isocyanate compound containing two or more isocyanates in the molecule can be exemplified as follows, such as 2,6-tolyl diisocyanate, 2,4. Φ tolyl diisocyanate, tolyl diisocyanate-trimethylolpropane Additives, t-cyclohexyl-1,2-monoisocyanate, m-phenylene diisocyanate, P-phenylene diisocyanate, hexamethylidene diisocyanate, -hexadecane Methylene triisocyanate, isoflurone diisocyanate, i,% naphthalene diisocyanate, tolyl diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane Diisocyanate, gasified diphenylmethane-4,4'-diisocyanate, lysine diisocyanate, lysine triisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenylΦ) phosphorothioate, m-tetramethyl phenylene dimethyl diisocyanate, bu tetramethyl. methyl phenyl monomethyl monoisocyanate, 1,6,11-Eleven Academy Tris cyanate vinegar, -monoisopropyl vinegar-4 -Isopropyl acetate, methylcyclohexyl, dicycloheptyl tricarboxylic acid ester, 2,2,4-trimethyl Stretched six methyl isocyanate, 2,4,4-trimethylhexamethylene diisocyanate extending methyl ester of a polyisocyanate and a polyhydric alcohol or mixtures of these adducts. Among them, from the viewpoint of generality and reactivity, 2,6-tolyl diisocyanate, 2,4-tolyl diisocyanate, tolyl diisocyanate-trimethylolpropane adduct, and hexamethylol Diisocyanate is preferably -18-200540001 (15) The hardened layer of the above-mentioned crosslinkable resin can be obtained by mixing a phenoxy resin and a polyfunctional isocyanate compound. In this case, it can be dissolved and mixed with an excellent solvent that dissolves both, such as It can be dissolved and mixed in methyl ethyl ketone, methyl isobutyl ketone, cellosolve acetate, ethyl acetate, etc., so that a heat-crosslinkable resin solution suitable for coating can be prepared, and this heat-crosslinking can be prepared. The cross-linked resin solution is formed on a transparent film by a wet coating method, and is cured by heat treatment to obtain a cured layer having excellent adhesion to a hydrophilic polymer. The best composition is a phenoxy resin and a polyfunctional isocyanate compound. The mole number of the hydroxyl group in the phenoxy resin is divided by the mole number of the isocyanate in the polyfunctional isocyanate compound. [NCO / OH] Those in the range of 0.2 to 3. Suitable for coating heat-crosslinkable resin solution. In order to control the leveling property of the film, other organic solvents can be added as leveling agents. The leveling agents can be widely used such as alcohol, ether, ester, ketone, amidine , Aliphatic or aromatic hydrocarbons, and preferred examples include methanol, ethanol, isopropanol, butanol, methyl isobutyl methanol, heptanol, octanol, nonanol, 3-methylbutanol, and propylene glycol , 3-methoxybutanol, 3-methyl-3-methoxybutanol, 3,5,5-trimethyl-1-hexanol, 2-ethyl-1-hexanol, cyclohexanol , Benzyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone, 1,4-cyclohexanedione, isoflur Ketones, pyrrolidone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylmethylene, cyclobutane, 1,3,5-trioxane, methyl acetate, ethyl acetate Ester, butyl acetate, pentyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, Butyl lactate, 3--19- 200540001 (16) methoxy Methyl ester, ethyl 3-ethoxypropionate, ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, dibenzyl ether, diethylene glycol diethyl ether, nitromethane, Nitroethane, acetonitrile, γ-butyrolactone, propylene glycol monomethyl ether acetate, toluene, xylene, hexane, cyclohexane, diethyl alcohol ethane, methyl 2-ethoxyacetate , 2-methoxyethanol, 2-butoxyethanol, ethyl acetate, Ν, Ν-dimethylacetamide, dimethylsulfene, Ν, Ν-dimethylformamide, and the like. In addition, in order to control the leveling performance, the addition of a local boiling point solvent at a boiling point of 11 ° C or more under normal pressure can significantly enhance the leveling effect. The boiling point of this temple 丨 cereals are more suitable for use such as 235-trioxane, diethylene glycol diethyl ether, methylhexyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone, 1,4-cyclo Hexanedione, cyclohexyl acetate, γ-butyrolactone, diethylacetoxyethane, ethyl 2-ethoxyacetate, 2-methoxyethanol, 2-butoxyethanol, ethyl acetate Ester, N, N-dimethylacetamide, dimethylmethylene I, N, N-dimethylformamide solvents, or these organic solvents and water can be used in combination of two or more kinds. The thickness of the above-mentioned related hardened layer is preferably 0.01 to 30 μm, more preferably 0.05 to 10 μm, and thinner than 0.01 μm makes it difficult to apply uniformly to the film, and thicker than 30 μm, the film is prone to cracking due to bending. Layer of Hydrophilic Polymer The hydrophilic polymer of the present invention is a polymer having an affinity for water as described in the text, and examples thereof include hydrophilic cellulose, such as methyl cellulose, carboxymethyl cellulose, and hydroxyl group. Cellulose, etc .; Polyvinyl alcohols, such as polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymer, polyvinyl acetal, polyethylene methylal, polyethylene benzyl, etc .; hydrophilic natural polymer compounds, Example -20- 200540001 (17) such as gelatin, casein, gum arabic; hydrophilic polyesters, such as partially tertiary polyethylene terephthalate; hydrophilic polyethylenes, such as poly-N-vinylpyrrolidone, polypropylene Phenamine, polyvinylimidazole, polyvinylpyrazole and the like. These may be used singly or in combination of two or more kinds. The hydrophilic polymer is preferably a composition similar to a polarized photon, for example, polyvinyl alcohols such as polyvinyl alcohol are preferred. Although the above-mentioned related polyvinyl alcohols are known to have large changes in characteristics due to alkalinization and degree of polymerization, the type is not particularly limited as long as sufficient adhesion with the substrate is ensured and a thin layer is formed. Polyvinyl alcohol, which is widely used in general, has a degree of alkalinity of 60 to 99.9 mol% and a degree of polymerization of 100 to 4,000. Considering the characteristics of adhesion and thin layer formation, the degree of alkalinity is preferably 7 0 to 9 9 · 5 m ο 1 ° /. The degree of polymerization is 300 to 3,500, more preferably the degree of alkalinity is 80 to 99.0 mol%, and the degree of polymerization is 400 to 3,000. The above-mentioned related polyvinyl alcohols include modified products, and examples thereof include positive modified products, introduction of modified products such as a carboxyl group, a silanol group, a thiol group, an amino group, and an acetamidine group, acetalization, Modified product of ketalization. To form a coating film on the surface of the hardened layer, the hydrophilic polymer is dissolved in a solvent and used as a solution. Water is preferably used as the solvent. In order to improve the solubility, it can also be dissolved by heating. The dissolved concentration is preferably from 2 to 50 parts by weight, and more preferably from 5 to 30 parts by weight per 100 parts by weight of water. After the solution of the hydrophilic polymer is coated on the above-mentioned hardened layer, it is heat-fixed. The higher the temperature and the longer the time, the stronger the heat-fixation. It is preferably 100 ° C for more than 1 minute, more preferably 100. ° C lasts for more than 5 minutes, preferably 100 ° C for more than 10 minutes. It is hoped that the adhesive layer -21-200540001 (18) can be formed without peeling. A layer of a hydrophilic polymer is formed, and the surface of the hardened layer is uniformly coated with the solution by a wet coating method and then dried. Examples of the wet coating method include a spin coating method, a Meyer bar coating method, The forward rotation roll coating method, the engraved roll coating method, the reverse roll coating method, and the like. When an aqueous solution of a hydrophilic polymer compound is formed into a thin layer by a wet coating method, foaming tends to occur and it is likely to cause coating defects. Therefore, a foam inhibitor is added to the aqueous solution of a hydrophilic polymer compound. It is preferable that the antifoaming agent suppresses bubbles generated from the solution. The antifoaming agent or the antifoaming agent is not particularly limited, and examples thereof include amine-based, silicon dioxide, polysiloxane, polysiloxane, and wax. . The thickness of the layer of the hydrophilic polymer is preferably 1 to 20 μm, more preferably 1 to 15 μm, and most preferably 1 to 10 μm. The manufacturing method of the laminated film of the present invention All the manufacturing methods of the laminated film of the present invention are as described above. The transparent film of a thermoplastic synthetic polymer is coated with a solution of a crosslinkable resin on at least one side and cured. A cured layer of a cross-linkable resin is formed, and then a solution of a hydrophilic polymer is applied on the surface of the cured layer and heat-fixed to form a layer of the hydrophilic polymer. Field of Use of Laminated Film The laminated film of the present invention provides a layer of a hydrophilic resin on the outermost surface through a hardened layer of a crosslinkable resin on at least one side of the transparent film to provide the above-mentioned related hydrophilicity. Polarized light bonded with resin layer and polaron-22- 200540001 (19) The surface of polarized photon that is not adhered with the layer of hydrophilic resin is generally protected with a thin film such as triethyl cellulose. The laminated film of the present invention is used as a polarizing plate having an optical compensation function, and it can form a liquid crystal display device having a wide viewing angle and excellent display quality such as contrast. It can be used for TFT liquid crystal display devices such as twisted nematic mode, vertical alignment mode, OCB (Optically Compensated Bend) alignment mode, on-board switching mode, etc. When applied to practical applications, it can be used as a polarizer. All applications, such as a liquid crystal display device, can be used to form a transmissive and reflective type, or a transflective type, which is formed by using a backlight or a reflective plate and a semi-transparent reflective plate on the lighting system, and other displays using a polarizing plate. The device includes a liquid crystal projector, a ferroelectric liquid crystal, an anti-ferroelectric liquid crystal, and an organic EL display device. The polarizing plate on which the laminated film of the present invention is mounted is bonded to the liquid crystal panel using an adhesive layer. At this time, it is prepared in the form of an adhesive layer on the polarizing plate. The exposed surface of the adhesive layer is falsely adhered to prevent pollution and the like. The separator can be formed to cover the adhesive layer. The adhesive layer may also contain, for example, resins of natural and synthetic materials, especially resins that impart adhesion, and fillers, pigments, and colorants made of glass fibers, glass beads, metal powders, and other inorganic powders. Additives, such as antioxidants, may also be adhesive layers containing fine particles and exhibiting light diffusivity. The attachment of the polarizing plate to the polarizing plate can be performed by an appropriate method, and examples thereof include a solvent made of one or a mixture of appropriate solvents such as toluene and ethyl acetate, and adjusted to the base polymer or its composition- 23- 200540001 (20) Dissolve or disperse the adhesive to a concentration of about 10 to 40% by weight. Thicken the adhesive. Use an appropriate spreading method such as casting method and coating method to spread the treatment board to form an adhesive layer, or It is spread on a carrier film such as polyethylene terephthalate to form an adhesive layer, and this adhesive layer is moved to a light board. The thickness of the adhesive layer can be appropriately determined according to the purpose of use and the adhesion, and is preferably 1 to 500 μm, more preferably 2 to 200 μm, and most preferably 10 to 100 μm. The separator of the adhesive layer can be a suitable thin material such as plastic film, rubber Ji, paper, cloth, non-woven fabric, net, foamed sheet and metal foil, etc. If necessary, it can be made of polysiloxane and long chain. Appropriate release agents such as alkane-based and molybdenum sulfide. [Embodiments] Examples The material properties described in this specification were obtained through the following evaluations. (1) Measurement of R 値, K 値 The phase difference R 値 of the product of the birefringence Δη and the film thickness d, and the phase difference in the vertical direction on the opposite side is K 値, measured by the trade name "KOBRA21-ADH" of Oji Measuring Instruments . R 値 is measured when the incident light is perpendicular to the surface of the film R = An · d = (nx-ny) xd, K = ((nx + ny) / 2-nz) χ 値, K 値 The unit is nm, nx, ny, and nz are defined here as follows. nx: the maximum refractive index in the plane of the film, special polarizing layer such as polarizing diol and biasing force, etc.

The inner part is made of steel, d, R -24-200540001 (21) ny: the refractive index in the direction of the maximum refractive index (nx) and the vertical orientation in the film plane nz: the refractive index in the positive direction of the film plane (2) Evaluation of adhesion with polyvinyl alcohol 15 parts by weight of polyvinyl alcohol resin (KURARAY PVA117, degree of polymerization 1 700, degree of alkalinity 98.5) were heated and dissolved in 85 parts by weight of water to prepare a polyvinyl alcohol solution. This polyvinyl alcohol solution was coated on a laminated film, and then uniformly developed by a Meyer bar coating method, and then dried in a 60 t: oven for 5 minutes to laminate a polyvinyl alcohol resin layer having a thickness of 6 μm. The adhesion between the polyvinyl alcohol resin layer and the laminated films obtained in the examples and comparative examples was obtained by bonding a cellophane tape made of NIC H IB AN to a region cut into 100 squares of 1 mm square. When tearing off in the vertical direction, it was evaluated whether or not peeling was caused. X: Insufficient adhesiveness When only one of the 100 is peeled off. 0: Adhesiveness is ensured without peeling. (3) Dimensional stability evaluation method As for the dimensional change of the laminated film, the evaluation device uses real made by LASERTEC. -time scanning laser microscope: trade name "1 LM2 1 D", measuring the initial size and the size after the heat resistance test. The test conditions are for 80 ° CDRY, 60 t: 9 0% R Η, each observed until Up to 1,000 hours, the evaluation criteria were set to three stages: no change (0), contraction, and expansion. (4) Evaluation as a polarizing plate Regarding the laminated film with excellent adhesion to polyvinyl alcohol according to the present invention, as a protective film for polarizers, a polarizing plate was prepared according to the following method, and implemented -25-200540001 (22) Environmental resistance Characteristic test (in Table 1, it is 0 when it is excellent). Polyvinyl alcohol film with a thickness of 120 μm was immersed in an aqueous solution containing 1 part of iodine, 2 parts of potassium iodide, and 4 parts of boric acid, and was stretched 4 times at 50 ° C to obtain polarized photons. The following (i) ~ (v In step), a polarizing plate is formed by bonding polarized photons and a hydrophilic polymer layer of a laminated film. How to make a polarizing plate (i) Laminate a B-layer film with a length of 30 cm and a width of 18 cm, and place the hydrophilic polymer layer on the glass plate with the upward direction. (Ii) The same size as the laminated film. The above-mentioned polarizer is immersed in a polyvinyl alcohol adhesive layer having a solid content of 2% by weight for 1 to 2 seconds. (iii) The excess adhesive adhered to the polarizer of (ii) above is gently removed, and it is placed on the laminated film sample of (i) above, and the laminated film and the adhesive are laminated in a manner of bonding. Configuration. (iv) Manually operate the roller to remove excess adhesive and air bubbles from the top of the φ laminate of the laminated polarizer and the laminated film to adhere. The pressure of the manual operation of the roller is about 2 ~ 3kg / cm2, the speed of the roller It is about 2m / min. • (v) Place the sample obtained in (iv) in a dryer at 80 ° C for 2 minutes to obtain a polarizing plate. (5) Measurement of optical characteristic polarization degree The measurement of transmittance uses Hitachi (Trade), trade name "U-4 000 S pectr 〇ph 〇t 〇meter". During the measurement, two polarizing plates are used to measure parallel and vertical transmission. The transmittance and polarization are calculated as follows. The parallel transmittance is the measured transmittance with the absorption axis of polarized light -26-200540001 (23) in parallel and the two pieces are superimposed. The vertical transmittance is the absorption axis of the polarized light with the vertical direction. Polarized transmittance measured with two overlaps = ((H1-H2) / (H1 + H2) 丨 丨 / 2 H1: Parallel transmittance, H2: Vertical transmittance Polarization plate Environmental resistance test The test conditions are for 80 ° C DRY, 60 ° C 90% RH, each observed until 1,000 Ohr, to evaluate the optical characteristics of polarization changes before and after the test. When the change in the degree of polarization is within 1%, the environmental resistance is determined to be 0, and it is judged to be excellent. Otherwise, it is determined to be X, and judged to be deteriorated. (6) Optical compensation effect of the liquid crystal display device The optical compensation effect was investigated using Fujitsu's LCD monitor VL-1 51 VA. In the liquid crystal cell, the polarizing plate obtained by the present invention is configured to have the same retardation axis arrangement as a commercially available state, and a commercially available product is used on the surface. The evaluation is compared with a commercially available product, and the comparison and the visual field angle stomach are compared. The person who can obtain the optical compensation effect is excellent (0), and the person who cannot obtain it is evaluated as inferior (X). Example 1 A reaction device provided with a stirrer, a thermometer, and a reflux cooler was charged with an aqueous sodium hydroxide solution and ion-exchanged water, and bis (3-methyl-4_ via-27- 200540001 (24) ylphenyl)- 3,3,5-trimethylcyclohexane and biscresol hydrazone were dissolved at a ratio of mol%), a small amount of bisulfite was added to chloroformin, and phosgene (Phosgene) was added at 20 ° C. Blow in over time, p-tert-butylphenol was added to make triethylamine to 30. (: The reaction is completed after stirring for about 3 hours, the organic phase is reversed, and the composition ratio of the copolymerized polycarbonate obtained by evaporating methane chloride to obtain a copolymerized polycarbonate is about the same as the monomer addition amount. 23 6 ° C. This copolymerized polycarbonate was dissolved in dichloromethane, and the glue solution was measured in%. The glue solution was cast on a steel drum, peeled off, and dried. The stretcher is stretched by a uniaxial stretching of 1.8 times in the longitudinal direction, the obtained uniaxial tension is 1 15 μm, the amount of residual solvent in the film is 1.3, and the tenter is stretched 2.1 times at 240 ° C in the transverse direction. The phase difference of the stretched film obtained by successive biaxial stretching in the transverse direction is K = 273 nm. On this stretched film, a crosslinkable layer is made of a crosslinkable resin, and the hardened layer is mixed with 20 Part by weight of phenoxy tree! PKHM-30 manufactured by CARBIDE CORPORATION, a solvent of methyl ethyl ketone and 20 parts by weight of 2-ethoxy, and 20 parts by weight are mixed as a polyfunctional isocyanide. Acid) made by Japan Polyurethane Co., Ltd. CORONET, coated with Meyer rod coating method, 1 Heat treated at 30 ° C for 5 minutes, 2 μm hardened layer. 50: 50 (, then emulsified with about 60 minutes, the ester should be taken after the addition should be completed, the same obtained, in addition, made into 18 weights, it was stretched at a continuous thickness of 230 ° C:%, this The film is stretched, so that R = 5 2nm, resin hardened UNION 40 0 parts by weight of ethyl acetate (hardener liquid, this coating liquid, forming a thickness of -28 · 200540001 (25) more than this hardened layer A thin layer made of a hydrophilic polymer is formed thereon. The thin layer is obtained by heating and dissolving 15 parts by weight of polyvinyl alcohol resin (KURARAY PVA117, degree of polymerization 1 700, degree of alkalinity 98.5) in 85 parts by weight of water. The aqueous solution is formed as a coating solution. This coating solution is coated with a Meyer bar coating method, and heat-treated at 100 ° C for 5 minutes to form a thin layer with a thickness of 2 μm, and the outermost surface of one side of a transparent thermoplastic synthetic polymer film is obtained. Laminated film (protective film for polarizers) with a film made of a hydrophilic polymer on it. For this protective film for polarizers, the temperature is 80 ° C DRY, 60 ° C 90% RH, each to 1,000hi. * Dimensional stability evaluation to date, but no size observed At the same time, the optical characteristics of the phase difference 値 and K 变化 were also measured, and no change was observed. The adhesion test between the protective film for polarizers and polyvinyl alcohol was performed, and the protective film for polarizers was hydrophilic. On the surface of the thin polymer layer, the polyvinyl alcohol solution was coated with a Meyer bar coating method, and dried in an oven at 60 ° C. for 5 minutes to form a polyvinyl alcohol layer with a thickness of 10 μτη on a protective film for polarizers. The adhesion test between the polyvinyl alcohol layer and the protective film for polarizers was performed by a cross-cut test, but excellent adhesion was obtained without peeling being observed at all. Next, a polarizing plate was produced using the protective film for polarizers described above. The sample of Example 1 had an excellent polarization degree of 99.2%, and was confirmed to have sufficient polarizing plate characteristics. In addition, in an environmental resistance test of 1,000 hours at 80 ° CDRY and 60 ° C 90% RH, No polarization characteristic was observed to be excellent. -29- 200540001 (26) A polarizing plate using the laminated film obtained by the present invention was mounted on a liquid crystal monitor. At this time, the present invention was made The laminated film was placed on the side of the liquid crystal cell, and was adhered through an adhesive, and it was confirmed that the display screen of the liquid crystal monitor obtained thereby had excellent contrast and wide viewing angle. Example 2 Equipped with a stirrer, a thermometer, and a flow The reaction device of the cooler was filled with an aqueous sodium hydroxide solution and ion-exchanged water, and bisphenol A and biscresol hydrazone were dissolved at a ratio of 50:50 (mol%), and a small amount of bisulfite was added, followed by adding Dichloromethane was blown with phosgene at 20 ° C for 60 minutes, and then p-tert-butylphenol was added to emulsify it. Triethylamine was added to stir at 3 for about 3 hours to end the reaction. After the reaction, the organic phase was taken out, and the methane chloride was evaporated to obtain a copolymerized polycarbonate. The composition ratio of the obtained copolymerized polycarbonate and the amount of monomers were the same. In addition, the glass transition point temperature of the polymer was 2 1 3 ° C. This copolymerized polycarbonate was dissolved in dichloromethane to prepare an 18% by weight dope solution. This dope solution was cast on a steel drum, and it was continuously peeled off and dried, and then used. The roller stretcher performs uniaxial stretching at a length of 1.8 times in the longitudinal direction at 2 0 ° C. The thickness of the obtained uniaxially stretched film is 119 μπα, and the amount of residual solvent in the film is 丨 2% by weight. The tenter was stretched 2.1 times in the transverse direction at 217 t, and the phase difference 的 of the stretched film obtained by the successive biaxial stretching was R = 49 nm, K = 268 nm. Then, it was performed with an example. 1 The same method was used to obtain a protective film for polarizing -30-200540001 (27). Evaluation of the protective film for polarizers was performed in the same manner as in Example 1 and the same excellent results as in Example 1 were obtained. The polarizing plate using the laminated film obtained by the present invention is mounted on a liquid crystal monitor. At this time, the method of setting the laminated film of the present invention on the liquid crystal cell side is adhered via an adhesive, and it is confirmed that the obtained The LCD display screen has excellent contrast and wide viewing angle. Comparative Example 1 Similar to Example 2, a copolymerized polycarbonate obtained by using bisphenol A and biscresol fluorene at a ratio of 50:50 (mol%) was used. This copolymerized polycarbonate was dissolved in dichloromethane to prepare an 18% by weight dope solution. This dope solution was cast on a steel drum, and it was continuously peeled off and dried, and then used. The roller stretcher was uniaxially stretched 1.8 times in the longitudinal direction at 210 ° C. The thickness of the obtained uniaxially stretched film was φ9 μηι, and the amount of residual solvent in the film was 1.2% by weight. This film was stretched 2.1 times in the transverse direction with a tenter at 217 ° C. The phase difference 値 of the stretched film obtained by successive biaxial stretching was% R = 51nm, κ = 27 3 nm 〇 Here, this stretched film is directly used as a protective film for polarizers. For this polarizer protective film, dimensional stability evaluations of 80 ° CDRY and 60 ° C 90% RH were performed up to 1,000 hours, but no dimensional change was observed, and the phase difference 値 and K 値 were also measured. No change in optical characteristics was observed. -31-200540001 (28) The adhesion test between the protective film for polarizers and polyvinyl alcohol was performed. For the surface of a thin layer of a hydrophilic polymer with a protective film for polarizers, a polyvinyl alcohol solution was used for Mayer rods. The coating method coater was dried in an oven at 60 ° C for 5 minutes to form a polyvinyl alcohol layer with a thickness of 0 μm on the protective film for polarizers. The adhesion between the polyvinyl alcohol layer and the protective film for polarizers In the test, a cross-cut test was performed, and the polyvinyl alcohol layer was completely peeled off, and sufficient adhesion between the protective film for polarizers and polyvinyl alcohol could not be obtained. Comparative Example 2 Similar to Example 2, a copolymerized polycarbonate obtained using bisphenol A and biscresol fluorene at a ratio of 50:50 (mol%) was used. This copolymerized polycarbonate was dissolved in dichloromethane to prepare an 18% by weight dope solution. This dope solution was cast on a steel drum, and it was continuously peeled off and dried, and then used. The roller stretcher was uniaxially stretched at 1.8 ° times in the longitudinal direction at 210 ° C. The thickness of the obtained uniaxially stretched film was φ 1 19 μm, and the amount of residual solvent in the film was 1.2% by weight. This film was stretched 2.1 times in the transverse direction with a tenter, and the phase difference 的 of the stretched film obtained by successively biaxial stretching was R = 54nm, _K = 2.70nm. A cross-linked resin is used to produce a hardened layer on this stretched film. The hardened layer is made of 20 parts by weight of a phenoxy resin, PKHM-30, manufactured by UNION CARBIDE CORPORATION, and 40 parts by weight of a methyl ethyl solvent. Ketone and 20 parts by weight of 2-ethoxyethyl acetate, 20 parts by weight of polyisocyanate (hardener), which is polybenzyl-32-200540001 (29) made from urethane After CORONET, a coating liquid was prepared. This coating liquid was coated with a Meyer bar coating method and heat-treated at 130 ° C for 5 minutes to form a hardened layer with a thickness of 2 μm. This stretched film is used here as a protective film for polarizers as it is. For this polarizer protective film, dimensional stability evaluations of 80 ° C DRY and 60 ° C 90% RH up to 1,000 hours were performed, but no dimensional change was observed, and phase differences 値, K 値 were also measured. No change in optical characteristics was observed. Next, the adhesion test between the protective film for polarizers and polyvinyl alcohol was performed. For the surface of the thin layer of the hydrophilic polymer having a protective film for polarizers, a polyvinyl alcohol solution was applied by a Meyer bar coating method. After drying in an oven at 60 ° C for 5 minutes, a polyvinyl alcohol layer with a thickness of 10 μm was formed on the protective film for polarizers. The adhesion test between the polyvinyl alcohol layer and the protective film for polarizers was subjected to a cross-cut test. The vinyl alcohol layer was completely peeled off, and sufficient adhesion between the protective film for polarizers and polyvinyl alcohol could not be obtained. Comparative Example 3 Similar to Example 2, a copolymerized polycarbonate obtained using bisphenol A and biscresol fluorene at a ratio of 50:50 (mol%) was used. This copolymerized polycarbonate was dissolved in dichloromethane to prepare an 18% by weight dope solution. This dope solution was cast on a steel drum, and it was continuously peeled off and dried, and then used. The roller stretcher was uniaxially stretched at 1.8 ° times in the longitudinal direction at 210 ° C. The thickness of the obtained uniaxially stretched film was 119 μm, and the amount of residual solvent in the film was 1.2% by weight. This film was stretched by 2 ten times in the transverse direction with a tenter at 2 1 7 ° C, and the phase difference 値 of the stretched film obtained by successively -33- 200540001 (30) biaxial stretching was R = 54nm, K = 2 7 Onm. Next, a thin layer made of a hydrophilic polymer is formed on the stretched film. The thin layer is made of 15 parts by weight of a polyvinyl alcohol resin (KURARAY PVA117, polymerization degree). 1 700, degree of alkalinity 98.5) The aqueous solution obtained by heating and dissolving in 85 parts by weight of water was formed into a coating solution. This coating solution was coated by a Meyer bar coating method and heat-treated at 100 ° C for 5 minutes to form a coating solution. With a thickness of 2 μm, a laminated film (a protective film for polarizers) having a film made of a hydrophilic polymer on the outermost surface of a transparent thermoplastic synthetic polymer film is obtained. For this polarizer protective film, dimensional stability evaluations of 80 ° C DRY and 60 ° C 90% RH up to 1,000 hours were performed, but no dimensional change was observed, and phase differences 値, K 値 were also measured. No change in optical characteristics was observed. Next, the adhesion test between the protective film for polarizers and polyvinyl alcohol was performed. For the surface of the thin layer of the hydrophilic polymer having a protective film for polarizers, a polyvinyl alcohol solution was applied by a Meyer bar coating method. In a 6 ° C oven for 5 minutes, a polyvinyl alcohol layer with a thickness of 10 μm was formed on the protective film for polarized photons. A cross-cut test was performed on the adhesion test between the polyvinyl alcohol layer and the protective film for polarized photons. Polyethylene The alcohol layer is completely peeled off, and sufficient adhesion between the protective film for polarizers and polyvinyl alcohol cannot be obtained. -34- 200540001

1 ______ (3I wash other 〇〇〇 cluck ^ si C 纮 昶 鼢 mmmmm ^ step s 运 纪 纪 _ 螗 Click e purple 〇 ± Π 〇〇 毖 mw lice mmm you produce s a > s #: s Adhesion of meter-long chase 鼷 III and polyvinyl alcohol layer XXXXXX Optical property stability Dimensional stability 0000 Thin layer soil condensed crosslinked resin hardened layer Example I Example 2 Comparative Example I Comparative Example 2 Comparative Example 3 -35- 200540001 (32) Example 3 Except that 100 mol% of bisphenol A was used as a monomer, 'the rest was performed the same operation as in Example 1' to obtain only from bis Polycarbonate prepared by 的 A, the glass transition point temperature of the obtained polycarbonate was 158 ° C ° This polycarbonate was dissolved in dichloromethane to make a 18% by weight dope solution. This glue solution was cast on a steel drum, and it was continuously peeled off and then dried. It was stretched by a roll stretcher at 1 55 ° C for 1.1 times in the longitudinal direction, and the obtained uniaxial tension was obtained. The thickness of the stretched film is 1 10 μm, and the amount of residual solvent in the film is 1 1% by weight. This film was stretched at a lateral direction of 1.15 VC with a tenter at 1.5 times. The phase difference 値 of the stretched film obtained by successive biaxial stretching was R = 55 nm. , K = 2 7 2 nm. Next, the same method as in Example 1 was performed to obtain a protective film for polarized light. The same method as in Example 1 was used to evaluate the protective film for polarized light, and the same excellent results as in Example 1 were obtained. Example 4 The same operation as in Example 2 was performed except that KURARAY PVA405 (basicity 80 mol%, polymerization degree 5 00) was used as the hydrophilic polymer compound, and the phase difference 由 r = 50 nm, K = A film made of a copolymerized polycarbonate made of bisphenol A and biscresol fluorene at 270 nm. Next, the same method as in Example 1 was performed to obtain a polarizer protection-36- 200540001 (33) film. The protective film for polarizers was evaluated in the same manner as in Example 1 and the same excellent results were obtained as in Example 1. Example 5 Except that KURARAY PVA124 (degree of alkalinity: 98.5 mol%, degree of polymerization: 2400) was used for high hydrophilicity Outside molecular compounds The rest were subjected to the same operation as in Example 2 to obtain a film formed of a copolymerized polycarbonate formed of bisphenol A and biscresol 芴 with a phase difference 値 R = 50nm and K = 270nm. In the same manner as in Example 1, a protective film for polarizers was obtained. The protective film for polarizers was evaluated in the same manner as in Example 1 and the same excellent results as in Example 1 were obtained.

Example 6 The same operation as in Example 2 was performed except that KURARAY PVA C-U8 (cationically modified product, degree of alkalinity 98.5 to 99.5 mol%, degree of polymerization 1 800) was used as the hydrophilic polymer compound to obtain Film made of copolymerized polycarbonate made of bisphenol A and biscresol 芴 with a retardation 値 R = 50nm and K = 270nm. Next, the same procedure as in Example 1 was performed to obtain a protective film for polarizers. The protective film for polarizers was evaluated in the same manner as in Example 1 -37- 200540001 (34), and the same excellent results as in Example 1 were obtained. Example 7 The same procedure as in Example 2 was performed except that KURARAY PVA M-1 15 (modified mercaptan introduction, degree of alkalinity 97.0 to 99.0 mol%, degree of polymerization 1 8 00) was used as the hydrophilic polymer compound. , A film formed of a copolymerized polycarbonate made of bisphenol A and biscresol 相位 with a phase difference 値 R = 50nm and K = 270nm was obtained. Next, the same procedure as in Example 1 was performed to obtain a protective film for polarizers. The protective film for polarizers was evaluated in the same manner as in Example 1 and the same excellent results as in Example 1 were obtained. The laminated film of the present invention is used as a polarizing plate having an optical compensation function, and can form a liquid crystal display device having a wide viewing angle and excellent display quality such as contrast. It can be used for TFT liquid crystal display devices such as twisted nematic mode, vertical alignment mode, OCB (Optically Compensated Bend) alignment mode, on-board switching mode, etc. When applied to practical applications, it can be used as a polarizing plate. All applications, such as liquid crystal display devices, can be used to form transmissive and reflective types, or transflective types using backlights or reflective plates and transflective reflective plates in lighting systems. Display devices using other polarizing plates can be used. Those using liquid crystal projectors, ferroelectric liquid crystals, anti-ferroelectric liquid crystals, and organic EL display devices are listed. According to the present invention, it is possible to provide a film made of a hydrophilic polymer compound on the outermost surface of one side of a transparent thermoplastic synthetic polymer film. (38) 200540001, and the size of the film is stable in the environment. A stabilizing protective film having a parallax characteristic can be provided. When a liquid crystal display element with a low number of components is reduced, there is a hardened layer between the transparent films, as a laminated film for a protective film for polarizers with excellent ring resistance. A polarizer with phase difference characteristics as an optical compensation function, excellent phase compatibility, and excellent adhesion to polarizers can be used to produce a polarizing plate with optical compensation functions, and the number of processing steps can be achieved. The effect of cost.

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Claims (1)

200540001 (1) X. Patent application scope 1. A laminated film characterized by the crosslinkability of at least one side of (A) a transparent film made of a thermoplastic synthetic polymer and (B) a transparent film (A) The hardened layer of the resin and the layer of the hydrophilic polymer on the surface of the (C) hardened layer (B). The transparent film described above satisfies the following formulae (1) and (2) (1). ; (nx— ny) xd < 300nm (2) -1 5 0 < {(nx + ny) / 2— nz} xd < 400nm where nx is the maximum refractive index in the plane of the film, and ny is between Represents the refractive index in the nx direction perpendicular to the inside of the film plane, nz is the refractive index in the positive direction of the film plane, and d is the thickness (nm) of the film, and is used to adhere to polarizers to make a polarizing plate. 2. The laminated film according to item 1 of the application, wherein the hydrophilic high molecular compound is polyvinyl alcohol. 3. The laminated film according to item 1 or item 2 of the patent application scope, wherein the curing layer of the crosslinkable resin is a layer obtained by curing a mixture of a phenoxy resin and an isocyanate compound. 4. The laminated film according to any one of claims 1 to 3, wherein the transparent film is made of polycarbonate. 5. For example, the laminated film according to item 4 of the patent application, wherein the polycarbonate -40-200540001 (2) ester is made of copolymerized polycarbonate, and the hydroxy compound constituting the monomer component of the copolymerized polycarbonate Is represented by the following formula (I), Here, 1 and R2 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 6 carbon atoms. 6. The laminated film according to item 5 of the patent application, wherein the proportion of the repeating units derived from the hydroxy compound (I) in the copolymerized polycarbonate accounts for 5 to 95 mol% of the total repeating units. 7. For example, the laminated film of item 5 or item 6, wherein the copolymerized polycarbonate is a mixture of two or more copolymerized carbonates, and the average molecular weight of the mixture is 2,000 to 1. 00,000. 8. For example, the laminated film of the first patent application scope is a transparent film made of a thermoplastic synthetic polymer, and at least one side of the transparent film is coated with a solution of a crosslinkable resin and cured to form a crosslinkable resin. A layer is formed by coating a hydrophilic polymer solution on the hardened layer and thermally fixing the layer to form a hydrophilic polymer. The transparent film described above satisfies the following formulae (1) and (2) (1). O < (nx— ny) xd < 3 OOnm (2) -1 5 0 < {(η x + ny) / 2— ηζ} xd < 400nm -41-200540001 (3) where nx is the in-plane area of the film The maximum refractive index, ny is a refractive index in a direction that is perpendicular to the film surface in the nx direction, nz is the refractive index in the positive direction of the film surface, and d is the thickness (nm) of the film. 9. A polarizing plate characterized by being formed of a polarized photon and a laminated film of item 1 of the patent application scope adhered to at least one side of the polarized photon. 10. A method of use, characterized in that the laminated film according to item 丨 of the patent application is used as a protective film for polarizers. -42- 200540001 Unclear statement without Jane J & amp:: The fee is the symbol of the chart. It refers to the design of the table. It refers to the design of the table. This refers to the CC. 78. If there is a chemical formula in this case, please disclose the best Chemical formula showing the characteristics of the invention: None-4-