TW201728650A - Resin composition and optical film using same - Google Patents

Abstract

Provided are: a resin composition which exhibits excellent transparency and coatability, while having low possibility of contaminating liquid crystals; and an optical film which uses this resin composition. A resin composition which contains a polyvinyl alcohol and a polyester, and wherein the polyester has, as a substituent, a carboxyl group and/or a salt of a carboxyl group. It is preferable that the polyvinyl alcohol is a homopolymer or a copolymer that comprises vinyl alcohol as an essential monomer; and it is also preferable that the polyvinyl alcohol has an acetoacetic acid ester group.

Description

Resin composition and optical film using the same

The present invention relates to a resin composition and an optical film using the same, and more particularly to a resin composition which is excellent in transparency and coating properties and has low liquid crystal contamination, and an optical film using the same.

The water-soluble polymer such as polyvinyl alcohol is widely used in various applications such as paints, inks, adhesives, optical films, and the like. For example, Japanese Patent Publication No. 1 and 2 propose a composite film comprising a layer of a water-dispersible polyester having a polyvinyl alcohol and a sulfooxy group, and Japanese Patent Document 3 proposes to contain a polyvinyl alcohol. And a coated film product of an aqueous binding layer of a water-dispersible copolyester.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Publication No. 2001-510110

Patent Document 2: Japanese Patent Publication No. 4204188

Patent Document 3: Japanese Patent Publication No. 2004-529750

A resin composition containing a polyvinyl alcohol, which is used for an optical film for a flat panel display, a coating material for an optical film, a sealing compound for a liquid crystal dropping method, and the like, in addition to high transparency or coatability, Low liquid crystal contamination is also required. However, the resin composition containing a polyvinyl alcohol is inevitably insufficient for such physical properties, and further improvement is required today.

Therefore, an object of the present invention is to provide a resin composition which is excellent in transparency and coating property and which has low liquid crystal contamination, and an optical film using the same.

As a result of intensive research, the present inventors have found that a resin composition containing a polyvinyl alcohol and a polyester having a specific structure is excellent in transparency and coating property, and liquid crystal contamination is low, and is suitable. The present invention is used for an optical film for a flat panel display, a coating material for an optical film, a sealing agent for a liquid crystal dropping method, and the like.

In other words, the resin composition of the present invention contains a resin composition of a polyvinyl alcohol and a polyester, and the polyester has a carboxyl group and/or a carboxyl group as a substituent.

In the resin composition of the present invention, the aforementioned polyvinyl alcohol system Vinyl alcohol can be used as a homopolymer or copolymer of the necessary monomers. Further, in the resin composition of the present invention, it is preferred that the polyvinyl alcohol has an acetamidine acetate group. Further, in the resin composition of the present invention, the degree of saponification of the polyvinyl alcohol is preferably 85 or more. Further, in the resin composition of the present invention, the content of the polyester is preferably from 0.5 to 50% by mass based on the solid content.

Further, the resin composition of the present invention preferably contains a crosslinking agent. Further, in the resin composition of the present invention, the crosslinking agent is preferably an oxazoline or a carbodiimide compound.

The optical film of the present invention is characterized by being composed of the resin composition of the present invention.

According to the present invention, it is possible to provide a resin composition which is excellent in transparency and coating property and which has low liquid crystal contamination, and an optical film using the same.

Best form for carrying out the invention

Hereinafter, the resin composition and the optical film of the present invention will be described in detail. The resin composition of the present invention contains a resin composition of a polyvinyl alcohol and a polyester, and a polyester having a carboxyl group and/or a carboxyl group as a substituent. Hereinafter, the polyvinyl alcohol and the polyester of the resin composition of the present invention will be described in detail.

<polyvinyl alcohol>

In the resin composition of the present invention, a polyvinyl alcohol may be a homopolymer or a copolymer of vinyl alcohol as a necessary monomer. In general, in addition to a polyvinyl alcohol polymerized as a polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl modified polyvinyl alcohol, acetamidine Acetate-modified polyvinyl alcohol, hydroxymethyl-modified polyvinyl alcohol, amine-modified polyvinyl alcohol, ester-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, guanamine Modified polyvinyl alcohol, styrylpyridinium modified polyvinyl alcohol, quaternary ammonium base modified polyvinyl alcohol, allyl modified polyvinyl alcohol, hydroxypropenyl modified polyvinyl alcohol, Carbamate-modified polyvinyl alcohol, ether-modified polyvinyl alcohol, phosphate-modified polyvinyl alcohol, acetal-modified polyvinyl alcohol, butyral-modified polyethylene Alcohol, stanol-modified polyvinyl alcohol, modified polyvinyl alcohol having a 1,2-diol structure in a side chain; having vinyl acetate and copolymerization a saponified product of a monomeric copolymer or the like. Among these, the acetamidine acetate-modified polyvinyl alcohol is crosslinked by heat treatment, and thus it is suitably used.

Examples of the copolymerizable single system include unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acrylic acid, and methacrylic acid, and esters thereof, vinyl, propylene, and the like. Α-olefin, allyl sulfonic acid, methallyl sulfonic acid, sodium allyl sulfonate, sodium methallyl sulfonate, sodium sulfonate, sodium sulfonate monoalkyl maleate, two Sodium sulfonate alkyl maleate, N-methylol acrylamide, acrylamide alkyl sulfonate alkali salt, N-vinyl pyrrolidone, N-vinyl pyrrolidone derivative, and the like.

In the resin composition of the present invention, the polyvinyl alcohol may be used singly or in combination of two or more kinds. The polystyrene-based weight average molecular weight (Mw) by gel permeation chromatography (GPC) of polyvinyl alcohol is 10,000 to 200,000, and the degree of saponification (hydrolysis rate) is 85 or more, particularly 85 to 100, and water resistance. It is better to improve the durability of the film and improve the durability of the film.

As the polyvinyl alcohol type, commercially available products can be used, and examples thereof include GOHSENOLNL-05, NH-18, NH-20, NH-26, NM-14, AH-17, A-300, GM-14L, and GL-. 05, KL-05, GH-23, KH-17 (Nippon Synthetic (NIPPON GOHEI) Chemical Industry Co., Ltd.); GOHSENXZ-100, Z-200, Z-300, Z-410, T-330H (Japanese Synthetic Chemistry Industrial Co., Ltd.); Nichigo G-Polymer OKS-1081, OKS-1083 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.); VF-17, V-S20 (manufactured by JAPAN VAM &POVAL); KURARAYPOVALPVA-103, PVA- 105, PVA-117, PVA-205, PVA-217, PVA-405, PVA-420 (KURARAY company); DENKA POVALK-05, K-17C, K-24E, H-12, H-17, B- 05, B-17 (made by Electric Chemical Industry Co., Ltd.), etc.

<polyester>

The polyester of the resin composition of the present invention has at least one of a carboxyl group as a substituent and a salt of a carboxyl group. Such polyesters are dissolved in water, and the water is dispersed and emulsified or dissolved in alkaline water. In the polyester of the resin composition of the present invention, the salt of the carboxyl group is an alkali metal salt, an ammonium salt or an amine salt. It is preferred that the effect of the present invention is obtained.

The acid value of the polyester formed by the carboxyl group in the polyester is preferably from 15 to 250 KOHmg/g. When the acid value is less than 15 KOHmg/g, the water dispersion of the polyester is not easy to be obtained at the same time, and the uniformity is lowered and the film formability is lowered. Further, when the acid value exceeds 250 KOHmg/g, the water resistance may be poor. The higher the acid value, the less scattering in the visible light region, and the finer particles become finer, thereby improving the affinity for water, so the compatibility of the polyvinyl alcohol is good and good.

In the polyester of the resin composition of the present invention, those having a carboxyl group in the substituent are preferably obtained by, for example, polycondensation of a trifunctional or higher polycarboxylic acid and one or two compounds of a hydroxyl group. .

Examples of the trifunctional or higher polycarboxylic acid compound include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, and 4-methylcyclohexene-1,2,3 tricarboxylic anhydride. Symmetrical benzenetricarboxylic acid and the like. These may be used alone or in combination of two or more types.

Examples of the compound having one or two of the above hydroxyl groups include an aliphatic polyalcohol, a polyhydroxy aromatic compound, a polyether diol, a polyester diol, a polyester polycarbonate diol, a polycarbonate diol, and a poly The olefin diol and the single terminal hydroxyl group of the compound are alkoxylated with an alkyl group having 1 to 25 carbon atoms. These may be used alone or in combination of two or more.

The aliphatic alcohol may be, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, or 2-butyl-2-ethyl-1,3- Propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1 , 5-pentanediol, 2-methyl -2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1 , an aliphatic diol such as 8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc.; cyclohexanedimethanol, cyclohexyl An alicyclic diol such as alkanediol, hydrogenated bisphenol A, hydrogenated bisphenol F, etc.; trimethylolethane, trimethylolpropane, hexitol, pentaerythritol, glycerin, polyglycerol, pentaerythritol And a trivalent or higher polyalcohol such as dipentaerythritol or tetramethylolpropane.

Examples of the polyether diols include vinyl oxide adducts such as diethylene glycol and triethylene glycol; and propylene oxide adducts such as dipropylene glycol and tripropylene glycol; and low molecular weight. A vinyl oxide of a polyalcohol and/or a propylene-based oxide adduct, polytetramethylene glycol or the like.

Examples of the polyester diols include low molecular weight diols, dicarboxylic acids in an amount smaller than the stoichiometric amount, ester-forming derivatives and/or lactones of the esters, anhydrides, halides, and the like. A class or a direct esterification reaction and/or a transesterification reaction of a hydroxycarboxylic acid obtained by subjecting the hydrolysis to ring opening.

Examples of the dicarboxylic acid system include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, and fumaric acid. Maleic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipate, 3-methyladipate, 3-methylglutaric acid, 2-methyloctanedioic acid, 3 , aliphatic dicarboxylic acids such as 8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid, dimer acid, etc.; phthalic acid, terephthalic acid, isophthalic acid Dicarboxylic acid, dimethylmalonic acid, glutaric acid, trimethyl adipate, 2,2-dimethylglutaric acid, itaconic acid, 1,3-cyclopentane dicarboxylate Acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, 1,4-naphthalene dicarboxylic acid, diferulic acid, 4, 4'-hydroxybenzene, diglycolic acid, thiodipropionic acid, hexahydroterephthalic acid, naphthalene 2,5-dicarboxylic acid, naphthalene 2,6-dicarboxylic acid, pyromellitic tetracarboxylic anhydride, etc. An aromatic dicarboxylic acid; an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid;

Examples of the polycarbonate diols include poly(1,6-hexene) carbonate and poly(3-methyl-1,5-pentene) carbonate, and examples of the polyolefin diols can be exemplified. Butadiene diol, hydrogenated polybutadiene diol, hydrogenated polyisoprene diol, and the like. Among the compounds having one or two hydroxyl groups in the same molecule, particularly a polyether diol and/or a polyester diol is preferred. The molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 3,000, preferably 500 to 2,000.

As the polyhydroxy aromatic compound, 4,4-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2- can be exemplified. Bis(4-hydroxyphenyl)butane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)anthracene, 4,4'-(1- Α-methylbenzylidene)bisphenol, 4,4'-(1-α-ethylbenzylidene)bisphenol, 1,1-bis(4-hydroxyphenol)cyclohexane, 9,9 - bis(4-hydroxyphenyl)fluorene, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, hydrogenated bisphenol compound, resorcinol, hydroquinone, 2,5-di-tert-butyl hydroquinone, 1,4-dihydroxynaphthalene, 1,2,4-trihydroxybenzene, 2-[bis(4-hydroxyphenyl)methyl]benzyl alcohol, Salicylic acid, benzodimethyl glycol, bishydroxyethoxybenzene, and the like.

The polyester polycarbonate diol system can be exemplified by poly A reaction product of a polyester glycol such as a lactone polyalcohol and an alkylene carbonate, a reaction product obtained by reacting an organic dicarboxylic acid with a reaction product of a vinyl carbonate and ethylene glycol, and the like.

Examples of the polyolefin diols include polybutadiene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol.

Further, the polyester of the resin composition of the present invention may be a method of graft-polymerizing a polymerizable unsaturated carboxylic acid onto a polyester, or an ethylene glycol or an end as seen in JP-A-62-240318. The monoesterification reaction of a polyester glycol which is a hydroxyl group with a tetracarboxylic dianhydride is obtained by a chain extension method.

In the resin composition of the present invention, commercially available products such as NICHIGOPOLYESTER WR-961, WR-1031 (manufactured by Nippon Synthetic Chemical Co., Ltd.), and PESURE JIN A-680, A-690, A- can be used as the polyester. 210, A-230, A-695GE (made by Takamatsu Oil Co., Ltd.); PLASCOATZ-730, Z-760 (made by Mutual Chemical Industry Co., Ltd.); VYLONAL MD-1100, MD-1200, MD-1245, MD-1335, MD -1480, MD-1500, MD-1930, MD-1985, MD-2000 (manufactured by Toyobo Co., Ltd.), and the like.

In the resin composition of the present invention, the polystyrene-based weight average molecular weight (Mw) by gel permeation chromatography (GPC) of polyester is 500 to 30,000, but from the viewpoint of water resistance, 1,000~ 10,000 is preferred.

In the resin composition of the present invention, the blend ratio of the polyvinyl alcohol to the polyester is 99.5 in terms of compatibility, from the viewpoint of compatibility. It is preferably from 0.5 to 50:50, and from the viewpoint of transparency and water resistance of the coating film, 95:5 to 60:40 is preferred.

In the resin composition of the present invention, by further adding a crosslinking agent, it is also possible to react with a carboxylate to improve water resistance and heat resistance. Examples of the crosslinking agent include an oxazoline compound, a carbodiimide compound, an epoxy compound, a propylene oxide compound, a vinyl ether compound, a polyamine, a polyalcohol, a polyphenol, and a polyfunctional thiol. Dicyanodiamine derivative, hydrazine compound, polyfluorene compound (dioxin, triterpene), aldehyde, methylol compound, activated vinyl compound, polyisocyanate compound, alkyl carbonate compound of phenolic compound , a polyvalent metal salt, a decane coupling agent, an organic titanium, an organic zirconium, etc., wherein the oxazoline and the carbodiimide compound are preferably reacted at a heat drying temperature of 100 to 120 °C.

In the resin composition of the present invention, commercially available products can be used as the crosslinking agent, for example, EPOCROS WS-300, WS-500, WS-700 (manufactured by Nippon Catalyst (NIPPON SHOKUBAI)); CARBODILITEV-02 , V-02-L2, SV-02, V-04, V-10, SW-12G, E-02, E-03A, E-05 (Nisshinbo (NISSHINBO) Chemical Co., Ltd.); SR-4GL, SR- 6GL (manufactured by SAKAMOTO YAKUHIN KOGYO); OLGA CHICKSZC-126, TC-315 (manufactured by MATSUMOTO FINE Chemical Co., Ltd.).

The resin composition of the present invention is obtained by mixing an aqueous solution or an aqueous dispersion of a polyvinyl alcohol and an aqueous solution, an aqueous dispersion or a water-dispersible latex of a polyester, and if necessary, a coupling agent or a surfactant. Wait.

As the above coupling agent, dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl ethyl dimethoxy decane, methyl ethyl diethoxy decane, methyl trimethoxy group can be used. Alkyl functional alkoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl three, such as decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl trimethoxy decane Alkenyl functional alkoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyl, ethoxy decane, allyltrimethoxydecane, etc. Trimethoxydecane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 2-methylpropenyloxypropane Trimethoxy decane, γ-glycidoxypropyltrimethoxy decane, γ-glycidoxypropylmethyldiethoxy decane, β-(3,4-epoxycyclohexyl)B Epoxy-functional alkoxydecane such as trimethoxy decane, N-β(aminoethyl)-γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N -phenyl - anthracenyl functional alkoxydecane such as γ-aminopropyltrimethoxydecane, thiol-functional alkoxydecane such as γ-mercaptopropyltrimethoxydecane, titanium tetraisopropoxide, and tetra-negative Titanium chelates such as titanium alkoxylates such as butoxytitanium, titanium dioctyloxybis(octyl glycol ester), titanium diisopropoxy bis(ethylacetamidine acetate), etc. a zirconium chelate compound such as zirconium acetonide or zirconium acetoacetate or zirconium hydride such as zirconium tributoxy stearate or an isocyanate decane such as methyl triisocyanate decane. .

As the surfactant, a fluorine-based surfactant such as a perfluoroalkyl phosphate or a perfluoroalkyl carboxylate or a higher fatty acid base can be used. Anionic surfactant such as salt, alkyl sulfonate or alkyl sulfate, cationic amine surfactant such as higher amine halogenated acid salt or fourth ammonium salt, polyethylene glycol alkyl ether, polyethylene a surfactant such as a nonionic surfactant such as a diol fatty acid ester, a sorbitan fatty acid ester or a fatty acid monoglyceride, an amphoteric surfactant or a polyoxonated surfactant, or a combination thereof Wait.

The resin composition of the present invention can be used as a light/thermosetting resin composition by further adding a radical polymerizable compound and a polymerization initiator, and if necessary, a sensitizing agent. It is expected that the water/thermosetting resin composition obtained has high water resistance and heat resistance.

The radical polymerizable compound is not particularly limited, and a conventional user can be used. For example, an unsaturated aliphatic hydrocarbon, an unsaturated polybasic acid, an unsaturated monobasic acid, an ester of a polyhydric or polyhydric phenol, an anhydride of an unsaturated polybasic acid, an unsaturated monobasic acid, and a decylamine of an aliphatic amine, an unsaturated aldehyde, Unsaturated aromatic compounds, unsaturated ketones, vinyl ethers, unsaturated quinones, anthraquinones, aliphatic coordinating dienes, macromolecules having a mono(meth)acrylonitrile group at the end of the polymer molecular chain Monomers, vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallylphosphonate, triallyl isocyanurate, Vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomer containing a hydroxyl group, and vinyl urethane of a polyisocyanate compound a compound, a vinyl monomer having a hydroxyl group, and a vinyl epoxy compound of an epoxy compound, The hydroxyl group contains a reaction product of a polyfunctional acrylate with another functional isocyanate, a polyfunctional acrylate having an acid value of a reactant having a hydroxyl group containing a polyfunctional acrylate and a dibasic acid anhydride, and the like. These polymerizable compounds may be used singly or in combination of two or more. Further, when two or more kinds are used in combination, the copolymerization may be carried out in advance as a copolymer.

The above-mentioned polymerization initiator may be exemplified by a light/thermal irradiation to make a radical polymerization initiator possible, for example, an acetophenone-based compound, a benzoin-based compound, or a benzophenone-based compound. a photoradical polymerization initiator such as a ketone compound such as a thioxanthone compound or a quinone compound; 2,2'-azobisisobutyronitrile, 2,2'-azobis(isobutyric acid) Azo, etc., azo, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-ethenyloxy-1-phenylethane) Starting agent; benzoyl peroxide, di-t-butyl benzoyl peroxide, tertiary butyl peroxy isobutyrate, bis(4-t-butylcyclohexyl) peroxygen A thermal radical polymerization initiator such as a peroxide-based initiator such as a dicarbonate or a peroxosulfate such as ammonium persulfate, sodium persulfate or potassium persulfate. These may be used alone or in combination of two or more.

As the sensitizer, a compound having a wavelength range acceptable for light curing by light irradiation can be expanded, and examples thereof include benzophenone, 3-hydroxybenzophenone, and 4-hydroxybenzophenone. 4-dihydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,5-dimethylbenzophenone, 3, 4-dimethylbenzophenone, 4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 3,3-dimethyl-4-methoxybenzophenone , benzophenones such as 4-phenylbenzophenone, acetophenone, 4-methoxyacetophenone, 2,4-dimethoxyacetophenone, 2,5-dimethoxyacetophenone, 2,6-dimethoxyacetophenone, 4,4-di Methoxyacetophenone, 4-ethoxyacetophenone, diethoxyacetophenone, 2,2-diethoxyacetophenone, 2-ethoxy-2-phenylacetophenone, Acetophenones such as 4-phenylacetophenone, onion, hydroxy onion, 1-nitro onion, amino onion, 2-chloro onion, 2-methyl onion, 2-ethyl Onion, onion, sulfonic acid, 1,2-benzopyrene, 1,4-hydroxy onion (醌茜), etc., onion, hydrazine, 1,2-benzopyrene, 9-cyanoguanidine, 9,10-Dicyanoguanidine, 2-ethyl-9,10-dimethoxyanthracene, 9,10-bis(phenylethyl)anthracene, etc., 2,3-dichloro-6- Dicyano-p-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, methoxyphenylhydrazine, 2,5-dichloro-p-benzoquinone, 2,6-dimethyl Alkaloids of 1,4-benzoquinone, 9,10-phenanthrenequinone, camphorquinone, 2,3-dichloro-1,4-naphthoquinone, ketone, etc., thioxanthone, 2-methylthioxanthene Sulphoxane, diphenyl, etc. of ketone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-isopropylthioxanthone Cycloheptanone, dibenzocycloheptene, dibenzo ring a cycloheptane such as dibenzosuberenol or dibenzocycloheptane, 2-methoxynaphthalene, benzoin isopropyl ether, 4-benzylidenebiphenyl, orthobenzoylbenzoic acid, orthophthalic acid Aromatic compounds such as methyl mercaptobenzoate, 4-benzylidene-4-methyl-diphenyl sulfide, benzoin, benzoin methyl ether, and coumarins and thiophenes of pigmentary sensitizing substances A azine, a pyridazine, an acridine or a xanthene compound.

The resin composition of the present invention is applied to glass, metal, paper, plastic, etc. by a known method such as a spin coater, a bar coater, a roll coater, a curtain coater, various printing, and dipping. Supported on the substrate. Moreover, once applied to a support substrate such as a film, it can also be copied to other The supporting method is not limited to the supporting substrate.

Further, as long as the effect of the present invention is not impaired, a coloring agent such as an acid generator, an alkali starter, an inorganic filler, an organic filler, a pigment, a dye, or the like may be added to the resin composition of the present invention, and defoaming may be added. Agent, tackifier, leveling agent, thixotropic agent, carbon compound, metal microparticles, metal oxide, flame retardant, plasticizer, light stabilizer, thermal stabilizer, anti-aging agent, elastomer particles, chain transfer Various resin additives such as a solvent, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, a mold release agent, a flow control agent, an adhesion promoter, and an unsaturated monomer.

Specific examples of the resin composition of the present invention include optical materials, coating materials, coating agents, lining agents, inks, resists, liquid resists, adhesives, and liquid crystal dripping represented by lenses for cameras and photographic lenses. Sealant, printing plate, insulating varnish, insulating plate, laminate, printed circuit board, semiconductor device. For LED packaging. LCD injection port. For organic EL. For optical components. For electrical insulation. For electronic parts. Separation film, etc., such as sealing agent, molding material, putty, glass fiber impregnating agent, filler, semiconductor. A passivation film for an solar cell, an interlayer insulating film, a protective film, a wafer used for backlighting of a liquid crystal display device, a lens portion of a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet used for a screen of a projection television or the like Or such a thin plate backlight, a protective film and spacer for a liquid crystal color filter, a DNA separation wafer, a microreactor, a nanobiodevice, a recording material for a hard disk, a solid-state imaging device, a solar cell , light-emitting diodes, organic light-emitting elements, light-emitting films, fluorescent films, MEMS components, actuators, full-phase diagrams, surface plasma An optical lens, an optical element, an optical connector, an optical waveguide, and a casting agent for optical molding of an element, a polarizing plate, a polarizing film, and a microlens, for example, a substrate-based metal, wood, rubber, or the like which can be suitably used as a coating agent Plastic, glass, ceramic products, etc.

Next, the optical film of the present invention will be described. The optical film of the present invention is composed of the resin composition of the present invention. The optical film of the present invention is formed by a conventional method for forming a film or a sheet which can be produced by a film or sheet which is not stretched (or alignment treatment) or can be produced by stretching (or alignment treatment). The film forming system can be a melt molding method (melt film formation method) such as extrusion molding or blow molding, or a tape casting method (cast film formation method or solution casting method).

When the optical film of the present invention is applied to a transparent support and the resin composition of the present invention is produced, the material of the transparent support can be exemplified by an inorganic material such as glass; diethyl ruthenium cellulose, triethylene fluorene cellulose (TAC) ), cellulose esters of propylene glycol, butyric cellulose, acetophenoxy cellulose, nitrocellulose, etc.; polyamine; polycarbonate; polyvinyl terephthalate, Polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyvinyl-1,2- Polyesters such as diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate, etc.; polystyrene based; polyvinyl, polypropylene, polymethyl Polyolefin such as pentene; acrylonitrile based resin such as polymethyl methacrylate; polycarbonate; polyfluorene; polyether oxime; polyether ketone; polyether quinone imine; polyoxyethylene Borneene resin Such as polymer materials. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, and preferably 1% or less. The inflection rate is preferably 1.45~1.70.

When the coating film formed by applying the resin composition of the present invention is irradiated with light, the irradiation conditions such as the wavelength, intensity, and irradiation time of the light to be irradiated are the activity of the photoinitiator and the photopolymerization property used. The activity of the resin or the like may be appropriately adjusted, and the light wavelength system usually has sufficient light to enter the inside. Therefore, the wavelength peak is preferably from 350 to 400 nm, and preferably the wavelength peak is from 360 to 380 nm. Further, as the light intensity of line 10 ~ 300mW / cm ² preferably, it is preferably 25 ~ 100mW / cm ^2, irradiation time based preferably 5 to 500 seconds, preferably 10 to 300 seconds.

When the coating film formed by coating the resin composition of the present invention is thermally cured, the heating conditions such as the heating temperature and the heating time may be appropriately adjusted by the activity of the radical polymerizable compound and the polymerization initiator, and the heating temperature may be appropriately adjusted. The temperature is 80~200°C, and the heating time is 30 seconds~60.

The shape and shape of the optical film of the present invention are not particularly limited, and a film having an optical film on a transparent support and used for optical coating is used, and a protective film for a polarizing plate or a retardation film used for a liquid crystal display device or the like can be exemplified. And various functional films such as an antireflection film and a low reflectance film used for a viewing angle expansion film and a plasma display panel, and various functional films used in an organic EL display or the like.

The optical film of the present invention is an optical recording layer for applying an optical film to a rewritable optical disk (CD±R, DVD±R, next generation high-density optical disk, etc.) of a support; it can be used as follows: various lenses; The optical filter of the display device; the various filters represented by the color filter and the color conversion filter; or the protective sealing film of the organic EL light-emitting element, the inorganic EL light-emitting element, or the electronic paper display body.

Example

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited to the examples. Further, the parts of the examples and the comparative examples mean the mass points.

[Examples 1 to 36 and Comparative Examples 1 to 14]

<Preparation of polyvinyl alcohol aqueous solution>

First, when 900.0 g of ion-exchanged water was stirred at room temperature, 100.0 g of the following polyvinyl alcohol of A-1 to A-7 was gradually added. After the solution was stirred at room temperature for 10 minutes, it was heated from an internal temperature of 85 to 90 ° C, and stirring was continued at this temperature for 1 hour. After confirming the dissolution of the polyvinyl alcohol, the aqueous polyvinyl alcohol solution was cooled to room temperature. Thereafter, the prepared aqueous polyvinyl alcohol solution was filtered through a 1 μm filter. However, the blending amounts of PV-1 to PV-7, B-1 to B-6, and B'-1 and B'-3 in the following Tables 1 to 8 are ratios of solid fractions (% by mass). , B'-2 is the total amount of liquid.

A-1 Japanese synthetic chemical industry gohsenol NL-05 (saponification degree 99)

A-2 Japanese synthetic chemical industry gohsenol GL-05 (saponification degree) 87)

A-3 Nichigo G-Polymer OKS-1083 (Saponification Degree 99) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

A-4 GOHSENX Z-300 (Saponification Degree 98) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

A-5 Japan Synthetic Chemical Industry GOHSENX Z-200 (saponification degree 98)

A-6 made in Japan Synthetic Chemical Industry gohsenol KL-05 (saponification degree 80)

A-7 GOHSENXT-330H manufactured by Japan Synthetic Chemical Industry (an saponification degree of 99, an anionic modification having a carboxyl group in the molecule)

<Modulation of Resin Composition>

First, the prepared polyvinyl alcohol aqueous solution, and the aqueous polyester solutions of B-1 to B-6 and B'-1 to B'-3 described in Tables 1 to 8 below, and Table 6 below. The cross-linking agents of C-1 to C-6 shown in Table 8 were mixed according to the blending of the same table, stirred at room temperature for 1 hour, and then filtered through a 1 μm filter to obtain Examples and Comparative Examples. Resin composition.

Aqueous solution of PV-1 A-1

Aqueous solution of PV-2 A-2

Aqueous solution of PV-3 A-3

Aqueous solution of PV-4 A-4

Aqueous solution of PV-5 A-5

Aqueous solution of PV-6 A-6

B-1 high pine oil (TAKAMATSUYUSI), PESUREJIN (trade name) A-690 (substituent: COOH, solids 2210%, acid value 50mgKOH / g)

B-2 manufactured by Nippon Synthetic Chemical Co., Ltd., polyester WR-961 (substituent: COOH, solids 30%, acid price 60 mgKOH/g)

B-3 Made by Japan Synthetic Chemical Industry, polyester WR-1031 (substituent: COOH, solids 30%, acid price 80 mgKOH/g)

B-4 Mutual Chemical (GOO CHEMICAL) Industrial, PLUS COAT (trade name) Z-730 (substituent: COOH, solids 25%, acid value 50 mgKOH/g)

B-5 high pine oil system, PESUREJINA-210 (substituent: COOH, solids 30%, acid price 70mgKOH / g)

B'-1 high pine oil, PESUREJINA-640 (substituent: SO ₃ Na, solids 25%)

B'-2 ADEKA, ADEKACIZER (trade name) PN-77 (phthalate)

B'-3 Mutual Chemical, PLUS COAT (trade name) Z-446 (substituent: SO ₃ Na, solid fraction 25%)

Aqueous solution of PV-7 A-7

B-6 high pine oil, PESUREJIN (trade name) A-230 (substituent: COOH, solids 30%, acid price 80mgKOH / g)

C-1 Japan Catalyst, EPOCROS (trade name) WS-700 (oxazoline; crosslinker, solids 25%)

C-2 Nisshin Spinning, CARBODILITE (trade name) V-02-L2 (carbodiimide compound; crosslinker, solids 40%)

C-3 Sakamoto YAKUHIN KOGYO Industrial, SR-4GL (epoxy compound; crosslinker, active ingredient 100%)

C-4 manufactured by Sakamoto Pharmaceutical Co., Ltd., SR-6GL (epoxy compound; crosslinker, active ingredient 100%)

C-5 Matsumoto FINE CHEMICAL, ORGATICS (trade name) ZC-126 (zirconyl chloride compound; crosslinker, solids 30%)

C-6 Matsumoto business system, ORGATICSTC-315 (titanium lactate; crosslinker, solids 44%)

With respect to each of the obtained resin compositions, the state after coating drying as the solution compatibility and the coating property, the state after the wet heat resistance test, and the voltage holding ratio (VHR) were evaluated. The results are combined and described in Tables 1 to 8 above. Also, the steps of each evaluation are as follows.

(solution compatibility)

The state of each resin composition was visually confirmed. The criterion is as follows Said.

○: transparent and uniform

△: white turbid

×: incompatible (separated from each other)

(coating property)

Each of the resin compositions was applied onto a glass substrate using a spin coater, and then prebaked in a hot plate at 70 ° C for 5 minutes and a hot plate at 90 ° C for 5 minutes, and then at 140 ° C. The substrate for evaluation was prepared by heating at 15 minutes. The film thickness was adjusted to a spin coating condition of 5.0 to 5.5 μm by a probe method.

a) the state after the coating of the coating film is dried

With respect to the obtained evaluation substrate, the state of the surface was visually confirmed and evaluated based on haze measurement. For the measurement, a haze meter NDH5000 manufactured by Nippon Denshoku Co., Ltd. was used, and the criterion was determined as follows.

○: The film is uniform and the haze is less than 1

△: The film is uniform, and the haze is 1 or more and less than 3

×: The film remains comprehensive and has a haze of 3 or more.

××: Partial peeling or dissolution of the film

b) Moisture and heat resistance test of coating film

The obtained evaluation substrate was subjected to conditions of 85 ° C and 85% RH. Next, the surface state of the substrate after being placed for 100 hours was evaluated in the same manner as in a). The criterion is determined to be the same as described above.

(VHR)

On the coating film obtained in the coating property test, the liquid crystal composition composed of the following liquid crystal compounds No. 1 to No. 11 was contacted, and after 60 hours at 60 ° C, resin dissolution property was taken out by taking out the liquid crystal composition. test. For the liquid crystal composition which was taken out, the VHR before and after the resin elution test was compared, and the rate of decrease of VHR was required, and the evaluation was carried out by the following criteria.

The liquid crystal composition was injected into TN cells for liquid crystal evaluation (cell thickness: 5 μm, electrode area: 8 mm × 8 mm alignment film JALS2096), and VHR was measured using VHR-1A (manufactured by Toyo Seiki Co., Ltd.). Measurement conditions, pulse voltage width: 60 μs, frame period: 16.7 ms, wave height: ±5 V, measurement temperature: 25 °C.

○: VHR exceeds 99%

△: VHR is 97~99%

×: VHR is less than 97%

From Tables 1 to 8, it is understood that the resin composition of the present invention is excellent in transparency and coating property, and liquid crystal contamination is low. Therefore, the resin composition of the present invention can be suitably used for an optical film or a liquid crystal dropping method sealant.

Claims (8)

A resin composition characterized by comprising a resin composition of a polyvinyl alcohol and a polyester, wherein the polyester has a carboxyl group and/or a carboxyl group as a substituent. The resin composition of claim 1, wherein the polyvinyl alcohol is a homopolymer or a copolymer having vinyl alcohol as an essential monomer. The resin composition of claim 1, wherein the aforementioned polyvinyl alcohol has an ethyl acetate group. The resin composition of claim 1, wherein the polyvinyl alcohol has a degree of saponification of 85 or more. The resin composition of claim 1, wherein the content of the polyester is 0.5 to 50% by mass in the solid content. The resin composition of claim 1, which further contains a crosslinking agent. The resin composition of claim 6, wherein the crosslinking agent is an oxazoline compound or a carbodiimide compound. An optical film characterized by being composed of the resin composition of claim 1.