WO2018096928A1

WO2018096928A1 - Curable resin composition for optical films, optical film and method for producing same

Info

Publication number: WO2018096928A1
Application number: PCT/JP2017/040256
Authority: WO
Inventors: 武士斉藤
Original assignee: 日東電工株式会社
Priority date: 2016-11-22
Filing date: 2017-11-08
Publication date: 2018-05-31

Abstract

The purpose of the present invention is to provide a curable resin composition for optical films, which is used for optical film applications where at least a polyvinyl alcohol-based polarizer is contained, and which is capable of forming a cured product layer that exhibits excellent optical durability even under harsh conditions such as a dew condensation environment or immersion in water. A curable resin composition for optical films, which contains (A) an active energy ray-curable component and (B) a chlorinated polyolefin. The chlorine content of the chlorinated polyolefin (B) is preferably 25-50% by weight; and the weight ratio of the active energy ray-curable component (A) to the chlorinated polyolefin (B) is preferably 100:1 to 100:40.

Description

Curable resin composition for optical film, optical film and method for producing the same

The present invention relates to an optical film in which a cured layer of a curable resin composition for an optical film is laminated on at least one surface of a curable resin composition for an optical film and a polyvinyl alcohol polarizer, and a method for producing the same. The optical film can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP.

Liquid crystal display devices are rapidly expanding in the market for watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, TVs, etc. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle. In particular, in applications such as TV, higher brightness, higher contrast, and wider viewing angle are required, and polarizing films are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.

As the polarizer, since it has a high transmittance and a high degree of polarization, for example, an iodine-based polarizer having a stretched structure by adsorbing iodine to polyvinyl alcohol (hereinafter also simply referred to as “PVA”) is most widely used. in use. In general, a polarizing film is used in which a transparent protective film is bonded to both surfaces of a polarizer with a so-called aqueous adhesive in which a polyvinyl alcohol-based material is dissolved in water (Patent Document 1 below). As the transparent protective film, triacetyl cellulose having a high moisture permeability is used. When the water-based adhesive is used (so-called wet lamination), a drying process is required after the polarizer and the transparent protective film are bonded together.

On the other hand, an active energy ray-curable adhesive has been proposed instead of the water-based adhesive. When manufacturing a polarizing film using an active energy ray hardening adhesive, since a drying process is not required, productivity of a polarizing film can be improved. For example, the present inventors have proposed a radical polymerization type active energy ray-curable adhesive using an N-substituted amide monomer as a curable component (Patent Document 2 below).

JP 2001-296427 A JP2012-052000A

The adhesive layer formed using the active energy ray-curable adhesive described in Patent Document 2 is sufficient for a water resistance test for evaluating the presence or absence of color loss or peeling after immersion in warm water at 60 ° C. for 6 hours, for example. It can be cleared. However, in recent years, the adhesive for optical films, for example, to evaluate the presence or absence of peeling when the end nail peeling after being immersed (saturated) in water, can be cleared more severe water resistance test Further improvement in water resistance is being demanded. Therefore, the adhesives for optical films reported up to now including the active energy ray-curable adhesive described in Patent Document 2 have room for further improvement in terms of water resistance. .

As mentioned above, the market demands higher optical durability for optical films, and the optical durability of optical films, especially changes in optical characteristics even under severe humidification conditions such as 85 ° C and 85% RH. There is a demand for an optical film with a small amount. Regarding the optical durability, the active energy ray-curable adhesive is superior to the water-based adhesive, but there is a room for further improvement in the conventionally known active energy ray-curable adhesive.

The present invention was developed in view of the above circumstances, and is used for optical film applications including at least a polyvinyl alcohol-based polarizer, and has optical durability even under harsh conditions such as in a dew condensation environment or in water. It aims at providing the curable resin composition for optical films which can form the cured | curing material layer excellent in the.

Furthermore, in the present invention, there is provided an optical film in which a cured product layer of the curable resin composition for an optical film is laminated on at least one surface of a polyvinyl alcohol-based polarizer, which is excellent in optical durability. For the purpose.

In order to solve the above-mentioned problems, the present inventors are concerned with the dyeability of a cured product layer resulting from a polarizer-derived iodine compound when a cured product layer such as an adhesive layer is laminated on a polyvinyl alcohol polarizer. investigated. As a result, it has been found that the above-mentioned problems can be solved by adding a specific component in the cured product layer and directly laminating the cured product layer on the polyvinyl alcohol polarizer.

That is, this invention relates to the curable resin composition for optical films containing an active energy ray hardening component (A) and a chlorinated polyolefin (B).

In the curable resin composition for an optical film, the chlorinated polyolefin (B) preferably has a chlorine content of 25 to 50% by weight.

In the curable resin composition for optical films, the weight ratio of the active energy ray-curable component (A) to the chlorinated polyolefin (B) is preferably 100: 1 to 100: 40.

In the present invention, a cured layer of a curable resin composition for an optical film containing an active energy ray-curable component (A) and a chlorinated polyolefin (B) is laminated on at least one surface of a polyvinyl alcohol polarizer. The present invention relates to an optical film.

The optical film is preferably one in which a transparent protective film is laminated on at least one surface of the polyvinyl alcohol polarizer via the cured product layer.

The optical film is preferably one in which the cured product layer is laminated on one side of the polyvinyl alcohol polarizer and a transparent protective film is laminated on the other side.

Furthermore, the present invention is a method for producing an optical film comprising a cured product layer obtained by curing a curable resin composition for an optical film on at least one surface of a polyvinyl alcohol-based polarizer, wherein the curable mold for an optical film is provided. The resin composition contains an active energy ray-curable component (A) and a chlorinated polyolefin (B), and the optical film curable resin composition is directly applied to at least one surface of the polyvinyl alcohol polarizer. Applying active energy rays from the coating process to be applied and the polyvinyl alcohol polarizer surface side or the coating surface side of the optical film curable resin composition to cure the optical film curable resin composition The manufacturing method of the optical film characterized by including the hardening process to make.

A polyvinyl alcohol-based polarizer is usually produced by uniaxially stretching polyvinyl alcohol by wet or dry method, followed by dyeing with an iodine compound and crosslinking with a crosslinking agent. When the active energy ray-curable component (A) and the chlorinated polyolefin (B) are contained in the curable resin composition constituting the cured product layer, the resulting cured product layer is derived from a polyvinyl alcohol polarizer. The dyeability due to the iodine compound is remarkably reduced, and functions as a protective layer that suppresses the liberation and diffusion of the iodine compound from the polarizer. As a result, when the curable resin composition according to the present invention is used for an optical film application including at least a polyvinyl alcohol polarizer, particularly for a polarizing film application, the optical durability of the optical film, particularly the polarizing film, is remarkably improved. To do.

As described above, the cured product layer of the curable resin composition for optical films according to the present invention has extremely low dyeability due to the iodine compound derived from the polyvinyl alcohol polarizer, and serves as a protective layer for the polyvinyl alcohol polarizer. Works effectively. Therefore, the optical film according to the present invention is excellent in optical durability even when the transparent protective film is not laminated on the polyvinyl alcohol polarizer. Further, in the optical film according to the present invention, even when the transparent protective film is laminated with the cured product layer as an adhesive layer, the adhesive layer effectively functions as a protective layer. Regardless of the optical durability of the optical film.

The curable resin composition for an optical film according to the present invention contains an active energy ray-curable component (A) and a chlorinated polyolefin (B).

<Active energy ray-curable component (A)>
The active energy ray-curable component (A) that can be used in the present invention can be broadly classified into electron beam curable, ultraviolet curable, and visible light curable. Moreover, as a form of hardening, it can be divided into a radical polymerization curable resin composition and a cationic polymerizable resin composition. In the present invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light. In particular, the active energy ray-curable component (A) that can be used in the present invention is particularly preferably visible light curable using visible light of 380 nm to 450 nm.

<1: Radical polymerization curable compound>
Examples of the radical polymerizable compound include compounds having a radical polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group. As these curable components, either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. As these radically polymerizable compounds, for example, compounds having a (meth) acryloyl group are suitable. In the present invention, (meth) acryloyl means an acryloyl group and / or methacryloyl group, and “(meth)” has the same meaning hereinafter. Examples of the compound having a (meth) acryloyl group include a (meth) acrylamide derivative having a (meth) acrylamide group and a (meth) acrylate having a (meth) acryloyloxy group. Examples of the compound having a (meth) acryloyl group are shown below, but various compounds can be selected and used without any particular limitation. In the active energy ray-curable resin composition of the present invention, the content of the radical polymerizable compound is preferably 10% by weight or more.

≪Monofunctional radical polymerizable compound≫
As a monofunctional radically polymerizable compound, for example, the following general formula (1)

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or a cyclic ether group, R ² and R ³ may form a cyclic heterocyclic ring). The number of carbon atoms in the alkyl moiety of the alkyl group, hydroxyalkyl group, and / or alkoxyalkyl group is not particularly limited, and examples thereof include 1 to 4 carbon atoms. Examples of the cyclic heterocycle that R ² and R ³ may form include N-acryloylmorpholine.

Specific examples of the compound represented by the general formula (1) include, for example, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl ( N-alkyl group-containing (meth) acrylamide derivatives such as (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N -N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as methylol-N-propane (meth) acrylamide; N-alkoxy group-containing (meth) acrylamide derivatives such as N-methoxymethylacrylamide and N-ethoxymethylacrylamide It is done. Examples of the cyclic ether group-containing (meth) acrylamide derivative include a heterocycle-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle, such as N-acryloylmorpholine, N -Acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like. Among these, N-hydroxyethylacrylamide and N-acryloylmorpholine are preferably used from the viewpoints of excellent reactivity, a cured product having a high modulus of elasticity, and excellent adhesion to a polarizer. it can.

Improved adhesion and water resistance between the polarizer and the curable resin layer, especially improved adhesion and water resistance when the polarizer and the transparent protective film are bonded via an adhesive layer, and a high polymerization rate From the viewpoint of improving productivity due to the above, the content of the compound represented by the general formula (1) in the curable resin composition is preferably 1 to 50% by weight, and preferably 3 to 20% by weight. Is more preferable. In particular, when the content of the compound described in the general formula (1) is too large, the water absorption of the cured product is increased, and the water resistance may be deteriorated.

Moreover, the curable resin composition used in the present invention may contain other monofunctional radically polymerizable compound as a curable component in addition to the compound represented by the general formula (1). Examples of the monofunctional radically polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl ( (Meth) acrylate, n-o Tadeshiru (meth) (meth) acrylic acid (1-20 carbon atoms) such as acrylates alkyl esters.

Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-isobornyl (Meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclopentenyl (meth) ) Polycyclic (meth) acrylates such as acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxy Ethyl (meth) acrylate Alkoxy groups such as 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, or phenoxy Group-containing (meth) acrylates; and the like. When the resin composition of the present invention is used as an adhesive for a polarizing film, it contains an alkoxy group or a phenoxy group such as phenoxyethyl (meth) acrylate and alkylphenoxypolyethylene glycol (meth) acrylate from the viewpoint of adhesion to a protective film. It is preferable to contain (meth) acrylate. The content is preferably 1% by weight to 30% by weight with respect to the resin composition.

Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate And [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and other hydroxy acids Containing (meth) acrylate; glycidyl (meth) acrylate, epoxy group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2- Halogen-containing (meth) acrylates such as hydroxypropyl (meth) acrylate; alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 3-oxetanylmethyl (meth) acrylate Contains oxetane groups such as acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, 3-butyl-oxetanylmethyl (meth) acrylate, 3-hexyloxoxanylmethyl (meth) acrylate (Meth) acrylate; (meth) acrylate having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and butyrolactone (meth) acrylate, neopentyl glycol (meth) acrylic acid adduct of hydroxypivalate, p-phenylphenol ( And (meth) acrylate. Of these, 2-hydroxy-3-phenoxypropyl acrylate is preferable because of its excellent adhesion to various protective films.

Also, examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.

Examples of the monofunctional radical polymerizable compound include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole, and vinyl morpholine.

When the resin composition contains a hydroxyl group-containing (meth) acrylate, carboxyl group-containing (meth) acrylate, phosphoric acid group-containing (meth) acrylate or the like having high polarity in the above compound, adhesion to various substrates is improved. To do. The content of the hydroxyl group-containing (meth) acrylate is preferably 1% by weight to 30% by weight with respect to the resin composition. When there is too much content, the water absorption rate of hardened | cured material may become high and water resistance may deteriorate. The content of the carboxyl group-containing (meth) acrylate is preferably 1% by weight to 20% by weight with respect to the resin composition. When there is too much content, since the optical durability of a polarizing film falls, it is unpreferable. Examples of the phosphoric acid group-containing (meth) acrylate include 2- (meth) acryloyloxyethyl acid phosphate, and the content is 0.1% by weight to 10% by weight with respect to the resin composition. preferable. When there is too much content, since the optical durability of a polarizing film falls, it is unpreferable.

Also, as the monofunctional radically polymerizable compound, a radically polymerizable compound having an active methylene group can be used. The radical polymerizable compound having an active methylene group is a compound having an active methylene group having an active double bond group such as a (meth) acryl group at the terminal or in the molecule. Examples of the active methylene group include an acetoacetyl group, an alkoxymalonyl group, and a cyanoacetyl group. The active methylene group is preferably an acetoacetyl group. Specific examples of the radical polymerizable compound having an active methylene group include 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate, and the like. Acetoacetoxyalkyl (meth) acrylate; 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) Examples include acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, and N- (2-acetoacetylaminoethyl) acrylamide. The radical polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.

≪Polyfunctional radical polymerizable compound≫
Examples of the bifunctional or higher polyfunctional radical polymerizable compound include N, N′-methylenebis (meth) acrylamide, tripropylene glycol di (meth) acrylate, and tetraethylene glycol diester which are polyfunctional (meth) acrylamide derivatives. (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) ) Acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate , Neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate (Meth) acrylic such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerin tetra (meth) acrylate An esterified product of an acid and a polyhydric alcohol, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene. Specific examples include Aronix M-220 (manufactured by Toagosei Co., Ltd.), light acrylate 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DCP-A (Kyoeisha Chemical Co., Ltd.) SR-531 (Sartomer), CD-536 (Sartomer) and the like are preferable. Moreover, various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are included as necessary. The polyfunctional (meth) acrylamide derivative is preferably contained in the curable resin composition because the polymerization rate is high and the productivity is excellent, and the crosslinkability when the resin composition is a cured product is excellent.

Radical polymerizable compounds should be used in combination with monofunctional radical polymerizable compounds and polyfunctional radical polymerizable compounds from the viewpoint of achieving both adhesion to polarizers and various transparent protective films and optical durability in harsh environments. Is preferred. In addition, since a monofunctional radically polymerizable compound has comparatively low liquid viscosity, the liquid viscosity of a resin composition can be reduced by making it contain in a resin composition. In addition, monofunctional radically polymerizable compounds often have functional groups that exhibit various functions, and by incorporating them into the resin composition, various functions are expressed in the resin composition and / or the cured product of the resin composition. Can be made. Since the polyfunctional radically polymerizable compound can three-dimensionally crosslink the cured product of the resin composition, the polyfunctional radical polymerizable compound is preferably contained in the resin composition. The ratio of the monofunctional radical polymerizable compound to the polyfunctional radical polymerizable compound is such that the polyfunctional radical polymerizable compound is mixed in the range of 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the monofunctional radical polymerizable compound. Is preferred.

<2: Cationic polymerization curable resin composition>
The cationic polymerizable compound used in the cationic polymerization curable resin composition includes a monofunctional cationic polymerizable compound having one cationic polymerizable functional group in the molecule and two or more cationic polymerizable functional groups in the molecule. And having a polyfunctional cationically polymerizable compound. Since the monofunctional cation polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be reduced by containing it in the resin composition. In addition, monofunctional cationically polymerizable compounds often have functional groups that develop various functions, and by incorporating them into the resin composition, various functions are exhibited in the resin composition and / or the cured product of the resin composition. Can be made. The polyfunctional cation polymerizable compound is preferably contained in the resin composition because the cured product of the resin composition can be three-dimensionally crosslinked. The ratio of the monofunctional cation polymerizable compound to the polyfunctional cation polymerizable compound is such that the polyfunctional cation polymerizable compound is mixed in the range of 10 to 1000 parts by weight with respect to 100 parts by weight of the monofunctional cation polymerizable compound. Is preferred. Examples of the cationic polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of the compound having an epoxy group include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound, and the cationic polymerization curable resin composition of the present invention is excellent in curability and adhesiveness. It is particularly preferable to contain an alicyclic epoxy compound. Examples of the alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate caprolactone-modified products and trimethylcaprolactone-modified products. And valerolactone-modified products, specifically, Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085 (above, Daicel Chemical Industries, Ltd., Cyracure UVR-6105, Cyracure UVR) -6107, Cyracure 30, R-6110 (above, manufactured by Dow Chemical Japan Co., Ltd.), etc. The compound having an oxetanyl group is a cationic polymerization compound of the present invention. The compound having an oxetanyl group is preferably contained because it has the effect of improving the curability of the curable resin composition or lowering the liquid viscosity of the composition, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl -3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, and the like, including Aron Oxetane OXT-101, Aron Oxetane OXT-121, Aron Oxetane OXT-211, Aron Oxetane OXT-221, Aron Oxetane OXT-212 (Above, manufactured by Toagosei Co., Ltd.) The compound having a vinyl ether group is preferably contained because it has the effect of improving the curability of the cationic polymerization curable resin composition of the present invention or lowering the liquid viscosity of the composition. As 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, vinyl ether of diethylene glycol, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxy Examples thereof include ethyl vinyl ether, ethoxyethyl vinyl ether, and pentaerythritol type tetravinyl ether.

The curable resin composition for an optical film according to the present invention contains a chlorinated polyolefin (B) together with an active energy ray-curable component (A).

<Chlorinated polyolefin (B)>
For use in optical film applications, the curable resin composition according to the present invention needs to be optically transparent, and is soluble in the active energy ray-curable component (A) as a polyolefin resin, and is separated into layers. It is important to select a chlorinated polyolefin (B) that does not cause precipitation. Polyolefin which has not been subjected to chlorination is not preferred because it has extremely low solubility in the compound (A) which is cured by irradiation with active energy rays.

Examples of the chlorinated polyolefin (B) used in the present invention include chlorinated polyethylene, chlorinated polypropylene, acrylic-modified or urethane-modified chlorinated polyolefin (B).

The chlorine content in the chlorinated polyolefin (B) is preferably 25 to 50% by weight, more preferably 30 to 45% by weight. If it is less than 25% by weight, the solubility in the compound (A) that is cured by irradiation with active energy rays may be reduced, and it may be difficult to form an optically transparent composition. If it exceeds 50% by weight, the change in optical properties under severe humidification conditions when used as a polarizing film becomes large, and the effects of the present invention may not be obtained. The chlorine content in the chlorinated polyolefin (B) can be measured according to JIS-K7229. More specifically, for example, it can be measured using an “oxygen flask combustion method” in which a chlorine-containing resin is combusted in an oxygen atmosphere, the generated gaseous chlorine is absorbed with water, and quantified by titration.

The weight average molecular weight of the chlorinated polyolefin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and most preferably 10,000 to 20,000. Things are used. If the molecular weight of the chlorinated polyolefin (B) is too low, the water resistance may not be sufficiently improved when the active energy ray-curable resin composition is cured. Moreover, when molecular weight is too high, the solubility with respect to the compound (A) hardened | cured by irradiation of an active energy ray will fall remarkably, and it may become difficult to form an optically transparent composition.

Examples of commercially available chlorinated polyolefins (B) include Super Clon series (Nippon Paper Chemical Co., Ltd.), Hardlen series (Toyobo Co., Ltd.), Elastlene series (Showa Denko Co., Ltd.), etc. It can be illustrated.

Among those available as a commercial product, “Super Clone 814HS”, “Super Clone 390S”, “Super Clone 3228S”, “Super Clone 803 MW”, “Super Clone 803 L” of Super Clone series (manufactured by Nippon Paper Chemicals), “Super Clon B”, “Hardlen 16-LP”, “Hardren 15-LP”, “Hardren CY-9124P” from the Hardren series (Toyobo), “Eraslen 404B” from the Elastlen series (made by Showa Denko) , “Elaslene 402B”, “Elaslene 401A”, etc. can be used more preferably. Especially, “Superclone 814HS” is soluble in the compound (A) that is cured by irradiation with active energy rays, and is severely humidified when made into a polarizing film. Of optical properties under various conditions It can be suitably used than for good balance.

In the curable resin composition for an optical film according to the present invention, the weight ratio of the compound (A) that is cured by irradiation with active energy rays and the chlorinated polyolefin (B) is preferably 100: 1 to 100: 40. When the weight ratio of the chlorinated polyolefin (B) is too small, the change in optical characteristics under severe humidification conditions, which is the effect of the present invention, may become large. On the other hand, when the weight ratio of the chlorinated polyolefin (B) is too large, the compatibility with the compound (A) that is cured by irradiation with active energy rays is reduced, and an optically transparent active energy ray-curable resin composition is obtained. It may not be formed. The weight ratio of the compound (A) that is cured by irradiation with active energy rays and the chlorinated polyolefin (B) is more preferably 100: 3 to 100: 30, and most preferably 100: 5 to 100: 15. .

<Aspects of radical polymerization curable resin composition>
The curable resin composition for optical films according to the present invention can also be referred to as an active energy ray-curable resin composition. When the active energy ray-curable resin composition uses an electron beam or the like as the active energy ray, the active energy ray-curable resin composition does not need to contain a photopolymerization initiator, but the active energy ray When ultraviolet rays or visible rays are used, it is preferable to contain a photopolymerization initiator.

≪Photopolymerization initiator≫
The photopolymerization initiator in the case of using the radical polymerizable compound is appropriately selected depending on the active energy ray. In the case of curing by ultraviolet light or visible light, a photopolymerization initiator for ultraviolet light or visible light cleavage is used. Examples of the photopolymerization initiator include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2 -Propyl) ketone, aromatic ketone compounds such as α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy- Acetophenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin methyl ether; Benzoin ethyl ether, benzoin Benzoin ether compounds such as isopropyl ether, benzoin butyl ether and anisoin methyl ether; aromatic ketal compounds such as benzyldimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1-phenone-1 , 1-propanedione-2- (o-ethoxycarbonyl) oxime, photoactive oxime compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichloro Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone; camphorquinone; halogenated ketone; acylphosphine Inokishido; and acyl phospholipase diisocyanate, and the like.

The blending amount of the photopolymerization initiator is 20% by weight or less with respect to the total amount of the curable resin composition. The blending amount of the photopolymerization initiator is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, and further preferably 0.1 to 5% by weight.

In addition, when the curable resin composition used in the present invention is used for visible light curable containing a radical polymerizable compound as a curable component, a photopolymerization initiator that is particularly sensitive to light of 380 nm or more is used. It is preferable to use it. A photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.

As said photoinitiator, the compound represented by following General formula (2);

(Wherein R ⁴ and R ⁵ represent —H, —CH ₂ CH ₃ , —iPr or Cl, and R ⁴ and R ⁵ may be the same or different), either alone or in general formula ( It is preferable to use together the compound represented by 2) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later. When the compound represented by the general formula (2) is used, the adhesiveness is excellent as compared with the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. Among the compounds represented by the general formula (2), diethylthioxanthone in which R ⁴ and R ⁵ are —CH ₂ CH ₃ is particularly preferable. The composition ratio of the compound represented by the general formula (4) in the curable resin composition is preferably 0.1 to 5% by weight with respect to the total amount of the curable resin composition, 0.5 to It is more preferably 4% by weight, still more preferably 0.9 to 3% by weight.

Further, it is preferable to add a polymerization initiation assistant as necessary. Examples of polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable. When a polymerization initiation assistant is used, the amount added is usually 0 to 5% by weight, preferably 0 to 4% by weight, most preferably 0 to 3% by weight, based on the total amount of the curable resin composition. .

Further, a known photopolymerization initiator can be used in combination as necessary. Since the transparent protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator. Specifically, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.

In particular, as a photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (2), a compound represented by the following general formula (3);

(Wherein R ⁶ , R ⁷ and R ⁸ represent —H, —CH ₃ , —CH ₂ CH ₃ , —iPr or Cl, and R ⁶ , R ⁷ and R ⁸ may be the same or different). It is preferable to use it. As the compound represented by the general formula (3), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907 manufacturer: BASF) which is also a commercially available product is suitable. Can be used. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF), 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferred because of its high sensitivity.

<Radical polymerizable compound having active methylene group and radical polymerization initiator having hydrogen abstraction action>
In the active energy ray-curable resin composition, when a radical polymerizable compound having an active methylene group is used as the radical polymerizable compound, it is preferably used in combination with a radical polymerization initiator having a hydrogen abstracting action. According to such a configuration, the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a high humidity environment or immediately after being taken out from water (non-dried state). The reason for this is not clear, but the following causes are considered. That is, the radical polymerizable compound having an active methylene group is taken into the main chain and / or side chain of the base polymer in the adhesive layer while polymerizing together with other radical polymerizable compounds constituting the adhesive layer. An agent layer is formed. In such a polymerization process, when a radical polymerization initiator having a hydrogen abstracting action is present, a base polymer constituting the adhesive layer is formed, while hydrogen is extracted from the radical polymerizable compound having an active methylene group to form a methylene group. Radicals are generated. And the methylene group which the radical generate | occur | produced, and the hydroxyl group of polarizers, such as PVA, react, and a covalent bond is formed between an adhesive bond layer and a polarizer. As a result, it is speculated that the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a non-dry state.

In the present invention, examples of the radical polymerization initiator having a hydrogen abstracting action include thioxanthone radical polymerization initiators and benzophenone radical polymerization initiators. The radical polymerization initiator is preferably a thioxanthone radical polymerization initiator. Examples of the thioxanthone radical polymerization initiator include compounds represented by the above general formula (2). Specific examples of the compound represented by the general formula (2) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. Among the compounds represented by the general formula (2), diethylthioxanthone in which R4 and R5 are —CH ₂ CH ₃ is particularly preferable.

When the active energy ray-curable resin composition contains a radical polymerizable compound having an active methylene group and a radical polymerization initiator having a hydrogen abstraction function, the total amount of the curable component is 100% by weight. The radical polymerizable compound having an active methylene group is preferably contained in an amount of 1 to 50% by weight, and the radical polymerization initiator is preferably contained in an amount of 0.1 to 10% by weight based on the total amount of the curable resin composition.

As described above, in the present invention, a radical is generated in the methylene group of a radical polymerizable compound having an active methylene group in the presence of a radical polymerization initiator having a hydrogen abstraction function, and the methylene group and a polarizer such as PVA are used. React with a hydroxyl group to form a covalent bond. Therefore, in order to generate radicals in the methylene group of the radical polymerizable compound having an active methylene group and to sufficiently form such a covalent bond, when the total amount of the curable component is 100% by weight, the radical having an active methylene group. The content of the polymerizable compound is preferably 1 to 50% by weight, and more preferably 3 to 30% by weight. In order to sufficiently improve the water resistance and improve the adhesion in a non-dry state, the radical polymerizable compound having an active methylene group is preferably 1% by weight or more. On the other hand, if it exceeds 50% by weight, the adhesive layer may be poorly cured. The radical polymerization initiator having a hydrogen abstracting action is preferably contained in an amount of 0.1 to 10% by weight, more preferably 0.3 to 9% by weight, based on the total amount of the curable resin composition. preferable. In order to sufficiently advance the hydrogen abstraction reaction, it is preferable to use a radical polymerization initiator in an amount of 0.1% by weight or more. On the other hand, if it exceeds 10% by weight, it may not completely dissolve in the composition.

<Photocationic polymerization initiator>
The cationic polymerization curable resin composition contains at least one compound selected from a compound having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group as described above as a curable component. Therefore, a cationic photopolymerization initiator is blended. This cationic photopolymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and starts a polymerization reaction of an epoxy group or an oxetanyl group. As the photocationic polymerization initiator, a photoacid generator and a photobase generator can be used, and a photoacid generator described later is preferably used. In addition, when the curable resin composition used in the present invention is used with visible light curability, it is particularly preferable to use a photocationic polymerization initiator that is highly sensitive to light of 380 nm or more. Is generally a compound that exhibits maximum absorption in the vicinity of 300 nm or shorter, and therefore, a photosensitizer that exhibits maximum absorption in light having a wavelength longer than that, specifically, longer than 380 nm should be blended. Thus, it is possible to respond to light having a wavelength in the vicinity and promote generation of cationic species or acid from the photocationic polymerization initiator. Examples of the photosensitizer include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes, and the like. Two or more types may be mixed and used. In particular, anthracene compounds are preferable because of their excellent photosensitization effect, and specific examples include anthracure UVS-1331 and anthracure UVS-1221 (manufactured by Kawasaki Kasei Co., Ltd.). The content of the photosensitizer is preferably 0.1% by weight to 5% by weight, and more preferably 0.5% by weight to 3% by weight.

<Other ingredients>
The curable resin composition used in the present invention preferably contains the following components.

<Acrylic oligomer>
The active energy ray-curable resin composition used in the present invention can contain an acrylic oligomer obtained by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound. By containing the component in the active energy ray-curable resin composition, the shrinkage of curing when the active energy ray is irradiated and cured on the composition is reduced, and the adhesive, the polarizer, the transparent protective film and the like are covered. Interfacial stress with the adherend can be reduced. As a result, it is possible to suppress a decrease in adhesiveness between the adhesive layer and the adherend. In order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the content of the acrylic oligomer is preferably 20% by weight or less based on the total amount of the curable resin composition. More preferably, it is less than or equal to weight percent. When there is too much content of the acrylic oligomer in curable resin composition, the fall of the reaction rate at the time of irradiating this composition with an active energy ray will be intense, and it may become a hardening defect. On the other hand, the acrylic oligomer is preferably contained in an amount of 3% by weight or more, more preferably 5% by weight or more based on the total amount of the curable resin composition.

The active energy ray-curable resin composition preferably has a low viscosity in consideration of the workability and uniformity during coating. Therefore, an acrylic oligomer obtained by polymerizing a (meth) acrylic monomer also has a low viscosity. Preferably there is. The acrylic oligomer having a low viscosity and capable of preventing curing shrinkage of the adhesive layer preferably has a weight average molecular weight (Mw) of 15000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. preferable. On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer is preferably 500 or more, more preferably 1000 or more, It is especially preferable that it is 1500 or more. Specific examples of the (meth) acrylic monomer constituting the acrylic oligomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl- 2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (Meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate (Meth) acrylic acid (carbon number 1-20) alkyl esters such as 4-methyl-2-propylpentyl (meth) acrylate and N-octadecyl (meth) acrylate, and further, for example, cycloalkyl (meth) acrylate (for example, Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, etc.), aralkyl (meth) acrylate (eg benzyl (meth) acrylate, etc.), polycyclic (meth) acrylate (eg 2-isobornyl (meth) acrylate, 2 -Norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylic acid ester (E.g. hydro (Methyl) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropylmethyl-butyl (meth) methacrylate, etc.), alkoxy group or phenoxy group-containing (meth) acrylic acid esters (2-methoxyethyl ( (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), epoxy Group-containing (meth) acrylic acid esters (for example, glycidyl (meth) acrylate), halogen-containing (meth) acrylic acid esters (for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 2- Trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc.), alkylaminoalkyl (meth) An acrylate (for example, dimethylaminoethyl (meth) acrylate etc.) etc. are mentioned. These (meth) acrylates can be used alone or in combination of two or more. Specific examples of the acrylic oligomer include “ARUFON” manufactured by Toagosei Co., Ltd., “Act Flow” manufactured by Soken Chemical Co., Ltd., “JONCRYL” manufactured by BASF Japan.

<Photo acid generator>
In the active energy ray-curable resin composition, a photoacid generator can be contained. When the active energy ray-curable resin composition contains a photoacid generator, the water resistance and durability of the adhesive layer can be dramatically improved as compared to the case where no photoacid generator is contained. . The photoacid generator can be represented by the following general formula (4).

General formula (4)

(However, L ⁺ represents any onium cation. X ⁻ represents PF6 ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate. anion, SCN ^- represents a counter anion selected from the group more consisting).

Next, the counter anion X- in the general formula (4) will be described.

Formula (4) counter anion X in ^- are but are not theoretically limited to, non-nucleophilic anion is preferred. When the counter anion X ⁻ is a non-nucleophilic anion, a nucleophilic reaction is unlikely to occur in cations coexisting in the molecule and various materials used in combination, and as a result, the photoacid generator itself represented by the general formula (4) It is possible to improve the aging stability of a composition using the same. The non-nucleophilic anion here refers to an anion having a low ability to cause a nucleophilic reaction. Examples of such anions include PF6 ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ^{− and the} like.

Specifically, “Syracure UVI-6922”, “Syracure UVI-6974” (manufactured by Dow Chemical Japan Co., Ltd.), “Adekaoptomer SP150”, “Adekaoptomer SP152”, “Adekaoptomer” “SP170”, “Adekaoptomer SP172” (manufactured by ADEKA Corporation), “IRGACURE250” (manufactured by Ciba Specialty Chemicals), “CI-5102”, “CI-2855” (manufactured by Nippon Soda Co., Ltd.), “Sun-Aid SI-60L”, “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-180L” (manufactured by Sanshin Chemical Co., Ltd.), “CPI-100P”, "CPI-100A" (San Apro Co., Ltd.), "WPI-06 "," WPI-113 "," WPI-116 "," WPI-041 "," WPI-044 "," WPI-054 "," WPI-055 "," WPAG-281 "," WPAG-567 " “WPAG-596” (manufactured by Wako Pure Chemical Industries, Ltd.) is a preferred specific example of the photoacid generator of the present invention.

The content of the photoacid generator is 10% by weight or less, preferably 0.01 to 10% by weight, and preferably 0.05 to 5% by weight with respect to the total amount of the curable resin composition. Is more preferable, and 0.1 to 3% by weight is particularly preferable.

<Photobase generator>
The photobase generator can function as a catalyst for a polymerization reaction of a radical polymerizable compound or an epoxy resin by changing the molecular structure by light irradiation such as ultraviolet light or visible light, or by cleaving the molecule. It is a compound that produces one or more basic substances. Examples of basic substances include secondary amines and tertiary amines. Examples of the photobase generator include the α-aminoacetophenone compound, the oxime ester compound, an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, an alcohol, and the like. Examples thereof include compounds having a substituent such as an oxybenzyl carbamate group. Of these, oxime ester compounds are preferred.

Examples of the compound having an acyloxyimino group include O, O'-diacetphenone oxime succinate, O, O'-dinaphthophenone oxime succinate, and a benzophenone oxime acrylate-styrene copolymer.

Examples of the compound having an N-formylated aromatic amino group and an N-acylated aromatic amino group include di-N- (p-formylamino) diphenylmethane, di-N (p-aceethylamino) diphenylmelane, Di-N- (p-benzoamido) diphenylmethane, 4-formylaminotoluylene, 4-acetylaminotoluylene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1-acetylaminonaphthalene, 1,5 -Diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1,5-diformylaminoanthraquinone, 3,3'- Dimethyl-4,4'-diformylaminobiphenyl, 4 4'-formylamino benzophenones.

Examples of the compound having a nitrobenzyl carbamate group or an alkoxybenzyl carbamate group include bis {{(2-nitrobenzyl) oxy} carbonyl} diaminodiphenylmethane, 2,4-di {{(2-nitrobenzyl) oxy} toluylene. Bis {{(2-nitrobenzyloxy) carbonyl} hexane-1,6-diamine, m-xylidine {{(2-nitro-4-chlorobenzyl) oxy} amide}.

The photobase generator is preferably at least one of an oxime ester compound and an α-aminoacetophenone compound, and more preferably an oxime ester compound. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable.

As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2- propenoyl] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethylidazole base) You can also.

<Compound containing either alkoxy group or epoxy group>
In the active energy ray-curable resin composition, a compound containing a photoacid generator, an alkoxy group, or an epoxy group can be used in the active energy ray-curable resin composition.

(Compound having epoxy group and polymer)
When using a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule, two functional groups having reactivity with the epoxy group are contained in the molecule. Two or more compounds may be used in combination. Here, examples of the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, and a primary or secondary aromatic amino group. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.

Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy derived from bisphenol F and epichlorohydrin. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Multifunctional epoxy resin such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin , Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. These epoxy resins may be halogenated and hydrogenated It may be. As commercially available epoxy resin products, for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., Epicron manufactured by DIC Corporation 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, manufactured by ADEKA Co., Ltd., Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel Chemical Co., Ltd., Epolide series, EHPE Series, YD series, YDF series, YDCN series, YDB series, phenoxy resins (polysynthesized from bisphenols and epichlorohydrin) Mud carboxymethyl at both ends with polyether having an epoxy group; and YP series), Nagase ChemteX Corporation of Denacol series manufactured by Kyoeisha although chemical Co. Epo light series are exemplified but not limited thereto. Two or more of these epoxy resins may be used in combination.

(Compounds and polymers having an alkoxyl group)
The compound having an alkoxyl group in the molecule is not particularly limited as long as it has one or more alkoxyl groups in the molecule, and known compounds can be used. Representative examples of such compounds include melamine compounds, amino resins, and silane coupling agents.

The compounding amount of the compound containing either an alkoxy group or an epoxy group is usually 30% by weight or less based on the total amount of the curable resin composition, and if the content of the compound in the composition is too large, the adhesiveness May decrease, and the impact resistance to the drop test may deteriorate. The content of the compound in the composition is more preferably 20% by weight or less. On the other hand, from the viewpoint of water resistance, the compound preferably contains 2% by weight or more, more preferably 5% by weight or more in the composition.

<Silane coupling agent>
When the curable resin composition used in the present invention is active energy ray curable, it is preferable to use an active energy ray curable compound as the silane coupling agent. Even if not, the same water resistance can be imparted.

Specific examples of silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycid as active energy ray-curable compounds. Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Examples thereof include silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

Preferred are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

As a specific example of the silane coupling agent that is not active energy ray-curable, a silane coupling agent (D1) having an amino group is preferable. Specific examples of the silane coupling agent (D1) having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane Γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane , Γ- (6-Aminohexyl) Minopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyl Amino group-containing silanes such as trimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutyrate) Reden) 3 may be mentioned ketimines type silanes such as (triethoxysilyl) -1-propanamine.

The silane coupling agent (D1) having an amino group may be used alone or in combination of two or more. Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- 1-propanamine is preferred.

The blending amount of the silane coupling agent is preferably in the range of 0.01 to 20% by weight, preferably 0.05 to 15% by weight, and preferably 0.1 to 10% with respect to the total amount of the curable resin composition. More preferably, it is% by weight. This is because when the blending amount exceeds 20% by weight, the storage stability of the curable resin composition is deteriorated, and when it is less than 0.1% by weight, the effect of adhesion water resistance is not sufficiently exhibited.

Specific examples of silane coupling agents that are not active energy ray-curable other than the above include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxy. Examples include silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and imidazolesilane.

<Compounds having a vinyl ether group>
When the curable resin composition used in the present invention contains a compound having a vinyl ether group, it is preferable because the adhesion water resistance between the polarizer and the adhesive layer is improved. The reason why such an effect is obtained is not clear, but it is presumed that one of the reasons is that the adhesive force between the polarizer and the adhesive layer is increased by the interaction of the vinyl ether group of the compound with the polarizer. The In order to further improve the adhesion water resistance between the polarizer and the adhesive layer, the compound is preferably a radical polymerizable compound having a vinyl ether group. The content of the compound is preferably 0.1 to 19% by weight with respect to the total amount of the curable resin composition.

<Compounds that produce keto-enol tautomerism>
The curable resin composition used in the present invention may contain a compound that causes keto-enol tautomerism. For example, in a curable resin composition containing a crosslinking agent or a curable resin composition that can be used by blending a crosslinking agent, an embodiment containing a compound that produces the keto-enol tautomerism can be preferably employed. Thereby, an excessive viscosity increase and gelation of the curable resin composition after blending the organometallic compound and the formation of a microgel product can be suppressed, and the effect of extending the pot life of the composition can be realized.

Various β-dicarbonyl compounds can be used as the compound that causes keto-enol tautomerism. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane- Β-diketones such as 3,5-dione; acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate propionyl acetates such as tert-butyl; isobutyryl acetates such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tert-butyl isobutylyl acetate; malonic acid esters such as methyl malonate and ethyl malonate Le acids; and the like. Among these, acetylacetone and acetoacetic acid esters are preferable compounds. Such compounds producing keto-enol tautomerism may be used alone or in combination of two or more.

The amount of the compound that generates keto-enol tautomerism is, for example, 0.05 to 10 parts by weight, preferably 0.2 to 3 parts by weight (for example, 0.3 parts by weight) with respect to 1 part by weight of the organometallic compound. Parts by weight to 2 parts by weight). If the amount of the compound used is less than 0.05 parts by weight relative to 1 part by weight of the organometallic compound, it may be difficult to achieve a sufficient use effect. On the other hand, when the amount of the compound used exceeds 10 parts by weight with respect to 1 part by weight of the organometallic compound, it may be difficult to express the desired water resistance due to excessive interaction with the organometallic compound.

<Polyrotaxane>
The curable resin composition of the present invention can contain a polyrotaxane. The polyrotaxane includes a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blockade disposed at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule. And a group. The cyclic molecule preferably has an active energy ray-curable functional group.

The cyclic molecule is not particularly limited as long as it is a molecule in which a linear molecule is included in a skewered manner in the opening and is movable on the linear molecule and has an active energy ray polymerizable group. In the present specification, “cyclic” of “cyclic molecule” means substantially “cyclic”. That is, the cyclic molecule may not be completely closed as long as it can move on the linear molecule.

Specific examples of the cyclic molecule preferably include cyclic polymers such as cyclic polyether, cyclic polyester, cyclic polyetheramine, and cyclic polyamine, and cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. It is done. Of these, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferred because they are relatively easily available and many types of blocking groups can be selected. Two or more cyclic molecules may be mixed in the polyrotaxane or in the adhesive.

In the polyrotaxane used in the present invention, the cyclic molecule has an active energy ray polymerizable group. Thereby, the polyrotaxane and the active energy ray-curable component react to obtain an adhesive having a movable crosslinking point even after curing. The active energy ray-polymerizable group of the cyclic molecule may be any group that can be polymerized with the active energy ray-curable compound. For example, radical polymerizable groups such as (meth) acryloyl group and (meth) acryloyloxy group may be used. Can be mentioned.

When cyclodextrin is used as the cyclic molecule, the active energy ray polymerizable group is preferably introduced to the hydroxyl group of cyclodextrin via any appropriate linker. The number of active energy ray polymerizable groups contained in one molecule of the polyrotaxane is preferably 2 to 1280, more preferably 50 to 1000, and still more preferably 90 to 900.

It is preferable that a hydrophobic modifying group is introduced into the cyclic molecule. By introducing the hydrophobic modifying group, the compatibility with the active energy ray-curable component can be improved. In addition, since hydrophobicity is imparted, when used in a polarizing film, water can be prevented from entering the interface between the adhesive layer and the polarizer, and the water resistance can be further improved. Examples of the hydrophobic modifying group include a polyester chain, a polyamide chain, an alkyl chain, an oxyalkylene chain, and an ether chain. Specific examples include groups described in [0027] to [0042] of WO2009 / 145073.

A polarizing film using a resin composition containing a polyrotaxane as an adhesive is excellent in water resistance. The reason why the water resistance of the polarizing film is improved is not clear, but is presumed as follows. That is, the ability of the crosslinking point to move due to the mobility of the cyclic molecules of polyrotaxane (so-called pulley effect) gives the cured adhesive flexibility and increases the adhesion of the polarizer to the surface irregularities. As a result, it is considered that water has been prevented from entering the interface between the polarizer and the adhesive layer. Furthermore, it is considered that the addition of hydrophobicity to the adhesive due to the polyrotaxane having a hydrophobic modifying group also contributed to preventing water from entering the interface between the polarizer and the adhesive layer.

The content of the polyrotaxane is preferably 2% by weight to 50% by weight with respect to the resin composition.

The curable resin composition has the following general formula (5):

(Wherein X is at least one selected from the group consisting of vinyl group, (meth) acryl group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy group, oxetane group and mercapto group) A functional group containing a reactive group, wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, aryl group, or heterocyclic group) can do. The compound described in the general formula (5) easily forms an ester bond with the hydroxyl group of the polyvinyl alcohol polarizer. Moreover, the compound as described in the said General formula (5) has further X containing a reactive group, and reacts with the other curable component contained in curable resin composition through the reactive group which X contains. That is, the boric acid group and / or boric acid ester group that the curable resin layer has are firmly bonded to the hydroxyl group that the polarizer has through a covalent bond. As a result, even if moisture is present at the interface between the polarizer and the curable resin layer, these are strongly interacting not only through hydrogen bonds and / or ionic bonds but also through covalent bonds. Water resistance between the curable resin layer and the curable resin layer is dramatically improved. Improvement in adhesion and water resistance between the polarizer and the cured product layer, in particular, from the viewpoint of improvement in adhesion and water resistance when the polarizer and the transparent protective film are bonded via the adhesive layer, a curable resin composition Among them, the content of the compound represented by the general formula (5) is preferably 0.001 to 50% by weight, more preferably 0.1 to 30% by weight, and 1 to 10% by weight. Most preferred.

<Organic metal compound>
When the curable resin composition of the present invention contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates and a polymerizable compound having a polymerizable functional group and a carboxyl group at the same time, polarized light This is preferable because the adhesion water resistance between the child and the adhesive layer is improved. The organometallic compound becomes an active metal species due to the presence of moisture, and as a result, the organometallic compound strongly interacts with both the polarizer and the active energy ray-curable component constituting the adhesive layer. As a result, even if moisture is present at the interface between the polarizer and the adhesive layer, since they interact strongly through the organometallic compound, the adhesive water resistance between the polarizer and the adhesive layer Will improve dramatically. Although the organometallic compound greatly contributes to the improvement of the adhesiveness and water resistance of the adhesive layer, the composition containing it has a short pot life due to the unstable liquid stability, and the productivity is reduced. There is a tendency to get worse. This is because the organometallic compound is highly reactive and comes into contact with moisture contained in a trace amount in the composition, causing hydrolysis and self-condensation reactions, resulting in self-aggregation and clouding of the composition liquid (aggregate) Generation, phase separation, and precipitation). However, when the composition contains a polymerizable compound having a polymerizable functional group and a carboxyl group together with an organometallic compound, it suppresses hydrolysis and self-condensation reactions of the organometallic compound, and the organometallic compound in the composition It is possible to dramatically improve the liquid stability. The ratio of the organometallic compound is preferably 0.05 to 15% by weight, more preferably 0.1 to 10% by weight, based on the total amount of the composition. When the blending amount exceeds 15% by weight, the storage stability of the composition may be deteriorated, or the ratio of components for adhering to a polarizer or a protective film may be relatively insufficient, resulting in a decrease in adhesiveness. Moreover, when it is less than 0.05% by weight, the effect of adhesion water resistance is not sufficiently exhibited. In the curable adhesive composition, when the total amount of the organometallic compound is α (mol), the content of the polymerizable compound having a compatible functional group and a carboxyl group is preferably 0.25α (mol) or more. 0.35α (mol) or more is more preferable, and 0.5α (mol) or more is particularly preferable. When the content of the polymerizable compound having a compatible functional group and a carboxyl group is less than 0.25α (mol), the stabilization of the organometallic compound becomes insufficient, the hydrolysis reaction and the self-condensation reaction proceed, and the pot life May become shorter. The upper limit of the content of the polymerizable compound with respect to the total amount α (mol) of the organometallic compound is not particularly limited, but for example, about 4α (mol) can be exemplified.

<Additives other than the above>
Moreover, various additives can be mix | blended with the curable resin composition used by this invention as another arbitrary component in the range which does not impair the objective and effect of this invention. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Plasticizers; UV absorbers; inorganic fillers; pigments; dyes and the like.

The above-mentioned additives are usually 0 to 10% by weight, preferably 0 to 5% by weight, and most preferably 0 to 3% by weight, based on the total amount of the curable resin composition.

<Curable resin composition for optical film>
The curable resin composition for an optical film according to the present invention has a bulk water absorption of 10% by weight or less when a cured product obtained by curing the composition is immersed in pure water at 23 ° C. for 24 hours. Is preferred. The bulk water absorption is expressed by the following equation.
Formula: {(M2-M1) / M1} × 100 (%),
However, M1: Weight of the cured product before immersion, M2: Weight of the cured product after immersion. Polarization when the polarizing film is placed in a severe high-temperature and high-humidity environment by setting the bulk water absorption to 10% by weight or less. The movement of water to the child is suppressed, and the increase in the transmittance of the polarizer and the decrease in the degree of polarization can be suppressed. The bulk water absorption is preferably 5% by weight or less, more preferably 3% by weight or less from the viewpoint of making the optical durability in a harsh environment at a high temperature more favorable for the adhesive layer of the polarizing film. Most preferably, it is 1% by weight or less. On the other hand, when the polarizer and the transparent protective film are bonded together, the polarizer retains a certain amount of moisture. When the curable adhesive comes into contact with moisture contained in the polarizer, repelling, bubbles, etc. Appearance defects may occur. In order to suppress poor appearance, it is preferable that the curable adhesive can absorb a certain amount of moisture. More specifically, the bulk water absorption is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more.

The viscosity of the curable resin composition used in the present invention is preferably 3 to 100 mPa · s, more preferably 5 to 50 mPa · s, and most preferably 10 to 30 mPa · s. When the viscosity of the curable resin composition is high, the surface smoothness after coating is poor and the appearance is poor, which is not preferable. The curable resin composition used in the present invention can be applied by adjusting the viscosity to a preferred range by heating or cooling the composition.

The curable resin composition of the present invention preferably has a high octanol / water partition coefficient (hereinafter referred to as logPow value). The logPow value is an index representing the lipophilicity of a substance and means the logarithmic value of the octanol / water partition coefficient. High logPow means that it is lipophilic, that is, low water absorption. The logPow value can also be measured (flask immersion method described in JIS-Z-7260), but calculated based on the structure of each compound that is a component (such as a curable component) of a curable adhesive for polarizing films. Can also be calculated. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft is used.
Based on the calculated value, the logPow value of the polarizing film curable adhesive in the present invention can be calculated by the following formula.
LogPow of curable adhesive = Σ (logPow × Wi)
logPowi: logPow value of each component of curable adhesive Wi: (number of moles of i component) / (total number of moles of each component of curable adhesive)
In the above calculation, among the components of the curable adhesive, components that do not form a skeleton of a cured product (adhesive layer) such as a polymerization initiator and a photoacid generator are excluded from the components in the above calculation. The logPow value of the curable adhesive for polarizing film of the present invention is preferably 1 or more, more preferably 1.5 or more, and most preferably 2 or more. Thereby, water resistance and humidification durability can be improved. On the other hand, the logPow value of the curable adhesive for polarizing film of the present invention is usually about 8 or less, preferably 5 or less, and more preferably 4 or less. If the logPow value is too high, appearance defects such as repelling and bubbles are likely to occur as described above, which is not preferable.

Furthermore, it is preferable that the curable resin composition of the present invention does not substantially contain a volatile solvent. By substantially not containing a volatile solvent, heat treatment becomes unnecessary, which is not only excellent in productivity, but also preferable because it can suppress deterioration of the optical characteristics of the polarizer due to heat. “Substantially free” means, for example, when the total amount of the curable resin composition is 100% by weight or less, it means that it is contained in an amount of less than 5% by weight, in particular, it is contained in an amount of less than 2% by weight. Shall.

The curable resin composition is preferably selected so that the Tg of the cured product layer formed by this, particularly the adhesive layer, is 60 ° C. or higher, and more preferably 70 ° C. or higher. Further, it is preferably 75 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. On the other hand, if the Tg of the adhesive layer becomes too high, the flexibility of the polarizing film is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 180 ° C. or lower. Tg <glass transition temperature> is measured under the following measurement conditions using a TA Instruments dynamic viscoelasticity measuring apparatus RSAIII.
Sample size: width 10mm, length 30mm,
Clamp distance 20mm,
Measurement mode: Tensile, Frequency: 1 Hz, Temperature rising rate: 5 ° C./min Dynamic viscoelasticity was measured and adopted as the temperature Tg of tan δ peak top.

The curable resin composition preferably has a storage elastic modulus of the cured product layer, particularly the adhesive layer formed thereby, of 1.0 × 10 ⁷ Pa or more at 25 ° C. More preferably, it is ⁸ Pa or more. The storage elastic modulus of the pressure-sensitive adhesive layer is preferably 1.0 × 10 ³ Pa to 1.0 × 10 ⁶ Pa. The storage elastic modulus of the adhesive layer affects the polarizer cracks when the polarizing film is subjected to a heat cycle (-40 ° C to 80 ° C, etc.). If the storage elastic modulus is low, defects in the polarizer cracks occur. Cheap. The temperature region having a high storage elastic modulus is more preferably 80 ° C. or less, and most preferably 90 ° C. or less. The storage elastic modulus is measured under the same measurement conditions using a dynamic viscoelasticity measuring device RSAIII manufactured by TA Instruments simultaneously with Tg <glass transition temperature>. The dynamic viscoelasticity was measured and the value of the storage elastic modulus (E ′) was adopted.

In addition, since the curable resin composition of the present invention has a curable component, curing shrinkage usually occurs when the curable resin composition is cured. The cure shrinkage rate is an index indicating the rate of cure shrinkage when forming the adhesive layer from the resin composition. When the cure shrinkage rate of the adhesive layer is increased, it is preferable to suppress the occurrence of poor adhesion due to interface strain when the curable resin composition is cured to form the adhesive layer. From the above viewpoint, it is preferable that the curing shrinkage rate of the cured product obtained by curing the t-resin composition having the effect of the present invention is 10% or less. The curing shrinkage rate is preferably small, and the curing shrinkage rate is preferably 8% or less, more preferably 5% or less. The cure shrinkage rate is measured by the method described in JP2013-104869A, and specifically, measured by the method using a cure shrinkage sensor manufactured by Centec Co., Ltd. described in the examples.

In addition, the curable resin composition used in the present invention preferably uses a material having low skin irritation as the curable component from the viewpoint of safety. Skin irritation is P.I. I. Judgment can be made with the index I. P. I. I is widely used to indicate the degree of skin injury and is measured by the Draise method. The measured value is displayed in the range of 0 to 8, and it is determined that the irritation is lower as the value is smaller. However, since the error of the measured value is large, it should be taken as a reference value. P. I. I is preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.

<Optical film>
The curable resin composition according to the present invention can be suitably used for optical film applications, particularly for polarizing film applications having at least a polyvinyl alcohol polarizer. Hereinafter, a polarizing film will be described as an example of an optical film.

<Polarizing film>
The polarizing film according to the present invention has a cured product layer of a curable resin composition for an optical film containing an active energy ray-curable component (A) and a chlorinated polyolefin (B) on at least one surface of a polyvinyl alcohol polarizer. Are stacked. In addition, this polarizing film may further laminate | stack a transparent protective film. For example, a transparent protective film may be laminated on at least one side of a polyvinyl alcohol polarizer via a cured product layer of a curable resin composition for optical films, and the cured on one side of a polyvinyl alcohol polarizer. A material layer may be laminated and a transparent protective film may be laminated on the other surface.

Furthermore, the polarizing film according to the present invention may be provided with an adhesive layer. The pressure-sensitive adhesive layer can be laminated at an arbitrary position. For example, the cured product layer may be laminated on a polyvinyl alcohol polarizer, and the pressure-sensitive adhesive layer may be formed thereon. The cured product layer may be laminated on the other surface, and the adhesive layer may be laminated on the other surface. Or you may laminate | stack an adhesive layer on the said protective film side of the polarizing film which consists of polarizer / the said hardened | cured material layer / protective film. Thus, an adhesive layer can be laminated | stacked on the arbitrary positions of a polarizing film.

The thickness of a polarizing film obtained by laminating a polyvinyl alcohol polarizer, a cured product layer of the composition of the present invention, a transparent protective film, and an adhesive layer is preferably 150 μm or less, more preferably 100 μm. It is as follows. When the thickness of the polarizing film is too thick, the dimensional change under high temperature and high humidity becomes large, and a problem of display unevenness occurs, which is not preferable.

The thickness of the cured product layer formed from the curable resin composition, particularly the adhesive layer, is preferably 0.01 to 3.0 μm. When the thickness of the cured product layer is too thin, the cohesive force of the cured product layer is insufficient and the peeling force is lowered, which is not preferable. When the thickness of the cured product layer is too thick, peeling is likely to occur when stress is applied to the cross section of the polarizing film, and peeling failure due to impact occurs, which is not preferable. The thickness of the cured product layer is more preferably 0.1 to 2.5 μm, and most preferably 0.5 to 1.5 μm.

The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. And polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is preferably 2 to 30 μm, more preferably 4 to 20 μm, and most preferably 5 to 15 μm. When the thickness of the polarizer is thin, the optical durability is not preferable. When the thickness of the polarizer is thick, the dimensional change under high temperature and high humidity becomes large, and a problem of display unevenness occurs, which is not preferable.

A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

In addition, the active energy ray-curable resin composition used in the present invention has an effect (optical durability in a severe environment under high temperature and high humidity) when a thin polarizer having a thickness of 10 μm or less is used as the polarizer. Satisfied) can be remarkably expressed. The polarizer having a thickness of 10 μm or less is relatively more affected by moisture than a polarizer having a thickness exceeding 10 μm, and has insufficient optical durability in a high-temperature and high-humidity environment, resulting in increased transmittance and degree of polarization. Decline is likely to occur. That is, when the polarizer of 10 μm or less is laminated with the adhesive layer having a bulk water absorption of 10% by weight or less according to the present invention, the movement of water to the polarizer is suppressed in a severe high temperature and high humidity environment. Thus, deterioration of optical durability such as an increase in transmittance of the polarizing film and a decrease in the degree of polarization can be remarkably suppressed. The thickness of the polarizer is preferably 1 to 7 μm from the viewpoint of thinning. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, and the thickness of the polarizing film can be reduced.

As the thin polarizer, typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- And a thin polarizing film described in Japanese Patent Application No. 269002 and Japanese Patent Application No. 2010-263692. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

As the thin polarizing film, among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, the one obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric acid aqueous solution as described in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 is preferable.

As the transparent protective film, those having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like are preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Examples of the polymer that forms the transparent protective film include polymer blends. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. . When content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.

As the transparent protective film, Tg (glass transition temperature) is preferably 115 ° C or higher, more preferably 120 ° C or higher, further preferably 125 ° C or higher, and particularly preferably 130 ° C or higher. When Tg is 115 ° C. or higher, the polarizing film can be excellent in durability. Although the upper limit of Tg of the said transparent protective film is not specifically limited, From viewpoints of a moldability etc., Preferably it is 170 degrees C or less.

The polarizer and the transparent protective film may be subjected to a surface modification treatment before laminating the curable resin composition. In particular, the polarizer is preferably subjected to surface modification treatment on the surface of the polarizer before the curable resin composition is applied or bonded. Examples of the surface modification treatment include treatment such as corona treatment, plasma treatment, and intro treatment, and corona treatment is particularly preferable. By performing the corona treatment, polar functional groups such as a carbonyl group and an amino group are generated on the surface of the polarizer, and adhesion with the curable resin layer is improved. Moreover, the foreign material on the surface is removed by the ashing effect, or the unevenness on the surface is reduced, so that a polarizing film having excellent appearance characteristics can be created.

When the surface modification treatment is performed on the polarizer, it is preferable that the surface roughness (Ra) of the surface of the polarizer is 0.6 nm or more. The surface roughness (Ra) is preferably 0.8 nm or more, and more preferably 1 nm or more. By setting the surface roughness (Ra) to 0.6 nm or more, the polarizer can be transported satisfactorily even when the surface of the polarizer is brought into contact with the guide roll in the manufacturing process of the polarizing film. The surface roughness (Ra) is preferably 10 nm or less, and more preferably 5 nm or less, because when the surface roughness (Ra) becomes too large, the hot water resistance deteriorates.

The measurement of the surface roughness (Ra) is a parameter representing the surface roughness by the calculated average roughness (average value of surface irregularities). The measurement of the surface roughness (Ra) is a value measured in a taping mode using an atomic force microscope (AFM) Nanoscope IV manufactured by Beco. As the cantilever, for example, a metrology probe: Tap300 (RTESP type) was used. The measurement range is 1 μm square.

The optical film according to the present invention, particularly the polarizing film, can be produced by the following production method.
A method for producing an optical film comprising a cured product layer obtained by curing a curable resin composition for an optical film on at least one surface of a polyvinyl alcohol-based polarizer, wherein the curable resin composition for an optical film is active A coating step that contains the energy ray curable component (A) and the chlorinated polyolefin (B), and that directly coats the curable resin composition for optical films on at least one surface of the polyvinyl alcohol polarizer, An optical device comprising a curing step of irradiating an active energy ray from a polyvinyl alcohol polarizer surface side or a coating surface side of a curable resin composition for an optical film to cure the curable resin composition for an optical film. A method for producing a film.

The method for applying the curable resin composition for optical films is appropriately selected depending on the viscosity of the curable resin composition and the desired thickness. For example, reverse coater, gravure coater (direct, reverse or offset), bar reverse Examples include coaters, roll coaters, die coaters, bar coaters, and rod coaters.

Usually, when laminating two films, it is customary to apply and laminate the adhesive composition on the laminating surface of one side of the film, but laminating after applying the adhesive layer to the laminating surface of both sides of the film By doing, the laminated | multilayer film excellent in the external appearance quality can be obtained. The coating method is preferably a post-metering coating method. In the present invention, the “post-metering coating method” means a method of obtaining a predetermined coating film thickness by applying an external force to the liquid film to remove excess liquid. In the manufacturing method of the polarizing film which concerns on this invention, when the external force concerning the liquid film which consists of curable resin compositions is given, foreign materials, such as a dust and dust which exist in a bonding surface, are scraped off. Specific examples of the post-metering coating method include a gravure roll coating method, a forward roll coating method, an air knife coating method, a rod / bar coating method, and the like. From the viewpoint of properties and the like, in the present invention, the coating method is preferably a gravure roll coating method using a gravure roll.

A polarizer and a transparent protective film can be bonded together through the curable resin composition coated as described above. Bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like. A method of laminating a protective film on both sides of a polarizer is a method of laminating a polarizer and one protective film and then bonding another protective film, and a method of attaching a polarizer and two protective films simultaneously. It is selected from the method of combining. Clogging bubbles generated when bonding are significantly reduced by adopting the former method, that is, a method of bonding another protective film after bonding a polarizer and one protective film. Is preferable.

The active energy rays used in the curing step can be broadly classified into electron beam curable, ultraviolet curable, and visible light curable. In the present invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light. In the production of the polarizing film according to the present invention, it is particularly preferable to use visible light of 380 nm to 450 nm.

In the polarizing film according to the present invention, the curable resin composition for an optical film is applied directly to the polarizer, and a transparent protective film is laminated on the coated surface of the curable resin composition for the optical film of the polarizer as necessary. -After bonding, active energy rays (electron beam, ultraviolet ray, visible light, etc.) are irradiated to cure the active energy ray-curable resin composition to form an adhesive layer. The irradiation direction of active energy rays (electron beam, ultraviolet ray, visible light, etc.) can be irradiated from any appropriate direction. Preferably, it irradiates from the coating surface side of the curable resin composition for optical films of a polarizer, or the transparent protective film side. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron beam, ultraviolet ray, visible light, etc.).

In the electron beam curability, any appropriate conditions can be adopted as the irradiation condition of the electron beam as long as the above-described curable resin composition for optical films can be cured. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the curable resin composition for an optical film and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetrating power through the sample is too strong and transparent protection is obtained. There is a risk of damaging the film and the polarizer. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the curable resin composition for optical films becomes insufficiently cured, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing. It is not possible to obtain the optical characteristics.

The electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition where a little oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, the transparent protective film surface where the electron beam first hits can be obstructed to prevent oxygen damage and prevent damage to the transparent protective film. An electron beam can be irradiated efficiently.

In the method for producing a polarizing film according to the present invention, active energy rays containing visible light having a wavelength range of 380 nm to 450 nm, particularly active energy rays having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm are used as active energy rays. It is preferable. In the case of using a transparent protective film (ultraviolet non-transparent type transparent protective film) imparted with ultraviolet absorbing ability in ultraviolet curable property and visible light curable property, light having a wavelength shorter than 380 nm is absorbed, so that the wavelength shorter than 380 nm is absorbed. Light does not reach the active energy ray-curable resin composition and does not contribute to the polymerization reaction. Furthermore, light having a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curling and wrinkling of the polarizing film. Therefore, when ultraviolet curable and visible light curable are employed in the present invention, it is preferable to use an apparatus that does not emit light having a wavelength shorter than 380 nm as an active energy ray generator, and more specifically, a wavelength range of 380. The ratio of the integrated illuminance of ˜440 nm to the integrated illuminance of the wavelength range of 250 to 370 nm is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100: 40. As the active energy ray according to the present invention, a gallium-encapsulated metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable. Or low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent bulb, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight A light source including visible light can be used, and ultraviolet light having a wavelength shorter than 380 nm can be blocked using a band pass filter. In order to prevent the polarization film from curling while improving the adhesive performance of the adhesive layer between the polarizer and the transparent protective film, a gallium-encapsulated metal halide lamp can be used and light with a wavelength shorter than 380 nm can be blocked. It is preferable to use an active energy ray obtained through a band pass filter or an active energy ray having a wavelength of 405 nm obtained using an LED light source.

The curable resin composition for an optical film according to the present invention can be suitably used particularly for forming an adhesive layer for bonding a polarizer and a transparent protective film having a light transmittance of a wavelength of 365 nm of less than 5%. is there. Here, the curable resin composition for an optical film according to the present invention contains the above-described photopolymerization initiator of the general formula (2), so that it is irradiated with ultraviolet rays through a transparent protective film having UV absorption ability. The adhesive layer can be formed by curing. Therefore, an adhesive bond layer can be hardened also in a polarizing film which laminated a transparent protective film which has UV absorption ability on both sides of a polarizer. However, as a matter of course, the adhesive layer can also be cured in a polarizing film in which a transparent protective film having no UV absorbing ability is laminated. In addition, the transparent protective film which has UV absorption ability means the transparent protective film whose transmittance | permeability with respect to light of 380 nm is less than 10%.

Examples of the method for imparting UV absorbing ability to the transparent protective film include a method of containing an ultraviolet absorber in the transparent protective film and a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.

Specific examples of the ultraviolet absorber include conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. .

In ultraviolet curable or visible light curable, it is preferable to heat the curable resin composition for an optical film (pre-irradiation heating) before irradiating with ultraviolet light or visible light, and in that case, heat to 40 ° C. or higher. It is preferable to heat to 50 ° C. or higher. In addition, it is also preferable to heat the curable resin composition for an optical film after irradiation with ultraviolet rays or visible light (heating after irradiation), in which case it is preferable to heat to 40 ° C. or higher, and warm to 50 ° C. or higher. More preferably.

When the polarizing film according to the present invention is produced in a continuous line, the line speed depends on the curing time of the curable resin composition, but is preferably 5 to 100 m / min, more preferably 10 to 50 m / min, and still more preferably 20 ~ 30 m / min. When the line speed is too low, the productivity is poor, or the damage to the transparent protective film is too great, and a polarizing film that can withstand the durability test cannot be produced. When the line speed is too high, the curable resin composition may not be sufficiently cured, and the target adhesiveness may not be obtained.

The polarizing film of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or more optical layers that may be used can be used. In particular, a reflective polarizing film or semi-transmissive polarizing film in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing film of the present invention, an elliptical polarizing film or circularly polarizing film in which a retardation film is further laminated on a polarizing film. A wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on a film or a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on the polarizing film is preferred.

An optical film obtained by laminating the above optical layer on a polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like. Appropriate bonding means such as an adhesive layer can be used for lamination. When adhering the above polarizing film and other optical films, their optical axes can be set at an appropriate arrangement angle in accordance with the target retardation characteristics.

The pressure-sensitive adhesive layer for adhering to other members such as a liquid crystal cell can be provided on the polarizing film described above or an optical film in which at least one polarizing film is laminated. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. For example, an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected. Can be used. In particular, those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.

The adhesive layer can be provided on one side or both sides of a polarizing film or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers, such as a different composition, a kind, and thickness, in the front and back of a polarizing film or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 100 μm, preferably 5 to 30 μm, and particularly preferably 10 to 20 μm.

The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, an appropriate thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, or a laminate thereof, or a silicone-based or long sheet as necessary. Appropriate ones according to the prior art, such as those coated with an appropriate release agent such as a chain alkyl type, fluorine type or molybdenum sulfide, can be used.

The polarizing film or optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing film or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing film or optical film by invention, and it can apply according to the former. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.

Appropriate liquid crystal display devices such as a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the polarizing film or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell. When providing a polarizing film or an optical film on both sides, they may be the same or different. Further, when forming the liquid crystal display device, for example, a single layer or a suitable layer such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.

Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

(Preparation of curable resin composition)
90 parts by weight of 1,9-nonanediol diacrylate (“Light acrylate 1,9ND-A” manufactured by Kyoeisha Chemical Co., Ltd.), chlorinated polyolefin (“Superclone 814HS (chlorine content: 41% by weight)” manufactured by Nippon Paper Chemicals Co., Ltd.) 10 parts by weight and 3 parts by weight of “IRGACURE907” manufactured by BASF as a photopolymerization initiator were stirred for 3 hours using a stirrer to obtain a curable resin composition A. In the curable resin composition A, the weight ratio of the active energy ray-curable component (A) 1,9-nonanediol diacrylate and the chlorinated polyolefin (B) Supercron 814HS is 100: 11. is there.

100 parts by weight of 1,9-nonanediol diacrylate (“Light acrylate 1,9ND-A” manufactured by Kyoeisha Chemical Co., Ltd.) and 3 parts by weight of “IRGACURE907” manufactured by BASF as a photopolymerization initiator were stirred for 3 hours using a stirrer. A curable resin composition B was obtained.

75 parts by weight of 1,9-nonanediol diacrylate (“Light acrylate 1,9ND-A” manufactured by Kyoeisha Chemical Co., Ltd.), chlorinated polyolefin (“Supercron 814HS (chlorine content: 41% by weight)” manufactured by Nippon Paper Chemicals Co., Ltd.) 25 parts by weight and 3 parts by weight of “IRGACURE907” manufactured by BASF as a photopolymerization initiator were stirred for 3 hours using a stirrer to obtain a curable resin composition C. In the curable resin composition C, the weight ratio of the active energy ray-curable component (A) 1,9-nonanediol diacrylate and the chlorinated polyolefin (B) Supercron 814HS is 100: 33. is there.

99 parts by weight of 1,9-nonanediol diacrylate (“Light acrylate 1,9ND-A” manufactured by Kyoeisha Chemical Co., Ltd.), chlorinated polyolefin (“Supercron 3228S (chlorine content: 28% by weight)” manufactured by Nippon Paper Chemicals Co., Ltd.) 1 part by weight and 3 parts by weight of “IRGACURE907” manufactured by BASF as a photopolymerization initiator were stirred for 3 hours using a stirrer to obtain a curable resin composition D. In the curable resin composition D, the weight ratio of the active energy ray-curable component (A) 1,9-nonanediol diacrylate and the chlorinated polyolefin (B) Supercron 3228S was 100: 1. is there.

99.9 parts by weight of 1,9-nonanediol diacrylate (Kyoeisha Chemical Co., Ltd. “Light acrylate 1,9ND-A”), chlorinated polyolefin (Toyobo Co., Ltd. “Hardlen CY-9124P (chlorine content 24% by weight)” ) 0.1 part by weight, 3 parts by weight of “IRGACURE907” manufactured by BASF as a photopolymerization initiator was stirred for 3 hours using a stirrer to obtain a curable resin composition E. In the curable resin composition E, the weight ratio of the active energy ray-curable component (A) 1,9-nonanediol diacrylate and the chlorinated polyolefin (B) hardlen CY-9124P was 100: 0. .1.

(Production of polarizer)
As a resin base material, an amorphous polyethylene terephthalate film (hereinafter referred to as PET film) having a thickness of 100 μm and a Tg of 75 ° C. isophthalic acid unit of 7 mol% was prepared. The surface of this film was subjected to corona treatment (58 W / m ² / min).
1% by weight of acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Gohsephimer Z200, average polymerization degree: 1200, saponification degree: 98.5 mol% or more, acetoacetylation degree: 5%) PVA (average polymerization degree: 4200, saponification degree: 99.2 mol%) was prepared, and an aqueous solution containing 5.5% by weight of PVA resin was prepared. This aqueous solution is applied to the corona-treated surface of the resin substrate so that the film thickness after drying is 9 μm, and dried for 10 minutes by hot air drying in an atmosphere of 60 ° C., and the PVA system having a thickness of 9 μm is formed on the resin substrate. A resin layer was formed. Thus, a laminate was produced.
The obtained laminate was first stretched 1.8 times in air at 130 ° C. (air-assisted stretching).
Next, the laminate was immersed in an aqueous boric acid solution having a liquid temperature of 30 ° C. for 30 seconds to insolubilize the PVA resin layer. The boric acid aqueous solution in this step had a boric acid content of 3 parts by weight with respect to 100 parts by weight of water.
Next, the laminate was dyed in a staining solution containing iodine and potassium iodide at a liquid temperature of 30 ° C. for an arbitrary time so that the single transmittance of the obtained polarizing film was 40 to 44%. The staining solution uses water as a solvent, iodine concentration in the range of 0.1 to 0.4% by weight, potassium iodide concentration in the range of 0.7 to 2.8% by weight, iodine and potassium iodide. The concentration ratio was 1: 7.
Next, the laminate was immersed in an aqueous boric acid solution at 30 ° C. for 60 seconds, and the PVA resin layer on which iodine was adsorbed was subjected to crosslinking treatment. The boric acid aqueous solution in this step had a boric acid content of 3 parts by weight with respect to 100 parts by weight of water and a potassium iodide content of 3 parts by weight with respect to 100 parts by weight of water.
Furthermore, the laminate was stretched in a boric acid aqueous solution at a stretching temperature of 70 ° C. and stretched 3.05 times in the same direction as in the previous air-assisted stretching (final draw ratio: 5.50 times). The boric acid aqueous solution in this step had a boric acid content of 4 parts by weight with respect to 100 parts by weight of water and a potassium iodide content of 5 parts by weight with respect to 100 parts by weight of water.
Next, the laminate is washed with an aqueous solution having a potassium iodide content of 4 parts by weight with respect to 100 parts by weight of water, dried with hot air at 60 ° C., and laminated with a PET film and a 3.7 μm polarizing film. Got the body.

(Transparent protective film)
A biaxial kneader containing 100 parts by weight of the imidized MS resin and 0.62 part by weight of a triazine-based ultraviolet absorber (trade name: T-712, manufactured by Adeka Co.) described in Production Example 1 of JP 2010-284840 A Was mixed at 220 ° C. to prepare resin pellets. The obtained resin pellets were dried at 100.5 kPa and 100 ° C. for 12 hours, extruded from a T-die at a die temperature of 270 ° C. with a single screw extruder, and formed into a film (thickness: 160 μm). Further, the film is stretched in the conveyance direction in a 150 ° C. atmosphere (thickness 80 μm), and after applying an easy-adhesive containing an aqueous urethane resin, the film is stretched in a direction perpendicular to the film conveyance direction in a 150 ° C. atmosphere. to obtain a transparent acrylic film having a thickness of 40 [mu] m (moisture permeability ^58g / m 2 / 24h).

<Humidification durability test>
The obtained polarizing film was exposed to an environment of 85 ° C. and 85% RH for 250 hours, and the degree of polarization before and after charging was measured using a spectrophotometer with an integrating sphere (V7100 manufactured by JASCO Corporation). The degree of change in polarization degree ΔP (%) = | (degree of polarization before injection (%)) − (degree of polarization after introduction (%)) | was determined. It was judged that the smaller the amount of change ΔP in the degree of polarization, the better the optical durability in a harsh humidified environment.

Example 1
A transparent acrylic film was bonded to the obtained polarizing film (on the side opposite to the PET film) through the curable resin composition A. Specifically, on a transparent acrylic film, the curable resin composition A is coated with an MCD coater (manufactured by Fuji Machine Co., Ltd., cell shape: honeycomb, number of gravure roll wires: 1000 / inch, rotational speed 140% / line speed). ) Was applied so as to have a thickness of 1.0 μm, and they were bonded using a roll machine. The line speed of the bonding was 25 m / min.
Thereafter, the visible light was irradiated from the acrylic film side to cure the curable resin composition. Subsequently, it heated-air-dried at 70 degreeC for 3 minute (s), and the polarizing film was obtained.
The amount of change ΔP in the degree of polarization after the durability test was 0.02%.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the curable resin composition A was changed to the active energy ray-curable resin composition B.
The amount of change ΔP in the polarization degree after the durability test was 0.21%.

(Example 2)
The same procedure as in Example 1 was performed except that the curable resin composition A was changed to the active energy ray-curable resin composition C.
The amount of change ΔP in the degree of polarization after the durability test was 0.02%.

(Example 3)
The same procedure as in Example 1 was performed except that the curable resin composition A was changed to the active energy ray-curable resin composition D.
The amount of change ΔP in the polarization degree after the durability test was 0.11%.

Example 4
The same procedure as in Example 1 was performed except that the curable resin composition A was changed to the active energy ray-curable resin composition E.
The amount of change ΔP in the degree of polarization after the durability test was 0.16%.

From the results of Examples 1 to 4 and Comparative Example 1 above, when the curable resin composition for a polarizing film contains the chlorinated polyolefin (B) together with the active energy ray-curable component (A), the cured product layer is interposed. Thus, it can be seen that the amount of change in the degree of polarization of the polarizing film in which the transparent protective film is laminated on the polarizer is suppressed to be extremely low, and the optical durability is excellent.

Claims

A curable resin composition for an optical film containing an active energy ray-curable component (A) and a chlorinated polyolefin (B).
2. The curable resin composition for an optical film according to claim 1, wherein the chlorinated polyolefin (B) has a chlorine content of 25 to 50% by weight.
3. The curable resin composition for an optical film according to claim 1, wherein the weight ratio of the active energy ray-curable component (A) and the chlorinated polyolefin (B) is 100: 1 to 100: 40.
An optical film in which a cured product layer of a curable resin composition for an optical film containing an active energy ray-curable component (A) and a chlorinated polyolefin (B) is laminated on at least one surface of a polyvinyl alcohol polarizer.
The optical film according to claim 4, wherein a transparent protective film is laminated on at least one surface of the polyvinyl alcohol polarizer via the cured product layer.
The optical film according to claim 4, wherein the cured product layer is laminated on one side of the polyvinyl alcohol-based polarizer, and a transparent protective film is laminated on the other side.
A method for producing an optical film comprising a cured product layer obtained by curing a curable resin composition for an optical film on at least one surface of a polyvinyl alcohol polarizer,
The curable resin composition for an optical film contains an active energy ray-curable component (A) and a chlorinated polyolefin (B),
A coating step of directly coating the curable resin composition for an optical film on at least one surface of the polyvinyl alcohol polarizer;
It includes a curing step of irradiating active energy rays from the polyvinyl alcohol polarizer surface side or the coating surface side of the optical film curable resin composition to cure the optical film curable resin composition. A method for producing an optical film.