TWI741141B - Adhesive composition for polarizing film, polarizing film, optical film and image display device - Google Patents

Abstract

The present invention uses an adhesive composition for a polarizing film, which contains an active energy ray curable component and a bubble inhibitor having a reactive group. It is preferable to use a polysiloxane-based bubble suppressor as the bubble suppressor, and the bubble suppressor preferably has a (meth)acrylic acid group as a reactive group. The bubble inhibitor may be one having a urethane bond, or one having a trimeric isocyanate ring structure.

Description

Adhesive composition for polarizing film, polarizing film, optical film and image display device

The present invention relates to an adhesive composition for a polarizing film, a polarizing film, an optical film, and an image display device. The polarizing film can be used alone or laminated as an optical film to form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP.

Background of the Invention The market for liquid crystal display devices for applications such as clocks, mobile phones, PDAs, notebook computers, computer monitors, DVD players, and TVs is rapidly expanding. The liquid crystal display device visualizes the polarization state through the switching of the liquid crystal, and uses a polarizer based on its display principle. Especially in TV and other applications, the pursuit of high brightness, high contrast, wide viewing angle, and the pursuit of high transmittance, high degree of polarization, high color reproducibility, etc. are also increasingly pursued in terms of polarizing films.

As a polarizer, iodine-based polarizers are the most commonly used in terms of high transmittance and high degree of polarization. For example, polyvinyl alcohol (hereinafter also referred to as "PVA") is formed by adsorbing iodine and extending it. structure. Generally speaking, a polarizing film is made by laminating a transparent protective film on both sides of a polarizer by a so-called water-based adhesive, and the water-based adhesive is made by dissolving a polyvinyl alcohol-based material in water (Patent Document below) 1). The transparent protective film is made of triacetyl cellulose with high moisture permeability. When the aforementioned water-based adhesive is used (so-called wet lamination), a drying step is required after bonding the polarizer and the transparent protective film.

On the other hand, an active energy ray curable adhesive has been proposed to replace the aforementioned water-based adhesive. When the active energy ray curable adhesive is used to manufacture the polarizing film, since the drying step is not required, the productivity of the polarizing film can be improved. For example, the inventors of the present invention have proposed a radical polymerization type active energy ray curable adhesive that uses an N-substituted amide-based monomer as a curable component (Patent Document 2 below).

Prior Art Documents Patent Documents Patent Document 1: Japanese Patent Laid-Open No. 2001-296427 Patent Document 2: Japanese Patent Laid-Open No. 2012-052000

Summary of the Invention Problems to be Solved by the Invention However, based on the viewpoint of improving the quality of displays, the market gradually requires polarizing films to reduce even the tiny bubbles that have not been regarded as a problem until now. There are many reasons for the generation of tiny bubbles. For example, in the film bonding step of polarizers and transparent protective films, even if there are no bubbles in the adhesive composition applied for bonding, it will be due to the bonding of the film. When air is sandwiched between each other, there are cases where tiny bubbles called "laminated bubbles" are generated between the polarizer and the transparent protective film. Therefore, in the past, the market has been seeking an adhesive composition for a polarizing film that can suppress the generation of laminated bubbles and can form an adhesive layer that can improve the quality of the display.

The present invention was developed in view of the above facts, and its purpose is to provide an adhesive composition for polarizing films as the raw material of the adhesive layer, which can at least improve the adhesion between the polarizer and the transparent protective film and reduce Laminated bubbles that exist between the two.

Means to Solve the Problem The inventors of the present invention have carefully studied to solve the above-mentioned problem and found that the above-mentioned object can be achieved by mixing a bubble inhibitor having a reactive group in the adhesive composition for polarizing film. Solve the problem of the present invention.

That is, the present invention relates to an adhesive composition for a polarizing film, which is characterized by containing an active energy ray curable component and a bubble inhibitor having a reactive group.

In the above-mentioned adhesive composition for polarizing films, the aforementioned bubble inhibitor is preferably a silicone-based bubble inhibitor having a reactive group.

In the above-mentioned adhesive composition for a polarizing film, it is preferable that the aforementioned bubble inhibitor has a (meth)acryloyl group as a reactive group.

In the above-mentioned adhesive composition for polarizing films, the above-mentioned bubble inhibitor is preferably one having a urethane bond.

In the above-mentioned adhesive composition for polarizing films, the above-mentioned bubble inhibitor is preferably one having a trimeric isocyanate ring structure.

In the above-mentioned adhesive composition for polarizing films, when the total amount of the composition is 100% by weight, the content of the aforementioned bubble inhibitor is preferably 0.01 to 0.6% by weight.

In the aforementioned adhesive composition for polarizing films, the surface tension before curing is preferably 30 mN/m or less.

In the above-mentioned adhesive composition for polarizing films, it is preferable that it contains at least a radical polymerizable compound as the active energy ray curable component.

The present invention also relates to a polarizing film, characterized in that a transparent protective film is laminated on at least one surface of the polarizing member via an adhesive layer, and the adhesive layer is made of the adhesive for polarizing film as described in any one of the foregoing The composition is hardened.

In the above-mentioned polarizing film, the thickness of the aforementioned adhesive layer is preferably 0.2 to 3 μm.

In the above-mentioned polarizing film, when the thickness of the adhesive layer is d (μm) and the content of the bubble inhibitor contained in the adhesive layer is y (wt%), the following formula (1) is satisfied: good. 0.1-0.02d≦y≦0.6-0.08d　(1)

And the present invention relates to an optical film characterized in that at least one layer of the polarizing film described in any of the foregoing is laminated; or it relates to an image display device characterized in that the polarizing film described in any of the foregoing is used Film or the aforementioned optical film.

Effects of the Invention Generally speaking, a polarizing film is manufactured by laminating a polarizer and a transparent protective film through an adhesive layer formed of an adhesive composition for a polarizing film. However, as mentioned above, when bonding the polarizer and the transparent protective film, There is a tendency to generate layered bubbles due to air being trapped, and the market requires them to be reduced. In the present invention, since the adhesive composition for polarizing film used as the raw material of the adhesive layer is blended with a bubble inhibitor having a reactive group, the surface free energy of the composition before curing can be reduced. Thereby, the wettability of the polarizer and the transparent protective film of the polarizing film adhesive composition is improved, and the polarizing film adhesive composition can also effectively deal with the extremely fine unevenness that exists on the surface of the polarizer and the transparent protective film. Wet and spread. As a result, the generation of laminated bubbles can be reduced when the polarizer and the transparent protective film are laminated.

In addition, in order to improve the coating properties when coating the adhesive composition on the film substrate, it is known that the adhesive composition is blended with a silane coupling agent such as a fluorine compound which is considered to have low surface free energy. . However, in general, when such a silane coupling agent is blended into an adhesive composition, the adhesive composition tends to decrease its adhesion to the film substrate to be attached. Regarding the reason, we speculate that even when the adhesive composition is cured to form an adhesive layer, the bubble inhibitor still remains on the surface of the film substrate as an uncured substance, which can contribute to the adhesive layer. The interaction with the adhesive force of the film substrate is not sufficiently generated.

However, in the present invention, a bubble inhibitor with a reactive group is blended into the adhesive composition to effectively reduce the surface free energy of the composition before curing, and after curing, the bubble inhibitor can pass through the reactive group of the bubble inhibitor. Incorporating the adhesive layer can reduce the build-up of bubbles and improve the adhesion of the adhesive layer to the polarizer and the transparent protective film of the attached object. As a result, when the adhesive composition for polarizing films of the present invention is used, it is possible to prevent appearance defects caused by the reduction of the laminated bubbles between the polarizer and the transparent protective film, and by improving the polarizer and the transparent protective film The adhesion between the film and the adhesive layer can improve the adhesion strength between the polarizer and the transparent protective film.

Modes for Carrying Out the Invention The adhesive composition for polarizing films of the present invention contains an active energy ray curable component and a bubble inhibitor having a reactive group.

<Active energy ray curable component> The active energy ray curable component that can be used in the present invention can be roughly classified into electron beam curable properties, ultraviolet curable properties, and visible light curable properties. In addition, the curing form can be divided into a radical polymerization curing type adhesive composition and a cation polymerizable adhesive composition. In the present invention, the active energy line with a wavelength range of 10 nm to less than 380 nm is recorded as ultraviolet light, and the active energy line with a wavelength range of 380 nm to 800 nm is recorded as visible light. In particular, the active energy ray curable component (A) that can be used in the present invention is particularly good in visible light curability using visible rays of 380 nm to 450 nm.

<1: Radical polymerizable curable compound> The radical polymerizable compound includes, for example, a compound having a carbon-carbon double bond-containing radical polymerizable functional group 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 may 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 addition, in the present invention, the term “(meth)acryloyl group” means an acryloyl group and/or methacryloyl group, and “(meth)” is synonymous below. Compounds having a (meth)acryloyl group include (meth)acrylamide derivatives having a (meth)acrylamido group, or (meth)acrylic acid having a (meth)acryloyloxy group ester. Although the compound which has a (meth)acryloyl group is illustrated below, it can select various and use, and is not specifically limited. In the active energy ray curable adhesive composition of the present invention, the content of the radical polymerizable compound is preferably 10% by weight or more.

(惟，R¹ 為氫原子或甲基，R² 及R³ 分別獨立為氫原子、烷基、羥烷基、烷氧基烷基或環狀醚基，且R² 及R³ 亦可形成環狀雜環)。烷基、羥烷基及/或烷氧基烷基之烷基部分之碳數並無特別限定，可舉例如1~4個者。又，亦可形成R² 及R³ 之環狀雜環，可舉例如N-丙烯醯基

啉。"Monofunctional radical polymerizable compound" The monofunctional radical polymerizable compound includes, for example, a compound represented by the following general formula (1): [Chemical formula 1]

(However, R ¹ is a hydrogen atom or a methyl group, 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, and R ² and R ³ can also form Cyclic heterocycle). The carbon number of the alkyl part of an alkyl group, a hydroxyalkyl group, and/or an alkoxyalkyl group is not specifically limited, For example, 1 to 4 can be mentioned. In addition, a ^{cyclic heterocyclic ring of R 2} and R ³ may also be formed, for example, N-acryloyl group

Morpholine.

啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、N-丙烯醯基吡咯啶等。該等之中，由反應性優異之觀點、可獲得高彈性模數之硬化物之觀點、及對偏光件之接著性優異之觀點來看，可適當地使用N-羥乙基丙烯醯胺、或N-丙烯醯基

啉。As specific examples of the compound represented by the general formula (1), for example, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl (Meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, etc. containing N-alkyl groups (Meth)acrylamide derivatives; N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxymethyl-N-propane (meth)propylene N-hydroxyalkyl (meth)acrylamide derivatives such as amide; N-methoxymethacrylamide, N-ethoxymethacrylamide, etc. containing N-alkoxy (methyl) ) Acrylamide derivatives, etc. In addition, examples of the cyclic ether group-containing (meth)acrylamide derivative include heterocyclic (meth)acrylamide derivatives in which the nitrogen atom of the (meth)acrylamide group forms a heterocyclic ring. For example, N-acryloyl

Pyroline, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine, etc. Among them, from the viewpoint of excellent reactivity, the viewpoint of obtaining a cured product with a high elastic modulus, and the viewpoint of excellent adhesion to the polarizer, N-hydroxyethyl acrylamide, Or N-acryloyl

Morpholine.

From the viewpoint of improving the adhesiveness and water resistance when the polarizing member and the transparent protective film are connected through the adhesive layer, and the productivity improvement caused by the faster polymerization speed, in the adhesive composition, the general formula (1) The stated compound content is preferably 1-50% by weight, more preferably 3-20% by weight. In particular, when the content of the compound described in the general formula (1) is too large, the water absorption rate of the cured product becomes higher, and the water resistance may deteriorate.

In addition, the adhesive composition used in the present invention may contain other monofunctional radical polymerizable compounds as curable components in addition to the compound represented by the general formula (1). As a monofunctional radically polymerizable compound, various (meth)acrylic acid derivatives which have a (meth)acryloyloxy group are mentioned, for example. Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-methyl-2-nitro Propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, (meth) ) N-pentyl acrylate, tertiary 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, (Meth) acrylic acid (carbon number 1-20) alkyl esters such as n-octadecyl (meth)acrylate.

In addition, the aforementioned (meth)acrylic acid derivatives include, for example, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, and other cycloalkyl (meth)acrylates; benzyl (meth)acrylate, etc. ( Aralkyl 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)acrylate, dicyclopentenoxyethyl (meth)acrylate, (meth)acrylic acid Polycyclic (meth)acrylates such as dicyclopentyl ester; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxy(meth)acrylate Ethyl methoxy ethyl, 3-methoxy butyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy ethyl (meth) acrylate, alkylphenoxy polyethylene Alcohol (meth)acrylate and other alkoxy or phenoxy-containing (meth)acrylates, etc. When the resin composition of the present invention is used as an adhesive for polarizing films, it is preferable to contain phenoxyethyl (meth)acrylate and alkylphenoxy polyethylene glycol from the viewpoint of adhesion to the protective film (Meth)acrylates, 2-hydroxy-3-phenoxypropyl acrylates and other (meth)acrylates containing alkoxy or phenoxy groups. The content is preferably 1% by weight to 30% by weight relative to the resin composition.

In addition, examples of the aforementioned (meth)acrylic acid derivatives include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate , 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, (meth)acrylic acid 10-hydroxydecyl ester, 12-hydroxylauryl (meth)acrylate and other (meth) hydroxyalkyl acrylates; or [4 (hydroxymethyl) cyclohexyl] methacrylate, cyclohexane dimethanol one (meth) Hydroxy (meth)acrylates such as acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc.; glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Epoxy-containing (meth)acrylate such as glycidyl ether; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl ethyl (meth)acrylate , Tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, 3-chloro-2-hydroxypropyl (Meth)acrylic acid esters and other halogen-containing (meth)acrylates; (meth)acrylic acid dimethylamino ethyl esters and other (meth)acrylic acid alkylamino alkyl esters; (meth)acrylic acid 3- Oxetanyl methyl ester, 3-methyl-oxetanyl methyl (meth)acrylate, 3-ethyl-oxetanyl methyl (meth)acrylate, (methyl) ) Oxetanyl (meth)acrylates such as 3-butyl-oxetanyl methyl acrylate and 3-hexyl-oxetanyl methyl (meth)acrylate; (Meth)acrylates with heterocycles such as tetrahydrofurfuryl acrylate and butyrolactone (meth)acrylate; or neopentyl glycol (meth)acrylate adducts of hydroxytrimethylacetate, (meth)acrylate Base) p-phenylphenol acrylate and the like. Among them, 2-hydroxy-3-phenoxypropyl acrylate is preferred because of its excellent adhesion to various protective films.

In addition, the monofunctional radical polymerizable compound can be exemplified by (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and other carboxyl-containing monomers. body.

、乙烯基吡

、乙烯基吡咯、乙烯基咪唑、乙烯基㗁唑、乙烯基

啉等具有含氮雜環之乙烯系單體等等。In addition, examples of monofunctional radical polymerizable compounds include internal vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactone, and methyl vinylpyrrolidone. ; Vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiper

Vinylpyridine

, Vinyl pyrrole, vinyl imidazole, vinyl azole, vinyl

Vinyl monomers with nitrogen-containing heterocycles such as morpholines, etc.

As long as the resin composition contains hydroxyl-containing (meth)acrylates, carboxyl-containing (meth)acrylates or phosphoric acid-containing (meth)acrylates, which have high polarity among the above-mentioned compounds, the adhesion to various substrates can be achieved. Will improve. The content of the hydrocarbon group-containing (meth)acrylate is preferably 1% by weight to 30% by weight relative to the resin composition. When the content is too much, the water absorption rate of the hardened material will become higher, and the water resistance may deteriorate. The content of the carboxyl group-containing (meth)acrylate is preferably 1% by weight to 20% by weight relative to the resin composition. When the content is too much, the optical durability of the polarizing film will decrease, so it is not good. Examples of the phosphoric acid group-containing (meth)acrylate include 2-(meth)acryloyloxyethyl acid phosphate, and the content thereof is preferably 0.1% by weight to 10% by weight relative to the resin composition. When the content is too much, the optical durability of the polarizing film will decrease, so it is not good.

In addition, as the monofunctional radical polymerizable compound, a radical polymerizable compound having an active methylene group can be used. The radically polymerizable compound having an active methylene group is a compound that has an active double bond group such as a (meth)acryloyl group at the terminal or in the molecule, and has an active methylene group. Examples of the active methylene group include acetylacetoxy, alkoxypropanedioxin or cyanoacetoxy. In addition, the aforementioned active methylene group is preferably acetylacetonyl. Specific examples of radically polymerizable compounds having active methylene groups include 2-acetylacetoxyethyl (meth)acrylate, 2-acetylacetoxypropyl (meth)acrylate , 2-Acetylacetoxy-1-methylethyl (meth)acrylate and other Acetylacetoxyalkyl (meth)acrylates; 2-Ethoxypropanedioxyloxyethyl (Meth)acrylate, 2-cyanoacetoxyethyl (meth)acrylate, N-(2-cyanoacetoxyethyl)acrylamide, N-(2-propaneacetoxy) Butyl)acrylamide, N-(4-acetylacetoxymethylbenzyl)acrylamide, N-(2-acetylacetaminoethyl)acrylamide, and the like. The radically polymerizable compound having a reactive methylene group is preferably acetoxyalkyl (meth)acrylate.

"Polyfunctional Radical Polymerizable Compounds" In addition, examples of polyfunctional radical polymerizable compounds having more than two functions include N,N'-methylenebis(formaldehyde) which is a polyfunctional (meth)acrylamide derivative. Base) acrylamide, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(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, diethylene glycol bis(methyl) )Acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentylerythritol penta(meth)acrylate Acrylic acid ester, dineopentaerythritol hexa(meth)acrylate, EO modified diglycerol tetra(meth)acrylate, etc. (meth)acrylic acid and polyol esterification products, 9,9-bis[4-( 2-(Meth)acryloyloxyethoxy)phenyl]茀, hydroxytrimethylacetate neopentyl glycol acrylate adduct, etc. As specific examples, 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 (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sartomer Co., Ltd.), CD-536 (manufactured by Sartomer Co., Ltd.), etc. are preferable. In addition, as required, various epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, and various (meth)acrylate monomers can be mentioned. In addition, the polyfunctional (meth)acrylamide derivative has a fast polymerization rate and is excellent in productivity. In addition, it has excellent crosslinkability when the resin composition is made into a cured product, so it is preferably contained in the adhesive composition.

From the standpoint of having both adhesion to polarizers and various transparent protective films, and optical durability in harsh environments, the radical polymerizable compound is a combination of a monofunctional radical polymerizable compound and a polyfunctional radical Polymerizable compounds are preferred. In addition, since the liquid viscosity of the monofunctional radical polymerizable compound is relatively low, if it is contained in the resin composition, the liquid viscosity of the resin composition can be reduced. In addition, the monofunctional radical polymerizable compound often has a functional group capable of exhibiting various functions, and if it is contained in the resin composition, the resin composition and/or the cured product of the resin composition can exhibit various functions. Since the polyfunctional radical polymerizable compound can cause three-dimensional crosslinking of the cured product of the resin composition, it is preferably contained in the resin composition. The ratio of the monofunctional radical polymerizable compound to the polyfunctional radical polymerizable compound is preferably to mix the polyfunctional radical polymerizable compound in the range of 10 parts by weight to 1000 parts by weight relative to 100 parts by weight of the monofunctional radical polymerizable compound .

<2: Cationic polymerizable adhesive composition> As the cationically polymerizable compound used in the cationically polymerizable adhesive composition, it can be classified as a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule , And a polyfunctional cationically polymerizable compound having two or more cationically polymerizable functional groups in the molecule. Since the liquid viscosity of the monofunctional cationic polymerizable compound is relatively low, the liquid viscosity of the resin composition can be reduced if it is contained in the resin composition. In addition, monofunctional cationically polymerizable compounds often have functional groups capable of exhibiting various functions. By including them in the resin composition, the resin composition and/or the cured product of the resin composition can exhibit various functions. Since the polyfunctional cationically polymerizable compound can cause three-dimensional crosslinking of the cured product of the resin composition, it is preferably contained in the resin composition. The ratio of the monofunctional cationically polymerizable compound to the polyfunctional cationically polymerizable compound is preferably to mix the polyfunctional cationically polymerizable compound in the range of 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the monofunctional cationically polymerizable compound. Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of compounds having epoxy groups include aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds. The cationic polymerizable adhesive composition of the present invention contains especially alicyclic epoxy compounds. Good, because of its excellent curability and adhesion. As the alicyclic epoxy compound, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexylmethyl 3,4-cyclic Caprolactone-modified products, trimethylcaprolactone-modified products, and valerolactone-modified products of oxycyclohexane carboxylates, etc., specifically, CELLOXIDE 2021, CELLOXIDE 2021A, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085 (above, manufactured by DAICEL Chemical Industry Co., Ltd.), Cyracure UVR-6105, Cyracure UVR-6107, Cyracure 30, R-6110 (above, manufactured by Dow Chemical Co., Ltd.), jer-828 (above , Japan Epoxy Resins Corporation) and so on. The compound having an oxetanyl group has the effects of improving the curability of the cationic polymerizable adhesive composition of the present invention and reducing the liquid viscosity of the composition, so it is preferable to contain the compound. Examples of compounds having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl )Methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, bis[(3-ethyl-3-oxetanyl)methyl]ether, 3-Ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenol phenol oxetane, etc., and commercially available 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.), etc. The compound having a vinyl ether group has the effects of improving the curability of the cationic polymerizable adhesive composition of the present invention and reducing the liquid viscosity of the composition, so it is preferable to contain the compound. Examples of compounds with vinyl ether groups include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethyl Glycol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, Ethoxy ethyl vinyl ether, neopentyl erythritol type tetravinyl ether, etc.

<Bubble inhibitor with reactive group> The bubbling inhibitor can be blended into the adhesive composition to produce a compound that reduces the surface tension of the adhesive composition, and thereby has the ability to reduce and adhere to the coating. The effect of bubbles between the bodies. The bubble inhibitor can use those that have the effect of reducing the surface tension of the adhesive composition when added to the adhesive composition, for example, polysiloxane-based bubble inhibitors with a polysiloxane skeleton such as polydimethylsiloxane, etc. (Meth)acrylic acid-based air bubble inhibitors formed by polymerization of (meth)acrylic acid esters, etc., and polyether-based air bubble inhibitors formed by polymerization of vinyl ether or cyclic ether, etc. , Fluorine bubble suppressant composed of fluorine-based compound with perfluoroalkyl group, etc.

Examples of the reactive group possessed by the bubble suppressor include polymerizable functional groups, and specific examples include radical polymerizable functional groups having ethylenic double bonds such as (meth)acrylic acid groups, vinyl groups, and allyl groups, Cationic polymerizable functional groups such as epoxy group, oxetanyl group, vinyl ether group, cyclic ether group, cyclic sulfide group, lactone group, etc., such as glycidyl group. From the viewpoint of reactivity in the adhesive composition, a bubble suppressor having a double bond as a reactive group is preferred, and a bubble suppressor having a (meth)propylene ethylene group is more preferred.

When considering the effect of suppressing the build-up of bubbles and the effect of improving adhesion, among the aforementioned bubble inhibitors, polysiloxane-based bubble inhibitors are preferred. In addition, when considering the adhesiveness of the adhesive layer in the bubble inhibitor, it is preferable to include a urethane bond or a trimeric isocyanate ring structure in the main chain skeleton or side chain. A commercially available product can also be suitably used as a polysiloxane-based bubble inhibitor, and for example, "BYK-UV3505" (manufactured by BYK Chem. Japan) made of propylene-based modified polydimethylsiloxane can be mentioned.

In order to take into account both the adhesive force of the resulting adhesive layer and the effect of reducing the build-up bubbles, when the total amount of the adhesive composition is 100% by weight, the content of the bubble inhibitor is preferably 0.01 to 0.6% by weight.

<The aspect of the radical polymerizable adhesive composition> When the active energy rays use electron beams, etc., the adhesive composition does not need to contain a photopolymerization initiator, but when the active energy rays use ultraviolet rays or visible rays In this case, the adhesive composition preferably contains a photopolymerization initiator.

啉丙烷-1等的苯乙酮系化合物；苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻丁基醚、大茴香偶姻甲基醚等的苯偶姻醚系化合物；苄基二甲縮酮等芳香族縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(鄰乙氧基羰基)肟等的光活性肟系化合物；9-氧硫

、2-氯9-氧硫

、2-甲基9-氧硫

、2,4-二甲基9-氧硫

、異丙基9-氧硫

、2,4-二氯9-氧硫

、2,4-二乙基9-氧硫

、2,4-二異丙基9-氧硫

、十二基9-氧硫

等的9-氧硫

系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基膦酸酯等。"Photopolymerization initiator" When a radical polymerizable compound is used, the photopolymerization initiator can be appropriately selected in accordance with active energy rays. When curing by ultraviolet or visible light, a photopolymerization initiator that is cleaved by ultraviolet or visible light can be used. Examples of the aforementioned photopolymerization initiator include benzil, diphenyl ketone, benzyl benzoic acid, and 3,3'-dimethyl-4-methoxydiphenyl Ketones and other diphenyl ketone compounds; 4-(2-hydroxyethoxy) phenyl(2-hydroxy-2-propyl) ketone, α-hydroxy-α,α'-dimethylacetophenone, 2 -Methyl-2-hydroxypropiophenone, α-hydroxycyclohexyl phenyl ketone and other aromatic ketone compounds; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-

Acetophenone compounds such as oxypropane-1; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, anisin methyl ether, etc. Benzoin ether compounds; aromatic ketal compounds such as benzyl dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1-phenone-1, 1-propanedione-2 -(O-ethoxycarbonyl) oxime and other photoactive oxime compounds; 9-oxysulfur

, 2-Chloro 9-oxysulfur

, 2-Methyl 9-oxysulfur

, 2,4-Dimethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, 2,4-Dichloro 9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Diisopropyl 9-oxysulfur

, Dodecyl 9-oxysulfur

9-oxysulfur

Series compounds; camphorquinone; halogenated ketones; acyl phosphine oxide; acyl phosphonate and the like.

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

In addition, when the adhesive composition used in the present invention is used as a visible light curable containing a radical polymerizable compound as a curable component, it is particularly suitable to use a photopolymerization initiator with high sensitivity to light above 380nm . The photopolymerization initiator with high sensitivity to light above 380nm will be described in detail later.

(式中，R⁴ 及R⁵ 表示-H、-CH₂ CH₃ 、-iPr或Cl，R⁴ 及R⁵ 可相同或相異)。在使用通式(2)所示化合物時，其接著性優於單獨使用對380nm以上的光有高感度之光聚合起始劑的情形。通式(2)所示化合物當中，以R⁴ 及R⁵ 為-CH₂ CH₃ 時的二乙基9-氧硫

尤佳。接著劑組成物中，相對於接著劑組成物之總量，通式(4)所示化合物之組成比率以0.1~5重量%為佳，以0.5~4重量%較佳，以0.9~3重量%更佳。As the aforementioned photopolymerization initiator, it is preferable to use the compound represented by the following general formula (2) alone or in combination with the compound represented by the general formula (2) and the photopolymerization initiator with high sensitivity to light of 380 nm or more described later: [ Chemical formula 2]

(In the formula, 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). When the compound represented by the general formula (2) is used, its adhesiveness is better than when a photopolymerization initiator with high sensitivity to light of 380 nm or more is used alone. Among the compounds represented by the general formula (2), when R ⁴ and R ⁵ are -CH ₂ CH ₃ , the diethyl 9-oxysulfide

Especially good. In the adhesive composition, relative to the total amount of the adhesive composition, the composition ratio of the compound represented by the general formula (4) is preferably 0.1 to 5 wt%, preferably 0.5 to 4 wt%, and 0.9 to 3 wt% % Is better.

In addition, it is suitable to add a polymerization initiation assistant as necessary. The polymerization initiation aid may include, for example, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylamine benzoic acid, methyl 4-dimethylamine benzoate, 4-dimethylamine benzoic acid Ethyl, isoamyl 4-dimethylaminobenzoate, etc., and ethyl 4-dimethylaminobenzoate is particularly preferred. When the polymerization initiation aid is used, its addition amount is generally 0-5 wt% relative to the total amount of the adhesive composition, preferably 0-4 wt%, and most preferably 0-3 wt%.

啉丙-1-酮、2-苄基-2-二甲胺基-1-(4-

啉苯基)-丁-1-酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮、2,4,6-三甲基苯甲醯基-二苯基-膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦等。In addition, well-known photopolymerization initiators can be used in combination as needed. The transparent protective film with UV absorption energy will not penetrate the light below 380nm, so the photopolymerization initiator should be a photopolymerization initiator with high sensitivity to light above 380nm. Specifically, for example, 2-methyl-1-(4-methylthiophenyl)-2-

Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phenylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

(Hydroxy)phenyl)-1-butanone, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl) -Phenylphosphine oxide, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium Wait.

(式中，R⁶ 、R⁷ 及R⁸ 表示-H、-CH₃ 、-CH₂ CH₃ 、-iPr或Cl，且R⁶ 、R⁷ 及R⁸ 可相同或相異)。通式(3)所示化合物可適當使用亦屬市售品的2-甲基-1-(4-甲硫基苯基)-2-

啉丙-1-酮(商品名：IRGACURE907，製造者：BASF)。除此之外，2-苄基-2-二甲胺基-1-(4-

啉苯基)-丁-1-酮(商品名：IRGACURE369，製造者：BASF)、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮(商品名：IRGACURE379，製造者：BASF)由於感度高，因此較為理想。In particular, in addition to the photopolymerization initiator of the general formula (2), the photopolymerization initiator preferably further uses a compound represented by the following general formula (3): [Chemical formula 3]

(In the formula, 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). The compound represented by the general formula (3) can suitably use 2-methyl-1-(4-methylthiophenyl)-2- which is also a commercially available product.

Phytopropan-1-one (trade name: IRGACURE907, manufacturer: BASF). In addition, 2-benzyl-2-dimethylamino-1-(4-

Phenylphenyl)-butan-1-one (trade name: IRGACURE369, manufacturer: BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4 -(4-

Linyl)phenyl]-1-butanone (trade name: IRGACURE379, manufacturer: BASF) is preferable because of its high sensitivity.

<The radical polymerizable compound with active methylene group and the radical polymerization initiator with hydrogen abstraction> In the above-mentioned adhesive composition, when a radical polymerizable compound with active methylene group is used as the radical polymerization In the case of sexual compounds, it is suitable to be used in combination with a radical polymerization initiator with hydrogen abstraction. With the aforementioned structure, especially even in a high humidity environment or just taken out of water (non-dried state), the adhesiveness of the adhesive layer of the polarizing film will still be significantly improved. This reason has not been clarified, but it can be presumed to be the following reason. That is, the radical polymerizable compound with active methylene groups polymerizes with other radical polymerizable compounds constituting the adhesive layer while being incorporated into the main chain and/or branch chain of the base polymer in the adhesive layer , Form an adhesive layer. In the aforementioned polymerization process, once a radical polymerization initiator with hydrogen abstraction is present, it will form the base polymer constituting the adhesive layer while abstracting hydrogen from the radical polymerizable compound with active methylene groups. Free radicals are generated in the methylene group. Then, the methylene group that generates free radicals reacts with the hydroxyl group of the polarizing member such as PVA to form a covalent bond between the adhesive layer and the polarizing member. As a result, it can be inferred that even in a non-dried state, the adhesiveness of the adhesive layer of the polarizing film will still be significantly improved.

系自由基聚合起始劑、二苯基酮系自由基聚合起始劑等。前述自由基聚合起始劑以9-氧硫

系自由基聚合起始劑為佳。作為9-氧硫

系自由基聚合起始劑，可舉例如上述通式(2)所示化合物。通式(2)所示化合物之具體例可舉出9-氧硫

、二甲基9-氧硫

、二乙基9-氧硫

、異丙基9-氧硫

、氯9-氧硫

等。通式(2)所示化合物當中，尤佳的是R⁴ 及R⁵ 為-CH₂ CH₃ 時的二乙基9-氧硫

。In the present invention, the radical polymerization initiator with hydrogen abstraction can include, for example, 9-oxysulfur

It is a radical polymerization initiator, a benzophenone-based radical polymerization initiator, etc. The aforementioned radical polymerization initiator is 9-oxysulfur

It is preferably a radical polymerization initiator. As 9-oxysulfur

The radical polymerization initiator includes, for example, the compound represented by the above-mentioned general formula (2). Specific examples of compounds represented by the general formula (2) include 9-oxysulfur

, Dimethyl 9-oxysulfur

, Diethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, Chlorine 9-oxysulfur

Wait. Among the compounds represented by the general formula (2), particularly preferred is diethyl 9-oxysulfur when ^{R 4} and R ⁵ are -CH ₂ CH ₃

.

In the case where the above-mentioned adhesive composition contains a radical polymerizable compound having a reactive methylene group and a radical polymerization initiator having a hydrogen abstraction effect, when the total amount of the curable component is 100% by weight, it is preferable It contains 1-50% by weight of the aforementioned radical polymerizable compound having active methylene groups, and preferably contains 0.1-10% by weight of a radical polymerization initiator relative to the total amount of the curable resin composition.

As mentioned above, in the present invention, in the presence of a radical polymerization initiator having a hydrogen abstraction effect, free radicals are generated from the methylene group of the radical polymerizable compound having a reactive methylene group, and the aforementioned methylene group and PVA The hydroxyl groups of the polarizer will react to form a covalent bond. Therefore, in order to generate free radicals at the methylene group of the radical polymerizable compound having active methylene groups and fully form the aforementioned covalent bonds, when the total amount of the curable component is 100% by weight, active methylene groups The radical polymerizable compound of the base preferably contains 1-50% by weight, and more preferably contains 3-30% by weight. In order to sufficiently improve the water resistance and improve the adhesiveness in a non-dry state, the radical polymerizable compound with active methylene group is preferably set to 1% by weight or more. On the other hand, if it exceeds 50% by weight, poor curing of the adhesive layer may occur. In addition, with respect to the total amount of the adhesive composition, the radical polymerization initiator with hydrogen abstraction is preferably contained in 0.1-10% by weight, more preferably 0.3-9% by weight. In order to allow the hydrogen abstraction reaction to proceed sufficiently, it is preferable to use 0.1% by weight or more of a radical polymerization initiator. On the other hand, if it exceeds 10% by weight, it may not completely dissolve in the composition.

<Photocationic polymerization initiator> The cationic polymerizable adhesive composition contains at least one selected from the group consisting of epoxy-containing compounds, oxetanyl-containing compounds, and vinyl ether group-containing compounds described above One compound is used as a curable component, and all of them can be cured by cationic polymerization, so a photocationic polymerization initiator is blended. The photocationic polymerization initiator is irradiated with active energy rays such as visible rays, ultraviolet rays, X-rays, electron rays, etc., to generate cationic species or Lewis acid, and initiate the polymerization reaction of epoxy groups and oxetanyl groups. As a photocationic polymerization initiator, a photoacid generator and a photobase generator can be used, and the photoacid generator mentioned later can be used suitably. In addition, when the adhesive composition used in the present invention is to be curable by visible light, it is preferable to use a photocationic polymerization initiator that is particularly sensitive to light above 380 nm. However, the photocationic polymerization initiator is generally Compounds that exhibit maximum absorption in the vicinity of 300 nm or shorter wavelength regions, so it can be blended with a photosensitive compound that exhibits maximum absorption for longer wavelength regions, specifically, light with wavelengths longer than 380 nm A chemical agent to sense light of a wavelength near it and promote the production of cationic species or acids derived from the photocationic polymerization initiator. Examples of photosensitizers include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes. They may also be used Mix two or more types to use. In particular, the anthracene compound is very desirable because of its excellent photosensitizing effect. Specifically, there are ANTHRACURE UVS-1331 and ANTHRACURE UVS-1221 (manufactured by Kawasaki Chemical Co., Ltd.). The content of the photosensitizer is preferably 0.1% to 5% by weight, preferably 0.5% to 3% by weight.

<Other components> The adhesive composition used in the present invention preferably contains the following components.

<Acrylic oligomer> The adhesive composition used in the present invention may contain, in addition to the curable component of the radical polymerizable compound, an acrylic oligomer formed by polymerization of (meth)acrylic monomers . By containing components in the adhesive composition, the curing shrinkage can be reduced when the composition is irradiated with active energy rays to harden the composition, and the interface stress with the adherend, such as the adhesive, the polarizer, and the transparent protective film, can be reduced. As a result, the adhesion between the adhesive layer and the adherend can be suppressed from decreasing. 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, and preferably 15% by weight or less, relative to the total amount of the adhesive composition. If the content of the acrylic oligomer in the adhesive composition is too large, the reaction rate when the composition is irradiated with active energy rays is drastically reduced, which may cause poor curing. On the other hand, with respect to the total amount of the adhesive composition, the acrylic oligomer is preferably contained at 3% by weight or more, and more preferably at 5% by weight.

When considering workability and uniformity during coating, the adhesive composition is preferably low viscosity, so the acrylic oligomer polymerized by the (meth)acrylic monomer is also preferably low viscosity. As an acrylic oligomer with low viscosity and capable of preventing the hardening and shrinkage of the adhesive layer, the weight average molecular weight (Mw) is preferably below 15,000, more preferably below 10,000, and most preferably below 5000. On the other hand, in order to sufficiently suppress the curing shrinkage of the cured layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer is preferably 500 or more, more preferably 1000 or more, and particularly preferably 1500 or more. Specific examples of the (meth)acrylic monomer constituting the acrylic oligomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth) ) Isopropyl acrylate, 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate Ester, tertiary butyl (meth)acrylate, n-pentyl (meth)acrylate, tertiary 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- (Meth)acrylic acid (carbon number 1-20) alkyl esters such as 2-propylpentyl (meth)acrylate and N-octadecyl (meth)acrylate; and, for example, cycloalkyl (methyl) ) Acrylate (for example, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, etc.), aralkyl (meth)acrylate (for example, benzyl (meth)acrylate, etc.), polycyclic (Meth) acrylate (e.g. 2-isobornyl (meth)acrylate, 2-norbornyl methyl (meth)acrylate, 5-norbornen-2-yl-methyl (meth)acrylate) , 3-Methyl-2-norbornylmethyl (meth)acrylate, etc.), hydroxyl-containing (meth)acrylates (such as hydroxyethyl (meth)acrylate, 2-hydroxy (meth)acrylate) Propyl ester, 2,3-dihydroxypropylmethyl-butyl (meth)methacrylate, etc.), (meth)acrylates containing alkoxy or phenoxy groups ((meth)acrylic acid 2 -Methoxyethyl, 2-ethoxyethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl Carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, etc.), epoxy-containing (meth)acrylates (for example, glycidyl (meth)acrylate, etc.), containing Halogen (meth)acrylates (e.g. 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl ethyl (meth)acrylate, tetrafluoroethyl (meth)acrylate Fluoropropyl ester, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, etc.), alkylaminoalkyl (meth)acrylate (e.g. Dimethylaminoethyl (meth)acrylate etc.) and the like. These (meth)acrylates can be used individually or in combination of 2 or more types. Specific examples of acrylic oligomers include "ARUFON" manufactured by Toagosei Co., Ltd., "ACTFLOW" manufactured by Soken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF JAPAN.

<Photo-acid generator> The above-mentioned adhesive composition may contain a photo-acid generator. When the photoacid generator is contained in the above-mentioned adhesive composition, the water resistance and durability of the adhesive layer can be improved drastically compared to the case where the photoacid generator is not contained. The photoacid generator can be represented by the following general formula (4).

(惟L^＋ 表示任意的鎓陽離子；且，X^- 表示選自於由PF6₆ ^- 、SbF₆ ^- 、AsF₆ ^- 、SbCl₆ ^- 、BiCl₅ ^- 、SnCl₆ ^- 、ClO₄ ^- 、二硫胺甲酸鹽陰離子、SCN^- 所構成群組中之相對陰離子)。General formula (4) [Chemical formula 4]

(L ⁺ but an arbitrary cation; and, X ^- represents a group selected consisting of _{^{PF6 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, two thiamin Formate anion, SCN ^- the relative anion in the group).

^{Next, the relative anion X-} in the general formula (4) will be explained.

^{The relative anion X-} in the general formula (4) is not particularly limited in principle, and non-nucleophilic anions are preferred. When the relative anion X ^{-is a} non-nucleophilic anion, it is not easy to produce a nucleophilic reaction with cations coexisting in the molecule or various materials used in combination, so the photoacid generator represented by the general formula (4) itself or the use of The diachronic stability of its composition. The so-called non-nucleophilic anion here refers to an anion with a low ability to initiate a nucleophilic reaction. Examples of such anions include _{^{PF6 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, two thiocarbamoyl anions, SCN ^- and the like.

As preferred specific examples of the photoacid generator of the present invention, specific examples include "Cyracure-UVI-6992" and "Cyracure-UVI-6974" (the above are made by Dow Chemical Co., Ltd.) , "ADEKA OPTOMER SP150", "ADEKA OPTOMER SP152", "ADEKA OPTOMER SP170", "ADEKA OPTOMER SP172" (above manufactured by ADEKA Co., Ltd.), "IRGACURE250" (Ciba Specialty Chemicals) company), "CI-5102", "CI-2855" (the above are manufactured by Soda Corporation in Japan), "SANEIDO SI-60L", "SANEIDO SI-80L", "SANEIDO SI-100L", "SANEIDO SI -110L", "SANEIDO SI-180L" (above manufactured by Sanxin Chemical Co., Ltd.), "CPI-100P", "CPI-100A" (above manufactured by Sanya Pro (SAN-APRO) Co., Ltd.), "WPI- 069", "WPI-113", "WPI-116", "WPI-041", "WPI-044", "WPI-054", "WPI-055", "WPAG-281", "WPAG-567" , "WPAG-596" (The above is made by Wako Pure Chemical Industries, Ltd.).

Relative to the total amount of the adhesive composition, the content of the photoacid generator is 10% by weight or less, preferably 0.01-10% by weight, preferably 0.05-5% by weight, and particularly preferably 0.1-3% by weight.

<Photobase generator> A photobase generator can change or crack the molecular structure by light irradiation such as ultraviolet rays or visible rays, and act as a catalyst for the polymerization reaction of radical polymerizable compounds or epoxy resins. Function to generate more than one kind of alkaline compounds. The basic substance is, for example, a secondary amine and a tertiary amine. As the photobase generator, for example, the above-mentioned α-aminoacetophenone compound, the above-mentioned oxime ester compound, or having an oxyimino group, an N-methylated aromatic amine group, and an N-acylated aromatic Compounds with substituents such as amino groups, nitrobenzyl carbamate groups, and alkoxybenzyl carbamate groups. Among them, oxime ester compounds are preferred.

Compounds having an oxyimino group include, for example, O,O'-benzophenone oxime succinate, O,O'-benzophenone oxime succinate, benzophenone oxime acrylate-styrene copolymer Things.

The compounds having N-formylated aromatic amine groups and N-formylated aromatic amine groups include, for example, two-N-(p-formylamino) diphenylmethane, two-N-(p-ethyl Amino) diphenylmethane, bis-N-(p-benzamide) diphenylmethane, 4-formamido stilbene, 4-acetamido stilbene, 2,4- Dimethamidostilbene, 1-methamidonaphthalene, 1-acetamido naphthalene, 1,5-dimethylamido naphthalene, 1-methamido anthracene, 1,4-dimethyl Aminoanthracene, 1-acetylaminoanthracene, 1,4-dimethylaminoanthraquinone, 1,5-dimethylaminoanthraquinone, 3,3'-dimethyl-4,4' -Dimethamidobiphenyl, 4,4'-dimethylamido diphenyl ketone, etc.

Examples of compounds having a nitrobenzylcarbamate group and an alkoxybenzylcarbamate group include bis{{(2-nitrobenzyl)oxy}carbonyl}diaminodiphenylmethane , 2,4-bis{{(2-nitrobenzyl)oxy}stilbene, bis{{(2-nitrobenzyloxy)carbonyl}hexane-1,6-diamine, stubble Amine {{(2-nitro-4-chlorobenzyl)oxy}amide}.

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

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

<A compound containing either an alkoxy group or an epoxy group> In the adhesive composition described above, a photoacid generator, and any one of an alkoxy group and an epoxy group may be used together in the adhesive composition The compound of the person.

(Epoxy group-containing compounds and polymers) 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, it can also be used in combination with two or more epoxy groups in the molecule. Compounds with more than one functional group reactive with epoxy groups. The functional group reactive with the epoxy group here includes, for example, a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amine group, and the like. Considering the three-dimensional hardenability, it is preferable to have two or more functional groups in one molecule.

Examples of polymers having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, and bisphenol F and epichlorohydrin. Derived bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy Resins, alicyclic epoxy resins, diphenyl ether type epoxy resins, hydroquinone type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, sulphur type epoxy resins, trifunctional epoxy resins , Multifunctional epoxy resins such as tetrafunctional epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, hydantoin epoxy resins, trimeric isocyanate epoxy resins, fats Group chain epoxy resins, etc., these epoxy resins may be halogenated or hydrogenated. Commercially available epoxy resin products include, for example, JERCoat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, Epiclon 830 manufactured by DIC Co., Ltd. manufactured by Japan Epoxy Resins Co., Ltd. EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., CELLOXIDE series manufactured by DAICEL Chemical Co., Ltd. (2021, 2021P, 2083, 2085, 3000, etc.), EPOLEAD series, EHPE Series, YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyhydroxy polyether synthesized from bisphenols and epichlorohydrin with epoxy groups at both ends) manufactured by Nippon Steel Chemical Company; YP series, etc.), DENACOL series manufactured by NAGASE CHEMTEX, Epolite series manufactured by Kyoeisha Chemical Company, etc., but not limited to these. These epoxy-based resins can also be used in combination of two or more kinds.

(Compound and polymer having an alkoxy group) As the compound having an alkoxy group in the molecule, there are no particular restrictions as long as it has one or more alkoxy groups in the molecule, and well-known ones can be used. Examples of such compounds include melamine compounds, amino resins, and silane coupling agents.

The blending amount of the compound containing either an alkoxy group and an epoxy group relative to the total amount of the adhesive composition is usually 30% by weight or less. If the content of the compound in the composition is too large, the adhesiveness will decrease. The impact resistance of the drop test may deteriorate. The content of the compound in the composition is preferably 20% by weight or less. On the other hand, from the viewpoint of water resistance, the composition preferably contains the compound at 2% by weight or more, and more preferably 5% by weight or more.

<Silane Coupling Agent> When the adhesive composition used in the present invention is curable with active energy ray, it is preferable to use an active energy ray curable compound for the silane coupling agent. The same water resistance.

Specific examples of silane coupling agents include vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4 epoxycyclohexyl) as active energy ray-curable compounds. ) Ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethyl Oxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methyl Acrylicoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc.

Suitable are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

In terms of specific examples of the silane coupling agent that is not curable by active energy rays, the silane coupling agent (D1) having an amine group is preferred. 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-amine ethyl) Yl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane , Γ-(2-aminoethyl)aminopropyl triisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyl trimethoxysilane, γ-(6-amine Hexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureapropyltrimethoxysilane, γ-ureapropyltriethoxy Silane, N-phenyl-γ-aminopropyl trimethoxysilane, N-benzyl-γ-aminopropyl trimethoxysilane, N-vinylbenzyl-γ-aminopropyl triethoxysilane, N-cyclohexylaminomethyl triethoxysilane, N-cyclohexylaminomethyl diethoxymethylsilane, N-phenylaminomethyl trimethoxysilane, (2-aminoethyl)aminomethyl Amino-containing silanes such as trimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; N-(1,3-dimethylbutylene)- 3-(Triethoxysilyl)-1-propylamine and other ketimine type silanes.

The silane coupling agent (D1) having an amine group may be used only by one type, or may be used in combination of multiple types. Among them, in order to ensure good adhesiveness, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl) Aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, N -(1,3-Dimethylbutylene)-3-(triethoxysilyl)-1-propylamine is preferred.

Relative to the total amount of the adhesive composition, the blending amount of the silane coupling agent is preferably in the range of 0.01-20% by weight, preferably 0.05-15% by weight, and more preferably 0.1-10% by weight. If the blending amount exceeds 20% by weight, the storage stability of the adhesive composition will deteriorate, and if it is less than 0.1% by weight, the adhesive water resistance effect cannot be fully exhibited.

Specific examples of non-active energy ray-curable silane coupling agents other than those mentioned above include 3-ureapropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyl bis Methoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, imidazole silane, etc.

<Compound with vinyl ether group> When the adhesive composition used in the present invention contains a compound having a vinyl ether group, the adhesion water resistance between the polarizing member and the adhesive layer will be improved, which is ideal. Although the reason for obtaining this effect is not clear, it can be presumed that one of the reasons is that the vinyl ether group of the compound interacts with the polarizing member to increase the adhesion between the polarizing member and the adhesive layer. In order to further improve the water resistance of the polarizer and the adhesive layer, the compound is preferably a radical polymerizable compound having a vinyl ether group. In addition, relative to the total amount of the adhesive composition, the content of the compound is preferably 0.1 to 19% by weight.

<The compound capable of producing keto-enol tautomerism> The adhesive composition used in the present invention may contain a compound capable of producing keto-enol tautomerism. For example, in an adhesive composition containing a cross-linking agent or in an adhesive composition that can be blended with a cross-linking agent, a form containing the above-mentioned compound capable of producing keto-enol tautomerism can be suitably adopted. Thereby, the viscosity of the adhesive composition after blending with the organometallic compound can be prevented from excessively increasing or gelling, and the formation of microgels can be suppressed, and the effect of extending the life of the composition can be achieved.

Various β-dicarbonyl compounds can be used as the above-mentioned compound capable of producing keto-enol tautomerism. Specific examples include acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexan-3,5-dione, 6-methylheptane-2,4-dione , 2,6-Dimethylheptane-3,5-dione and other β-diketones; methyl acetylacetate, ethyl acetylacetate, isopropyl acetylacetate, tertiary butyl acetylacetate Acetyl acetates; ethyl propylacetate, ethyl propylacetate, isopropyl propylacetate, tertiary butyl propylacetate and other propylacetates; ethyl isobutylacetate , Ethyl isobutyryl acetate, isobutyl isopropyl acetate, tertiary butyl isobutyryl acetate and other isobutyryl acetate; methyl malonate, ethyl malonate and other malonic acid esters. Among them, suitable compounds may be exemplified by acetone and acetone acetate. The compound capable of producing keto-enol tautomerism may be used alone or in combination of two or more kinds.

The use amount of the compound that can produce keto-enol tautomerism is, for example, 0.05 parts by weight to 10 parts by weight, preferably 0.2 parts by weight to 3 parts by weight (for example, 0.3 parts by weight) relative to 1 part by weight of the organometallic compound. Parts~2 parts by weight). If the usage amount of the above-mentioned compound is less than 0.05 part by weight relative to 1 part by weight of the organometallic compound, it may be difficult to fully exert the effect of use. On the other hand, if the amount of the compound used exceeds 10 parts by weight relative to 1 part by weight of the organometallic compound, there will be excessive interactions with the organometallic compound, making it difficult to exhibit the desired water resistance.

<Polyrotaxane> The adhesive composition of the present invention may contain polyrotaxane. The polyrotaxane has a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule, and an end capping group, and the end capping group is arranged in such a way that the cyclic molecule will not be separated from the linear molecule At both ends of the linear molecule. The cyclic molecule preferably has a functional group that is hardened by active energy rays.

The cyclic molecule is not particularly limited as long as the opening of the linear molecule is surrounded by a thorn, can move on the linear molecule, and has an active energy ray polymerizable group. In addition, in this specification, the "cyclic" of the "cyclic molecule" means that it is substantially "cyclic." That is, as long as it can move on a linear molecule, the cyclic molecule may be incompletely closed.

Specific examples of cyclic molecules include cyclic polymers such as cyclic polyethers, cyclic polyesters, cyclic polyetheramines, and cyclic polyamines; and α-cyclodextrin, β-cyclodextrin, and γ-ring Cyclodextrins such as dextrin. Among them, from the viewpoint that it is relatively easy to obtain and can choose a variety of end-capping groups, it is preferably cyclodextrin such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Two or more types of cyclic molecules may be mixed in the polyrotaxane or the adhesive.

In the polyrotaxane used in the present invention, the cyclic molecule has an active energy ray polymerizable group. Thereby, even after the polyrotaxane reacts with the active energy ray curable component and is cured, an adhesive with a movable crosslinking point can be obtained. The active energy ray polymerizable group possessed by the cyclic molecule may be a group that can be polymerized with the above-mentioned active energy ray curable compound, and examples thereof include (meth)acryloyl groups and (meth)acryloyloxy groups. Base polymerizable group.

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

It is preferable to introduce a hydrophobic modifying group into the cyclic molecule. By introducing a hydrophobic modifying group, the compatibility with active energy ray curable components can be improved. In addition, since it can be imparted with hydrophobicity, when used as 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 polyester chains, polyamide chains, alkyl chains, oxyalkylene chains, ether chains, and the like. Specific examples include the bases described in [0027] to [0042] of WO2009/145073.

A polarizing film using a resin composition containing polyrotaxane as an adhesive has excellent water resistance. Although the reason for the improved water resistance of the polarizing film is not clear, it can be presumed as follows. That is, we believe that the mobility of the cyclic molecules of polyrotaxane causes the cross-linking point to move (the so-called pulley effect), thereby imparting flexibility to the cured adhesive and increasing the density of the unevenness on the surface of the polarizer. As a result, it prevents water from invading the interface between the polarizer and the adhesive layer. In addition, it is also speculated that the hydrophobicity of the adhesive can be imparted to the adhesive by the polyrotaxane having a hydrophobic modifying group, which also helps prevent water from entering the interface between the polarizer and the adhesive layer.

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

(惟，X為含有選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、及巰基所構成群組中之至少1種反應性基之官能基，且R⁹ 及R¹⁰ 分別獨立表示氫原子，或是亦可具有取代基的脂肪族烴基、芳基或雜環基)。通式(5)記載之化合物容易與聚乙烯醇系偏光件所具有之羥基形成酯鍵。又，前述通式(5)所記載之化合物更具有含反應性基之X，透過X所含之反應性基而可與接著劑組成物中含有之其他硬化性成分反應。即，硬化性樹脂層所具有的硼酸基及/或硼酸酯基可透過共價鍵與偏光件所具有之羥基強固接著。藉此，即便偏光件與硬化性樹脂層之界面有水分存在，因其等不僅透過氫鍵及/或離子鍵，還透過共價鍵強固地相互作用，故偏光件與硬化性樹脂層之間的接著耐水性會飛躍性地提升。從提升偏光件與硬化物層之接著性及耐水性的觀點，尤其是從在透過接著劑層來接著偏光件與透明保護薄膜的情況下提升接著性及耐水性的觀點來看，接著劑組成物中，通式(5)記載之化合物含量以0.001~50重量%為佳，0.1~30重量%較佳，1~10重量%尤佳。The aforementioned adhesive composition may contain a compound represented by the following general formula (5): [Chemical formula 5]

(However, X is selected from the group consisting of vinyl, (meth)acryloyl, styryl, (meth)acrylamido, vinyl ether, epoxy, oxetanyl, And a functional group of at least one reactive group in the group consisting of a mercapto group, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom, or an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group that may have a substituent). The compound described in the general formula (5) easily forms an ester bond with the hydroxyl group of the polyvinyl alcohol-based polarizer. In addition, the compound described in the aforementioned general formula (5) further has X containing a reactive group, and can react with other curable components contained in the adhesive composition through the reactive group contained in X. That is, the boric acid group and/or borate group of the curable resin layer can be strongly bonded to the hydroxyl group of the polarizing member through a covalent bond. Thereby, even if moisture exists at the interface between the polarizing member and the curable resin layer, it interacts strongly not only through hydrogen bonds and/or ionic bonds, but also through covalent bonds. Therefore, the polarizer and the curable resin layer interact strongly with each other. The subsequent water resistance will be greatly improved. From the viewpoint of improving the adhesion and water resistance between the polarizer and the cured layer, especially from the viewpoint of improving the adhesion and water resistance when the polarizer and the transparent protective film are bonded through the adhesive layer, the adhesive composition Among them, the content of the compound described in the general formula (5) is preferably 0.001-50% by weight, preferably 0.1-30% by weight, and particularly preferably 1-10% by weight.

<Organic metal compound> When the adhesive composition of the present invention contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelate, and a polymer having a polymerizable functional group and a carboxyl group In the case of a sexual compound, the water resistance of the polarizer and the adhesive layer can be improved, so it is preferred. The organometallic compound becomes an active metal species due to the inclusion of moisture. As a result, the organometallic compound strongly interacts with both the polarizer and the active energy ray curable component constituting the adhesive layer. Thereby, even if moisture exists at the interface between the polarizing member and the adhesive layer, since it interacts strongly through the organometallic compound, the adhesive water resistance between the polarizing member and the adhesive layer is greatly improved. The organometallic compound greatly contributes to the adhesion and water resistance of the adhesive layer. However, the composition containing the compound becomes unstable due to liquid stability, which tends to shorten the service life and deteriorate the productivity. It is speculated that one of the reasons for this is the high reactivity of the organometallic compound, and its contact with a trace amount of moisture contained in the composition will initiate a hydrolysis reaction and a self-condensation reaction. Phase separation, precipitation). However, when the composition contains both an organometallic compound and a polymerizable compound having a polymerizable functional group and a carboxyl group, the hydrolysis reaction and self-condensation reaction of the organometallic compound can be suppressed, and the liquid of the organometallic compound in the composition can be stabilized. Sex has improved dramatically. The ratio of the organometallic compound is preferably 0.05 to 15% by weight of the total composition, and preferably 0.1 to 10% by weight. This is because when the blending amount exceeds 15% by weight, the storage stability of the composition deteriorates, and the ratio of the components for adhesion to the polarizer or the protective film is relatively insufficient, which may reduce the adhesiveness. When it is less than 0.05% by weight, the effect of subsequent water resistance may not be fully exerted. In the curable adhesive composition, when the total amount of organometallic compounds is α (mol), the content of polymerizable compounds having polymerizable functional groups and carboxyl groups is preferably 0.25α (mol) or more, 0.35α (mol) The above is preferable, and 0.5α (mol) or more is particularly preferable. If the content of the polymerizable compound having a polymerizable functional group and a carboxyl group is less than 0.25α (mol), the stabilization of the organometallic compound may be insufficient, resulting in the progress of the hydrolysis reaction and the self-condensation reaction and the shortening of the service life. In addition, the upper limit of the content of the polymerizable compound relative to the total amount α (mol) of the organometallic compound is not particularly limited, and may be, for example, about 4α (mol).

<Polychlorinated olefin> Polychlorinated olefin may also be blended in the adhesive composition of the present invention. At this time, the dyeability of the resulting adhesive layer derived from the iodine compound of the polyvinyl alcohol polarizer will be significantly reduced, and it can function as a protective layer that inhibits the release and diffusion of the iodine compound from the polarizer. . As a result, when the adhesive composition of the present invention is used for polarizing film applications, the optical durability of the polarizing film will be significantly improved. In addition, the adhesive composition of the present invention must be optically transparent. Therefore, the polyolefin resin should preferably be a polychlorinated olefin that is soluble in active energy ray curable components and does not cause layer separation or precipitation. Polyolefins that are not chlorinated are not good because they have significantly lower solubility for curable components that are hardened by irradiation with active energy rays.

Examples of polychlorinated olefins that can be used in the present invention include chlorinated polyethylene, chlorinated polypropylene, acrylic-modified or urethane-modified polychlorinated olefins.

The chlorine content in the polychlorinated olefin is preferably 25-50% by weight, more preferably 30-45% by weight. If it is less than 25% by weight, the solubility of the active energy ray curable component may decrease, and it may become difficult to form an optically transparent composition. If it exceeds 50% by weight, under the severe humidification environment when the polarizing film is made, the change in its optical characteristics becomes large, and the effects of the present invention may become impossible to obtain. The chlorine content in polychlorinated olefins can be measured in accordance with JIS-K7229. More specifically, it can be measured by, for example, the "oxygen flask combustion method", that is, the chlorine-containing resin is burned in an oxygen environment, and the generated gas chlorine is absorbed by water, and then the amount is determined by titration.

In addition, the weight average molecular weight of the chlorinated polyolefin is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and it is best to use the range of 10,000 to 20,000. Once the molecular weight of the polychlorinated olefin is too low, the water resistance may not be sufficiently improved when the cured product is made. If the molecular weight is too high, the solubility of the active energy ray curable component will be significantly reduced, and it may become difficult to form an optically transparent composition.

As for polychlorinated olefins, commercially available products that can be obtained include, for example, SUPERCHLON series (manufactured by Nippon Paper & Chemical Corporation), HARDLEN series (manufactured by Toyobo Co., Ltd.), ELASLEN series (manufactured by Showa Denko Corporation), and the like.

Among the commercially available products, it is more appropriate to use SUPERCHLON series (manufactured by Nippon Paper & Chemical Corporation) "SUPERCHLON 814HS", "SUPERCHLON 390S", "SUPERCHLON 803MW", "SUPERCHLON 803L", "SUPERCHLON B"; HARDLEN series (Toyobo "HARDLEN 16-LP" and "HARDLEN 15-LP" manufactured by the company); and "ELASLEN 404B", "ELASLEN 402B", "ELASLEN 401A", especially "SUPERCHLON 814HS" of the ELASLEN series (manufactured by Showa Denko) It is excellent in the balance between the solubility of active energy ray curable components and the stability of optical properties under severe humidification conditions when making polarizing films, making it more suitable for use.

、2,6-二三級丁基-4-甲苯酚等聚合抑制劑；聚合起始助劑；界面活性劑；可塑劑；紫外線吸收劑；無機填充劑；顏料；染料等。<Additives other than the above> In addition, the adhesive composition used in the present invention may be blended with various additives as other optional components within a range that does not impair the purpose and effects of the present invention. As such additives, for example, epoxy resin, polyamide, polyamide imide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene Polymers or oligomers such as diene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, polysiloxane-based oligomers, and polysulfide-based oligomers; Phenothi

, 2,6-Di-tertiary butyl-4-cresol and other polymerization inhibitors; polymerization initiators; surfactants; plasticizers; ultraviolet absorbers; inorganic fillers; pigments; dyes, etc.

Relative to the total amount of the adhesive composition, the above-mentioned additives are usually 0-10% by weight, preferably 0-5% by weight, and most preferably 0-3% by weight.

<Adhesive composition for polarizing film> In order to effectively suppress the generation of laminated bubbles, the surface tension of the adhesive composition for polarizing film of the present invention before curing is preferably 30 mN/m or less. The method of measuring the surface tension of the adhesive composition before curing will be described in detail later.

The adhesive composition for polarizing films of the present invention preferably has an overall water absorption rate of 10% by weight or less after immersing the cured product obtained by curing the composition in pure water at 23° C. for 24 hours. The overall water absorption is expressed by the following formula. Formula: {(M2-M1)/M1}×100(%) However, M1: the weight of the cured product before immersion; M2: the weight of the cured product after immersion. By setting the overall water absorption rate to 10% by weight or less, it is possible to prevent water from moving to the polarizer when the polarizing film is placed in a severe high-temperature and high-humidity environment, and to suppress the increase in the transmittance of the polarizer and the degree of polarization. reduce. From the viewpoint of improving the optical durability of the adhesive layer of the polarizing film under severe environments at high temperatures, the aforementioned overall water absorption is preferably 5% by weight or less, more preferably 3% by weight or less, 1% by weight or less is best. On the other hand, when bonding the polarizer and the transparent protective film, the polarizer already retains a certain amount of moisture, so when the hardening type adhesive comes into contact with the moisture contained in the polarizer, it may cause dents, bubbles, and other appearance defects. situation. In order to suppress poor appearance, the hardened adhesive should absorb a certain amount of water. More specifically, the overall water absorption is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more.

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

The adhesive composition of the present invention preferably has a higher octanol/water partition coefficient (hereinafter referred to as logPow value). The logPow value is an index indicating the lipophilicity of a substance, which means the logarithmic value of the octanol/water partition coefficient. High logPow means lipophilicity, which means low water absorption. Although the logPow value can be measured (the flask permeation method described in JIS-Z-7260), it can also be calculated by calculating the structure of each compound based on the constituent components (curable components, etc.) of the curable adhesive for polarizing films . In this manual, the logPow value calculated by ChemDraw Ultra manufactured by Cambridgesoft is used. Based on the above calculated value, the logPow value of the curable adhesive for polarizing films of the present invention can be calculated by the following formula. The logPow of the hardening adhesive=Σ(logPowi×Wi) logPowi: the logPow value of each component of the hardening adhesive Wi: (the number of moles of the i component)/(the total number of moles of each component of the hardening adhesive) When the above calculation is performed, among the components of the hardening adhesive, the components that do not form the skeleton of the hardened product (adhesive layer), such as the polymerization initiator or the photoacid generator, will be excluded from the above calculated components. The logPow value of the curable adhesive for polarizing films of the present invention is preferably 1 or more, preferably 1.5 or more, and most preferably 2 or more. This can improve adhesion resistance and humidification durability. On the other hand, the logPow value of the curable adhesive for polarizing films of the present invention is usually about 8 or less, and preferably 5 or less, and more preferably 4 or less. If the logPow value is too high, as described above, it is easy to cause poor appearance such as sinking or bubbles, which is undesirable.

Furthermore, the adhesive composition of the present invention is preferably substantially free of water or volatile solvents. Since it does not substantially contain a volatile solvent and does not require heat treatment, it not only has excellent productivity, but also suppresses the deterioration of the optical properties of the polarizer due to heat, which is preferable. The so-called "substantially free" means that, for example, when the total amount of the adhesive composition is 100% by weight or less, the content is less than 5% by weight, and in particular, the content is less than 2% by weight.

In addition, the adhesive composition should be selected so that the Tg of the cured product layer formed by the foregoing, especially the adhesive layer, becomes 60°C or higher, more preferably 70°C or higher, more preferably 75°C or higher, and more preferably 100°C Above, it is more preferably above 120°C. On the other hand, if the Tg of the adhesive layer becomes too high, the flexibility of the polarizing film will decrease. Therefore, the Tg of the adhesive layer is preferably 300°C or less, more preferably 240°C or less, and more preferably 180°C or less. Tg<Glass transition temperature> is measured using the dynamic viscoelasticity measuring device RSAIII manufactured by TA INSTRUMENTS under the following measuring conditions. Sample size: width 10mm, length 30mm, clamping distance 20mm, measuring mode: stretching, frequency: 1Hz, heating rate: 5°C/min, for dynamic viscoelasticity measurement, and use the temperature Tg as the peak top of tanδ.

In addition, the storage elastic modulus of the cured product layer formed by the aforementioned adhesive composition, especially the adhesive layer, is preferably 1.0×10 ⁷ Pa or more ^{at 25° C., and preferably 1.0×10 8} Pa or more. The storage elastic modulus of the adhesive layer should be 1.0×10 ³ Pa~1.0×10 ⁶ Pa. The storage elastic modulus of the adhesive layer will affect the cracks of the polarizer when the polarizing film is thermally cycled (from -40°C to 80°C, etc.). When the storage elastic modulus is low, the polarizer cracks are likely to occur. The temperature zone with high storage elastic modulus is preferably below 80°C, and the best below 90°C. The storage elastic modulus is measured at the same time as Tg<Glass Transition Temperature>, using the dynamic viscoelasticity measuring device RSAIII manufactured by TA INSTRUMENTS under the same measuring conditions. The dynamic viscoelasticity is measured and the storage elastic modulus (E') value is used.

In addition, since the adhesive composition of the present invention has a curable component, curing shrinkage usually occurs when the adhesive composition is cured. The curing shrinkage rate is an index indicating the curing shrinkage rate when the adhesive layer is formed from the resin composition. If the curing shrinkage rate of the adhesive layer is increased, when the adhesive composition is cured and the adhesive layer is formed, interface deformation may occur and poor bonding may occur, so it is preferable to suppress this. From the above viewpoint, the cured product obtained by curing the resin composition having the effects of the present invention preferably has the curing shrinkage rate of 10% or less. In addition, the aforementioned curing shrinkage rate is preferably low, and the aforementioned curing shrinkage rate is preferably 8% or less, and more preferably 5% or less. The above-mentioned curing shrinkage rate is measured by the method described in Japanese Patent Laid-Open No. 2013-104869, and specifically measured by the method described in the examples using a curing shrinkage sensor manufactured by Sentech.

In addition, from the viewpoint of safety, the adhesive composition used in the present invention preferably uses a material with less skin irritation as the hardening component. Skin irritation can be judged by P.I.I index. P.I.I is a widely used index that indicates the degree of skin damage, and is measured by the Cui's test (Draize method). The measured value is expressed in the range of 0-8. The smaller the value, the lower the irritation. However, the error of the measured value is large, so it is good as a reference value. P.I.I is preferably 4 or less, preferably 3 or less, and most preferably 2 or less.

<Optical Film> The adhesive composition of the present invention can be suitably used for optical film applications, and is particularly suitable for polarizing film applications including at least a polyvinyl alcohol-based polarizer. Hereinafter, as an example of an optical film, a polarizing film will be described as an example.

<Polarizing film> The polarizing film of the present invention is obtained by laminating a transparent protective film on at least one surface of a polarizer with an adhesive interposed therebetween, and the adhesive layer is obtained by curing the polarizing film adhesive composition. For example, a transparent protective film may be laminated on one side of the polyvinyl alcohol-based polarizer via the cured layer of the polarizing film adhesive composition, or it may be laminated on both areas of the polyvinyl alcohol-based polarizer. Transparent protective film.

In addition, the polarizing film of the present invention may also have an adhesive layer. The adhesive layer can be laminated at any position, for example, after the above-mentioned hardened layer is laminated on the polyvinyl alcohol-based polarizer, then an adhesive layer is formed on it, or it can be hardened on one of the area layers of the polyvinyl alcohol-based polarizer. The object layer, and an adhesive layer on another area. Alternatively, the adhesive may be laminated on the protective film side of the polarizing film composed of the polarizer/the hardened material layer/protective film. As mentioned above, the adhesive can be layered on any position of the polarizing film.

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

The thickness of the cured product layer formed by the above-mentioned adhesive composition, especially the adhesive layer, is preferably 0.2 to 3 μm. When the thickness of the hardened layer is too thin, the peeling force will decrease due to insufficient cohesion of the hardened layer, which is not preferable. When the thickness of the hardened layer is too thick, peeling easily occurs when stress is applied to the cross section of the polarizing film, and peeling failure due to impact may occur, which is not preferable. The thickness of the adhesive layer is preferably 0.3 to 2 μm, and 0.4 to 1.5 μm is the best.

In addition, when the thickness of the adhesive layer is d (μm) and the content of the bubble inhibitor contained in the adhesive layer is y (wt%), when the following formula (1) is satisfied, the suppression of laminated bubbles can be considered The effect and the adhesion improvement effect are better. 0.1-0.02d≦y≦0.6-0.08d　(1) When y<0.1-0.02d, the adhesion improvement effect of the adhesive layer is good, but the laminated bubbles tend to increase; and when y>0.6-0.08d At this time, the effect of suppressing the build-up bubbles of the adhesive layer is good, but the adhesion improvement effect tends to deteriorate. In addition, in the above formula (1), the thickness d (μm) of the adhesive layer is preferably 0.2≦d≦3, preferably 0.3≦d≦2, and more preferably 0.4≦d≦1.5.

The polarizer is not particularly limited, and various polarizers can be used. As the polarizer, for example, hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, ethylene-vinyl acetate copolymer-based partially saponified films, etc., adsorb iodine or dichroic dyes, etc. The dichroic material is uniaxially stretched, and polyene-based alignment films such as dehydrated polyvinyl alcohol or dehydrated polyvinyl chloride. Among them, a polarizer composed of a polyvinyl alcohol-based film and dichroic substances such as iodine is preferred. The thickness of the polarizer is preferably 2-30μm, more preferably 4-20μm, most preferably 5-15μm. When the thickness of the polarizer is thin, the optical durability will decrease and it is not good. When the thickness of the polarizer is thick, the dimensional change under high temperature and high humidity becomes large, and the display unevenness is caused, which is not good.

A polarizer made of polyvinyl alcohol-based film dyed with iodine and then uniaxially stretched, for example, can be made in the following way: polyvinyl alcohol is dipped in an aqueous solution of iodine to dye, and then stretched to 3 to 7 times the original length . It can also be immersed in an aqueous solution of boric acid, potassium iodide, etc. according to needs. In addition, the polyvinyl alcohol-based film can be immersed in water for washing before dyeing. By washing the polyvinyl alcohol-based film with water, the dirt on the surface of the polyvinyl alcohol-based film and the anti-caking agent can be cleaned. In addition, the swelling of the polyvinyl alcohol-based film also has the effect of preventing uneven dyeing and other unevenness. Stretching may be performed after dyeing with iodine, or it may be stretched while dyeing, or it may be dyed with iodine after stretching. It can also be extended in an aqueous solution of boric acid, potassium iodide, etc., or in a water bath.

In addition, regarding the adhesive composition used in the present invention, if a thin polarizer with a thickness of 10 μm or less is used as a polarizer, its effect can be remarkably exerted (it can satisfy the optical durability in the severe environment of high temperature and high humidity) . The above-mentioned polarizers with a thickness of less than 10μm are relatively more affected by moisture than those with a thickness of more than 10μm, and the optical durability in the environment of high temperature and high humidity is not sufficient, and it is easy to cause increase in transmittance or polarization. The degree is reduced. That is, when the above-mentioned polarizing member of 10 μm or less is laminated with the adhesive having an overall water absorption rate of 10% by weight or less of the present invention, the movement of water to the polarizing member is suppressed in an environment of severe high temperature and high humidity, thereby enabling Significantly suppress the deterioration of optical durability such as the increase in the transmittance of the polarizing film and the decrease in the degree of polarization. From the viewpoint of thinning, the thickness of the polarizer is preferably 1~7μm. Such a thin polarizer has less unevenness in thickness, is excellent in visibility, and has a small dimensional change. In addition, the thickness of the polarizing film can be reduced in thickness, which is very desirable from the viewpoint.

Representative examples of thin polarizers include those described in Japanese Patent Laid-Open No. 51-069644, or Japanese Patent Laid-Open No. 2000-338329, Handbook WO2010/100917, Specification of PCT/JP2010/001460, or Japanese Patent The thin polarizing film of Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692. These thin polarizing films can be produced by a manufacturing method including a step of extending a polyvinyl alcohol-based resin (hereinafter, also referred to as a PVA-based resin) layer and a resin substrate for stretching in the state of a laminate and a step of dyeing. As long as this method is used, even if the PVA-based resin layer is thin, it can be stretched without being broken due to stretching by being supported by the stretching resin base material.

In the manufacturing method of the aforementioned thin polarizing film that includes the step of stretching in the state of the laminate and the step of dyeing, from the viewpoint that it can be stretched at a high magnification to improve the polarization performance, it is preferable to use the manual such as WO2010/100917 , PCT/JP2010/001460 specification, or Japanese Patent Application No. 2010-269002 specification or Japanese Patent Application No. 2010-263692 specification described in Japanese Patent Application No. 2010-263692. It is particularly desirable to use the method described in Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692, which includes a step of performing aerial extension as a supplement before extension in an aqueous solution of boric acid. By.

The transparent protective film is preferably one that is excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropy. Examples include: polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose; polymethyl methacrylate Acrylic polymers such as esters; styrene polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); and polycarbonate polymers. In addition, the following polymers can also be cited as examples of polymers forming the above-mentioned transparent protective film: polyethylene, polypropylene, polyolefins having cyclic or even norbornene structures, such as polyolefin polymerization of ethylene-propylene copolymers Amine-based polymers such as vinyl chloride polymers, nylon and aromatic polyamides, imine-based polymers, turbid polymers, polyether-based polymers, polyetheretherketone-based polymers, and Benzene sulfide polymer, vinyl alcohol polymer, chlorinated vinylene polymer, vinyl butyral polymer, aryl ester polymer, polyoxymethylene polymer, epoxy polymer or the above-mentioned polymers The blends and so on. The transparent protective film may contain one or more arbitrary appropriate additives. Examples of additives include ultraviolet absorbers, antioxidants, slip agents, plasticizers, mold release agents, anti-colorants, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. In the transparent protective film, the above-mentioned thermoplastic resin content is preferably 50-100% by weight, preferably 50-99% by weight, more preferably 60-98% by weight, particularly preferably 70-97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, the inherent high transparency of the thermoplastic resin may not be sufficiently exhibited.

As a transparent protective film, the Tg (glass transition temperature) is preferably 115°C or higher, more preferably 120°C or higher, more preferably 125°C or higher, and particularly preferably 130°C or higher. With a Tg of 115°C or higher, it can become a polarizing film with excellent durability. The upper limit of Tg of the above-mentioned transparent protective film is not particularly limited, but it is preferably 170°C or lower from the viewpoint of moldability and the like.

The polarizer and the transparent protective film may be subjected to surface modification treatment before laminating the above-mentioned adhesive composition. In particular, the polarizer is preferably subjected to surface modification treatment on the surface of the polarizer before applying the adhesive composition or bonding. Surface modification treatment can include corona treatment, plasma treatment and ITRO treatment (flame silane treatment), etc., and corona treatment is particularly preferred. By performing corona treatment, polar functional groups such as carbonyl groups or amine groups can be generated on the surface of the polarizer, thereby improving the adhesion with the curable resin layer. In addition, surface foreign matter can be removed due to the ashing effect, and surface irregularities can be reduced, so a polarizing film with excellent appearance characteristics can be made.

When performing surface modification treatment on the polarizer, it is advisable to apply the surface roughness (Ra) of the polarizer surface to 0.6nm or more. The aforementioned surface roughness (Ra) is preferably 0.8 nm or more, more preferably 1 nm or more. As a result, the aforementioned surface roughness (Ra) is 0.6 nm or more, so in the manufacturing step of the polarizing film, even when the surface of the polarizing member is brought into contact with the guide roller, the polarizing member can still be transported well. In addition, if the surface roughness (Ra) becomes too large, the temperature and water resistance will deteriorate. Therefore, the surface roughness (Ra) is preferably 10 nm or less, and more preferably 5 nm or less.

The measurement of the aforementioned surface roughness (Ra) is to calculate the average roughness (average value of the surface irregularities) to express the parameter of the surface roughness. The surface roughness (Ra) is measured using an atomic force microscope (AFM) Nanoscope IV manufactured by Veeco in the Tapping mode. The cantilever holder is to use, for example, the Metrology Probe probe: Tap300 (RTESP type). The measuring range is 1μm square.

The polarizing film of the present invention can be manufactured according to the manufacturing method including the following steps: coating step, coating the adhesive composition on at least one side of the polarizing member and the transparent protective film; bonding step, laminating the polarizing member and the transparent protective film Film; and the next step, irradiating active energy rays from the side of the polarizer surface or the surface of the transparent protective film to harden the adhesive composition to obtain an adhesive layer, and the polarizer and the transparent protective film are bonded through the adhesive layer.

The method of coating the adhesive composition for polarizing films can be appropriately selected depending on the viscosity of the composition or the desired thickness. Examples include reverse coaters, gravure coaters (direct, reverse, or indirect), and bar reverse coaters. Cloth machine, roll coater, die coater, bar coater, rod coater, etc. The viscosity of the adhesive composition used in the present invention is preferably 3-100 mPa·s, more preferably 5-50 mPa·s, and most preferably 10-30 mPa·s. When the viscosity of the curable resin composition is high, the surface smoothness after application is poor, and poor appearance may occur, which is undesirable. The curable resin composition used in the present invention can be applied after heating or cooling the composition and adjusting the viscosity to a preferable range.

Generally, when two films are laminated, the adhesive composition is generally applied to the film bonding surface on one side and laminated. However, by coating the adhesive layer on the film bonding surfaces on both sides and then laminating, A laminated film with excellent appearance grade can be produced. The coating method is the later metering coating method. In the present invention, the "post-metering coating method" refers to a method in which an external force is applied to a liquid film to remove excess liquid and obtain a predetermined coating film thickness. In the manufacturing method of the polarizing film of the present invention, when the external force is applied to the liquid film composed of the adhesive composition, foreign matter such as dirt or dust present on the bonding surface is removed. As specific examples of post-metering coating methods, gravure roll coating methods, forward roll coating methods, air knife coating methods, rod/rod coating methods, etc. can be cited, but the accuracy of foreign matter removal From the viewpoint of uniformity of coating film thickness, etc., in the present invention, the aforementioned coating method is preferably a gravure roll coating method using a gravure roll.

The polarizer and the transparent protective film can be bonded through the adhesive composition after coating as described above. The bonding of the polarizer and the transparent protective film can be performed using a roll laminate. The method of layering the protective film on the two areas of the polarizer can be selected from the following methods: the method of laminating the polarizer and one protective film and then laminating the other protective film; and the method of laminating the polarizer and two protective films at the same time . The trapped air bubbles generated during bonding can be significantly reduced by the former method, which is ideal, that is, the method of bonding a polarizer and a protective film and then bonding another protective film.

The active energy rays used in the curing step can be roughly divided into electron beam curing properties, ultraviolet curing properties, and visible light curing properties. In the present invention, the active energy line with a wavelength range of 10 nm to less than 380 nm is recorded as ultraviolet light, and the active energy line with a wavelength range of 380 nm to 800 nm is recorded as visible light. When manufacturing the polarizing film of the present invention, it is particularly suitable to use visible light of 380nm~450nm.

The polarizing film of the present invention is to directly coat the polarizer and/or transparent protective film with the adhesive composition for the polarizing film, and after bonding the polarizer and the transparent protective film, irradiate active energy rays (electron rays, ultraviolet rays, visible rays) Etc.) to harden the adhesive composition to form an adhesive layer. The irradiation direction of active energy rays (electron rays, ultraviolet rays, visible rays, etc.) can be irradiated from any appropriate direction. It is preferable to irradiate from the side of the transparent protective film. If irradiated from the side of the polarizer, the polarizer may deteriorate due to active energy rays (electron beams, ultraviolet rays, visible rays, etc.).

Regarding the electron beam curability, as long as the electron beam irradiation conditions are conditions capable of curing the above-mentioned polarizing film adhesive composition, any appropriate conditions can be adopted. For example, during electron beam irradiation, the accelerating voltage should be 5kV~300kV, more preferably 10kV~250kV. When the accelerating voltage is lower than 5kV, the electron beam will not reach the adhesive composition for polarizing film and there is a risk of insufficient curing; and when the accelerating voltage exceeds 300kV, the penetration force through the sample will be too strong, and there will be resistance to the transparent protective film or polarized light. Pieces are in danger of causing harm. The amount of irradiation is 5-100 kGy, preferably 10-75 kGy. When the irradiation dose is less than 5kGy, the adhesive composition for polarizing film will not harden enough; when it exceeds 100kGy, it will damage the transparent protective film or the polarizer, reduce the mechanical strength or produce yellowing, and fail to obtain the predetermined optical properties.

Electron beam irradiation is usually carried out in an inert gas, however, if necessary, it can also be carried out in the atmosphere or with a small amount of oxygen introduced. Although it depends on the material of the transparent protective film, by properly introducing oxygen, an oxygen barrier can be deliberately created on the surface of the transparent protective film that the electron beam will initially contact, preventing damage to the transparent protective film, and effectively The adhesive is irradiated with electron rays.

In the manufacturing method of the polarizing film of the present invention, the active energy ray is preferably the ray containing the visible light in the wavelength range of 380nm~450nm, especially the active energy ray that uses the most irradiated amount of visible light in the wavelength range of 380nm to 450nm Better. Among UV curability and visible light curability, if a transparent protective film (transparent UV non-transparent protective film) with UV absorption energy is used, it will absorb light with a wavelength shorter than 380nm, so the wavelength is shorter than 380nm. Light cannot reach the adhesive composition and does not help its polymerization reaction. In addition, the light with a wavelength shorter than 380nm absorbed by the transparent protective film will be converted into heat energy, which causes the transparent protective film itself to generate heat, which causes the polarizing film to produce curls, wrinkles and other undesirable causes. Therefore, when ultraviolet curability and visible light curability are used in the present invention, it is better to use a device that does not emit light with a wavelength shorter than 380nm as the active energy ray generating device. More specifically, it is calculated based on the product of the wavelength range of 380~440nm. The ratio of the illuminance to the cumulative illuminance of the wavelength range of 250 to 370 nm is preferably 100:0 to 100:50, preferably 100:0 to 100:40. As the active energy line of the present invention, a metal halide lamp enclosed with gallium and an LED light source with a wavelength range of 380 to 440 nm are suitable. Alternatively, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, incandescent bulbs, xenon lamps, halogen lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, gallium lamps, excimer lasers or Sunlight and other light sources including ultraviolet and visible light can also be used with a band-pass filter to shield ultraviolet light with a wavelength shorter than 380nm. In order to improve the bonding performance of the adhesive layer between the polarizer and the transparent protective film, while preventing the polarizing film from curling, it is advisable to use a metal halide lamp enclosed in gallium and pass through a bandpass filter that can block light with a wavelength shorter than 380nm. Active energy ray, or active energy ray with a wavelength of 405nm obtained by using an LED light source.

The adhesive composition for polarizing films of the present invention is particularly suitable for forming an adhesive layer that can bond a polarizer and a transparent protective film with a light transmittance of less than 5% at a wavelength of 365 nm. At this time, the adhesive composition for polarizing film of the present invention contains the photopolymerization initiator of the above general formula (2), and when irradiated with ultraviolet light through a transparent protective film having UV absorption energy, it can be cured to form an adhesive layer . Therefore, even for a polarizing film in which a transparent protective film with UV absorbing energy is layered on both areas of the polarizer, the adhesive layer can be hardened. Of course, it is also possible to harden the adhesive layer for a polarizing film formed by laminating a transparent protective film that does not have UV absorbing energy. In addition, the so-called transparent protective film with UV absorption energy means a transparent protective film with a transmittance of less than 10% for 380nm light.

As a method of imparting UV absorbing energy to the transparent protective film, for example, a method of containing an ultraviolet absorber in the transparent protective film, and a method of containing a surface treatment layer of the ultraviolet absorber on the surface of the transparent protective film.

系化合物等。Specific examples of ultraviolet absorbers include, for example, well-known oxybenzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, and nickel aluminum compounds. Synthetic salt compounds, three acridine

Department of compounds and so on.

Regarding ultraviolet curability or visible light curability, it is preferable to heat the polarizing film adhesive composition before irradiating ultraviolet or visible light (heating before irradiation). In this case, it is better to heat to 40°C or higher. The temperature is preferably above 50°C. In addition, it is also suitable to heat the adhesive composition for polarizing film after irradiating ultraviolet rays or visible rays (heating after irradiation). In this case, it is better to heat to 40°C or higher, and to heat to 50°C or higher.

When the polarizing film of the present invention is manufactured on a continuous production line, the production line speed will depend on the curing time of the adhesive composition, but it is preferably 5-100m/min, and preferably 10-50m/min, 20-30m/min. min is better. When the production line speed is too low, it will lack productivity or cause excessive damage to the transparent protective film, making it impossible to produce a polarizing film that can withstand durability tests, etc. When the line speed is too high, the curing of the adhesive composition may be insufficient, and the desired adhesiveness may not be obtained in some cases.

In actual use, the polarizing film of the present invention can be used as an optical film laminated with other optical layers. The optical layer is not particularly limited, and one or more layers such as reflectors and semi-transmissive plates, retardation plates (including 1/2 and 1/4 wavelength plates), viewing angle compensation films, etc. can be used. An optical layer of a liquid crystal display device or the like is formed. Particularly preferred is a reflective polarizing film or semi-transmissive polarizing film formed by laminating a reflective plate or a semi-transmissive reflector on the polarizing film of the present invention, and an elliptical polarizing film formed by laminating a phase difference plate on the polarizing film Or a circular polarizing film, a wide viewing angle polarizing film formed by laminating a viewing angle compensation film on a polarizing film, or a polarizing film formed by laminating a brightness enhancement film on a polarizing film.

The optical film formed by laminating the above-mentioned optical layer on the polarizing film can also be formed in a sequential manner in the manufacturing process of liquid crystal display devices, etc., but the optical film is pre-laminated into an optical film in terms of quality stability and assembly operations. It is more advantageous and has the advantage of improving the manufacturing steps of liquid crystal display devices and the like. It can be laminated with an appropriate bonding method such as an adhesive layer. When the above-mentioned polarizing film and other optical films are bonded, the optical axis of the polarizing film and other optical films can be arranged at an appropriate angle according to the desired retardation characteristics.

On the aforementioned polarizing film or an optical film laminated with at least one layer of polarizing film, an adhesive layer for bonding with other components such as liquid crystal cells can also be provided. The adhesive forming the adhesive layer is not particularly limited. For example, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based can be appropriately selected and used. Such polymers as the base polymer. It is particularly preferable to use materials that have excellent optical transparency like acrylic adhesives, can exhibit adhesive properties such as moderate wettability, cohesiveness, and adhesion, and have excellent weather resistance and heat resistance.

The adhesive layer can be arranged on one side or both sides of the polarizing film and the optical film in the form of an overlapping layer of layers of different compositions or types. Moreover, when it is installed on both sides, the front and back of the polarizing film or the optical film can also be made into adhesive layers with different compositions, types, or thicknesses. The thickness of the adhesive layer can be appropriately determined according to the purpose of use and adhesion, etc., generally 1-100μm, preferably 5-30μm, especially 10-20μm.

The exposed surface of the adhesive layer can be temporarily attached and covered with a separator to prevent it from being contaminated before it is actually used. This prevents contact with the adhesive layer under normal operating conditions. As the separator, in addition to the above-mentioned thickness conditions, suitable articles according to conventional knowledge can be used, for example, plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, foam sheets or metal foils, and laminates of these can be used. Suitable sheet materials are coated with suitable release agents such as polysiloxane-based, long-chain alkane-based, fluorine-based, or molybdenum sulfide, etc., as required.

The polarizing film or optical film of the present invention can be suitably used in the formation of various devices such as liquid crystal display devices. The formation of the liquid crystal display device can be performed according to conventional knowledge. That is, the liquid crystal display device is generally formed by appropriately assembling the liquid crystal cell, the polarizing film or the optical film, and the component parts such as the lighting system according to the demand, and installing the driving circuit. In the present invention, in addition to the use of the polarizing film or The optical film is not particularly limited except for this point, and it can be based on conventional knowledge. Regarding the liquid crystal cell, any type such as TN type, STN type, and π type can be used.

It is possible to form a liquid crystal display device in which a polarizing film or an optical film is arranged on one side or both sides of a liquid crystal cell, or an appropriate liquid crystal display device using a backlight or a reflective plate as an illumination system. At this time, the polarizing film or optical film of the present invention can be arranged on one side or both sides of the liquid crystal cell. When polarizing films or optical films are arranged on both sides, they may be the same or different. In addition, when forming a liquid crystal display device, one layer or two or more layers such as diffuser, anti-glare layer, anti-reflection film, protective plate, ridge array, lens array sheet, light diffuser, and backlight can be arranged in an appropriate position. Wait for appropriate parts. Example

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

啉作為活性能量線硬化性成分，並使用0.5重量%之BYK公司製「BYK-UV3570」作為具有反應性基之氣泡抑制劑，使用3重量%之IRGACURE 907、2重量%之KAYACURE　DETX-S2作為聚合起始劑，攪拌3小時後獲得接著劑組成物A。(Preparation of curable resin composition) 54.5 wt% of 1,9-nonanediol diacrylate, 10 wt% of hydroxyethyl acrylamide, and 30 wt% of acrylamide are used

As a curable component of active energy rays, 0.5% by weight of BYK "BYK-UV3570" is used as a bubble inhibitor with a reactive group, and 3% by weight of IRGACURE 907 and 2% by weight of KAYACURE DETX-S2 are used as The polymerization initiator was stirred for 3 hours to obtain an adhesive composition A.

<Preparation of Polarizer> A 45 μm polyvinyl alcohol film with an average degree of polymerization of 2400 and a degree of saponification of 99.9 mol% was immersed in 30°C warm water for 60 seconds to swell it. Next, it was immersed in a 0.3% aqueous solution of iodine/potassium iodide (weight ratio=0.5/8), and the film was dyed while extending it to 3.5 times. Thereafter, stretching was performed in a borate aqueous solution at 65°C so that the total stretching ratio became 6 times. After stretching, drying was performed in an oven at 40°C for 3 minutes to obtain a polyvinyl alcohol-based polarizer X (thickness 18 μm).

<Production of thin polarizer> In order to produce a thin polarizer, first, a laminate formed by forming a 24μm thick PVA layer on an amorphous PET substrate is subjected to air-assisted stretching at a stretching temperature of 130°C to produce a stretched laminate Then, the colored laminate is formed by dyeing the stretched laminate, and the colored laminate is stretched integrally with the amorphous PET substrate by stretching in boric acid water at a stretching temperature of 65 degrees, so that the total stretch magnification becomes 5.94 After magnification, an optical thin film laminate including a 10 μm thick PVA layer was produced. An optical thin film laminate (total thickness 40 μm) including a PVA layer with a thickness of 5 μm for forming the thin polarizer Y can be produced. The PVA molecule of the optical thin film laminate is formed on the PVA layer of the amorphous PET substrate. The two-stage extension is highly aligned, and the iodine adsorbed by dyeing is highly aligned in one direction in the form of polyiodide ion complexes.

系紫外線吸收劑(艾迪科(ADEKA)公司製、商品名：T-712)0.62重量份，製作出樹脂顆粒。將所製得之樹脂顆粒在100.5kPa、100℃下乾燥12小時，再以單軸擠製機在塑模溫度270℃下從T型模擠出，成形為薄膜狀(厚度160μm)。並且於150℃的氣體環境下將該薄膜往其輸送方向延伸(厚度80μm)，接著塗佈含水性胺甲酸酯樹脂之易接著劑之後，於150℃的氣體環境下往與薄膜輸送方向正交之方向延伸，而製得厚度40μm(透濕度58g/m² /24h)之透明丙烯酸薄膜(Acryl)。 (ii)COP；使用厚度52μm之環狀聚烯烴薄膜(日本ZEON公司製)。 (iii)TAC；使用厚度60μm之三乙醯纖維素薄膜(富士軟片公司製)。<Transparent protective film> (i) Acryl; 100 parts by weight of the imidized MS resin described in Production Example 1 of Japanese Patent Laid-Open No. 2010-284840 was mixed with a biaxial kneader at 220°C and three acridines

0.62 parts by weight of an ultraviolet absorber (manufactured by ADEKA, trade name: T-712) to prepare resin pellets. The prepared resin pellets were dried at 100.5 kPa and 100°C for 12 hours, and then extruded from a T-die with a uniaxial extruder at a molding temperature of 270°C to be formed into a film (thickness 160 μm). And the film is stretched in the conveying direction (thickness 80μm) in a gas atmosphere at 150°C, and then coated with an easy-adhesive agent of water-containing urethane resin, and then in a gas environment at 150°C in the same direction as the film conveying direction. Extending in the opposite direction, a transparent acrylic film (Acryl) with a thickness of 40 μm (water permeability of 58 g/m ^{2 /24h) was prepared.} (ii) COP: A cyclic polyolefin film with a thickness of 52 μm (manufactured by ZEON, Japan) is used. (iii) TAC: A 60 μm thick triacetyl cellulose film (manufactured by Fuji Film Co., Ltd.) was used.

<Peeling force> The polarizing film is cut out to a size of 200 mm parallel to the extending direction of the polarizer and 15 mm in the straight direction, and the polarizing film is bonded to the glass plate. Next, make a cut mark between the transparent protective film (the first protective film or the second protective film) and the polarizer with a cutter, and use the Tensilon testing machine to move the protective film and the polarizer at a peeling speed of 300mm/min to 90 degrees Peel off in the direction and measure the peel strength (N/15mm).

<Bubble before lamination> Take the sample immediately after applying the adhesive, observe both sides with an optical microscope, and count the number of bubbles. Calculate the number of bubbles in the range of 5cm×5cm, and confirm the total number of bubbles on the coated surface.

<Layered bubbles> Observe the two sides of the polarizing film with an optical microscope and count the number of bubbles. Calculate the number of bubbles in the range of 5cm×5cm, and confirm the total number of bubbles on both sides.

<Surface tension> It was measured by the hanging drop method using Drop Master (Kyowa Interface Science Co., Ltd.).

Example 1 Using an MCD coater (manufactured by Fuji Machinery Co., Ltd.) (mesh shape: honeycomb, gravure roll line number: 1000 lines/inch, rotation speed 180%/pair line speed), the first protective film (Acryl ) And the second protective film (COP) were coated with the adhesive composition A so as to have a thickness of 0.5 μm, and were bonded to both sides of the polarizer X using a roll press. After that, the above-mentioned visible light is irradiated on both sides with an active energy ray irradiation device from the side (both sides) of the laminated transparent protective film to harden the hardening type adhesive, and then it is dried in hot air at 70°C for 3 minutes to obtain Polarizing films with transparent protective films on both sides of the polarizer. The speed of the lamination production line is 25m/min.

Example 2 Adhesive composition B was used, except for the adhesive composition A used in Example 1 that the bubble inhibitor with a reactive group was changed to 0.5% by weight of BYK company "BYK-UV3505", the rest For the same composition.

Comparative Example 1 The evaluation was carried out in the same manner as in Example 1 except that the adhesive composition C was changed. The aforementioned adhesive composition C was composed of the adhesive composition A except for the BYK company "BYK-UV3570" , And the rest are of the same composition. Comparative Example 2 Adhesive composition D was used, except that for the adhesive composition A used in Example 1, the bubble inhibitor with a reactive group was changed to 0.5% by weight of a polyether modified polymer without a reactive group. Except for the "401LS Additive" of the silica-based bubble inhibitor, the rest have the same composition.

Example 3 Evaluation was performed in the same manner as in Example 1, except that TAC was used as the first protective film.

Comparative Example 3 The evaluation was performed in the same manner as in Example 3 except that the adhesive composition C was used instead of the adhesive composition A.

Example 4, Comparative Example 4 Except that each adhesive composition described in Table 1 was used instead of the adhesive composition A, a thin polarizer Y was used instead of the polarizer X, and the polarizing film manufactured by the following method was used, the implementation was followed Example 1 was evaluated in the same way.

Each of the adhesive compositions described in Table 1 was coated on the surface of the thin polarizer Y including the optical film laminate of the thin polarizer Y, and the first protective film was laminated, followed by drying at 50°C for 5 minutes. Next, after peeling off the amorphous PET substrate, each adhesive composition described in Table 1 was applied to the peeling surface, and the second protective film was laminated and then cured by ultraviolet rays to produce a thin type. Polarizing film of polarizer Y.

Example 5 and Comparative Example 5 The evaluation was performed in the same manner as in Example 1, except that each adhesive composition described in Table 1 was used instead of the adhesive composition A.

[Table 1]

林，興人公司製「ACMO」、 羥基三甲基乙酸新戊二醇丙烯酸酯加成物，共榮社化學公司製「LIGHT ACRYLATE HPP-A」、 2-羥-3-苯氧丙基丙烯酸酯，東亞合成公司製「M5700」、 雙酚A型環氧樹脂，商品名「jER-828」，Japan Epoxy Resins公司製、 3-乙基-3-苯氧甲基氧雜環丁烷，商品名「ARON OXETANE OXT-211」，東亞合成公司製； 具有反應性基之氣泡抑制劑為： 具有丙烯醯官能基之改質聚二甲基矽氧烷之聚矽氧系氣泡抑制劑(含有胺甲酸酯鍵及三聚異氰酸酯環結構)，BYK公司製「BYK-UV3505」、 具有丙烯醯官能基之聚酯改質聚二甲基矽氧烷之聚矽氧系氣泡抑制劑(含有胺甲酸酯鍵及三聚異氰酸酯環結構)，BYK公司製「BYK-UV3570」； 不具有反應性基之氣泡抑制劑為： 聚醚改質聚矽氧系氣泡抑制劑，Dow Cornin Toray公司製「401LS Additive」； 聚合起始劑為： IRGACURE 907，BASF公司製、 KAYACURE DETX-S，日本化藥公司製、 以六氟磷酸三芳基鋶鹽作為主成分的有效成分50%之碳酸伸丙酯溶液，商品名「UVI-6992」，陶氏化學公司製。In Table 1, the active energy ray curable components are: 1,9-nonanediol diacrylate, "LIGHT ACRYLATE 1.9ND-A" manufactured by Kyoeisha Chemical Co., Ltd., and hydroxyethyl acrylamide, manufactured by Hingren Co., Ltd. HEAA", acrylic

Lin, "ACMO" made by Xingren Company, hydroxytrimethylacetate neopentyl glycol acrylate adduct, "LIGHT ACRYLATE HPP-A" made by Kyoeisha Chemical Company, 2-hydroxy-3-phenoxypropyl acrylic acid Ester, "M5700" manufactured by Toagosei Co., Ltd., bisphenol A epoxy resin, trade name "jER-828", manufactured by Japan Epoxy Resins, 3-ethyl-3-phenoxymethyloxetane, product The name "ARON OXETANE OXT-211", manufactured by Toagosei Co., Ltd.; The bubble inhibitor with a reactive group is: Polysiloxane-based bubble inhibitor of modified polydimethylsiloxane with acrylic functional group (containing amine Formate bond and triisocyanate ring structure), BYK "BYK-UV3505" made by BYK, a polysiloxane-based air bubble inhibitor (containing urethane Acid ester bond and triisocyanate ring structure), BYK company "BYK-UV3570"; bubble inhibitor without reactive group: polyether modified polysiloxane bubble inhibitor, Dow Cornin Toray company "401LS"Additive"; the polymerization initiator is: IRGACURE 907, manufactured by BASF Corporation, KAYACURE DETX-S, manufactured by Nippon Kayaku Co., a 50% propylene carbonate solution of active ingredient with triarylsulfonium hexafluorophosphate as the main component, Trade name "UVI-6992", manufactured by The Dow Chemical Company.

Examples 6 to 18 For the composition B used in Example 2, the content y (weight %) of the bubble inhibitor contained in the adhesive layer was changed to that described in Table 2, and the thickness d ( μm) was changed to those described in Table 2, except that it was evaluated in the same manner as in Example 2.

[Table 2]

Claims (12)

A polarizing film, characterized in that a transparent protective film is laminated on at least one surface of a polarizing member through an adhesive composition obtained by curing an adhesive composition for a polarizing film, and the adhesive composition for a polarizing film contains active energy ray hardening Sexual components and bubble inhibitors with reactive groups. The polarizing film of claim 1, wherein the aforementioned bubble inhibitor is a silicone-based bubble inhibitor having a reactive group. The polarizing film according to claim 1, wherein the aforementioned bubble inhibitor has a (meth)acrylic acid group as a reactive group. The polarizing film of claim 1, wherein the aforementioned bubble inhibitor has a urethane bond. The polarizing film of claim 1, wherein the aforementioned bubble inhibitor has a trimeric isocyanate ring structure. Such as the polarizing film of claim 1, wherein when the total amount of the composition is 100% by weight, the content of the aforementioned bubble inhibitor is 0.01 to 0.6% by weight. The polarizing film of claim 1, wherein the surface tension of the aforementioned composition before curing is 30 mN/m or less. The polarizing film of claim 1, wherein the composition contains at least a radical polymerizable compound as the active energy ray curable component. The polarizing film according to any one of claims 1 to 8, wherein the thickness of the aforementioned adhesive layer is 0.2 to 3 μm. Such as the polarizing film of any one of claims 1 to 8, which is When the thickness of the adhesive layer is d (μm) and the content of the bubble inhibitor contained in the adhesive layer is y (wt%), the following formula (1) is satisfied: 0.1-0.02d≦y≦ 0.6-0.08d (1). An optical film characterized in that at least one layer of polarizing film as claimed in any one of claims 1 to 10 is laminated. An image display device, characterized in that the polarizing film according to any one of claims 1 to 10 or the optical film according to claim 11 is used.