TW201710422A - Curable adhesive composition for polarizing film, polarizing film, manufacturing method for said polarizing film, optical film, and image display device - Google Patents

Abstract

Provided is a curable adhesive composition for a polarizing film that is for adhering a transparent protective film to at least one surface of a polarizer, said curable adhesive composition for a polarizing film containing: an active energy ray curable component; and an alkoxysilane group-containing compound that has a viscosity of at least 15 mPa?s.

Description

Curable adhesive composition for polarizing film, polarizing film, manufacturing method thereof, optical film, and image display device Field of invention

The present invention relates to a hardenable adhesive composition for a polarizing film for forming the above-mentioned adhesive layer in a polarizing film in which a polarizer and a transparent protective film are laminated through an adhesive layer. Further, the present invention relates to a polarizing film using the above adhesive layer. The polarizing film can be used alone or as an optical film to form an image display device such as a liquid crystal display (LCD), an organic EL display device, a CRT or a PDP.

Background of the invention

In watches, mobile phones, PDAs, notebook personal computers, personal computer monitors, digital video players (DVD players), TVs, etc., liquid crystal display devices are rapidly expanding. The liquid crystal display device is capable of visualizing the polarization state by switching the liquid crystal, and a polarizer is used for the display principle. Especially in the use of TV, etc., it is required to have higher brightness, high contrast, and wide viewing angle. In polarizing films, higher and higher transmittance, high polarization, higher color reproducibility, etc. are required. .

The polarizing material has a high transmittance and a high degree of polarization. For example, an iodine-based polarizer having a structure in which polyvinyl alcohol (hereinafter, also simply referred to as "PVA") is adsorbed and extended is generally used most widely. . Usually biased In the optical film, a so-called water-based adhesive which is obtained by dissolving a polyvinyl alcohol-based material in water is used, and a transparent protective film is bonded to both surfaces of a polarizer (Patent Document 1 below). As the transparent protective film, cellulose triacetate or the like having a high moisture permeability can be used. When the water-based adhesive is used (so-called wet lamination method), after the polarizer is bonded to the transparent protective film, a drying step is necessary.

On the other hand, it has been proposed to use an active energy ray-curable adhesive instead of the above-mentioned water-based adhesive. When a polarizing film is produced using an active energy ray-curable adhesive, since the drying step is not required, the productivity of the polarizing film can be improved. For example, it has been proposed to disclose a radical polymerization type active energy ray-curable adhesive composition using an N-substituted quinone imine monomer as a curable component (Patent Document 2 below). Such an adhesive composition exhibits excellent durability in a severe environment under high humidity and high temperature, but in the market, the actual situation is gradually required to further improve adhesion and/or water resistance. Agent composition.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2006-220732

Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-287207

Summary of invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a cured adhesive composition for a polarizing film, which is related to a polarizing member and The transparent protective film has good adhesion and forms an adhesive layer having excellent water resistance even under severe conditions such as a dew condensation environment.

Moreover, an object of the present invention is to provide a polarizing film which is formed by using an adhesive layer formed of a cured adhesive composition for a polarizing film and a transparent protective film on a polarizing member; An optical film of the polarizing film; and an image display device using the polarizing film or the optical film.

In order to solve the above problems, the inventors of the present invention have found that the above object can be attained by using the following cured composition for a polarizing film, and the present invention has been completed.

That is, the present invention relates to a hardenable adhesive composition for a polarizing film, which is used for adhering a transparent protective film to at least one side of a polarizing member, characterized by containing an active energy ray hardening component and having a viscosity of 15 mPa. . Alkoxyalkylene-containing compounds above s.

In the cured adhesive composition for a polarizing film, the main chain of the alkoxyalkyl group-containing compound is preferably an acrylic polymer structure.

The curable adhesive composition for a polarizing film preferably further contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal nips.

In the hardenable adhesive composition for a polarizing film, the metal of the organometallic compound is preferably titanium.

The hardenable adhesive composition for a polarizing film preferably contains the metal alkoxide as the organometallic compound, and the metal The number of carbon atoms of the organic group of the alkoxide is preferably 4 or more, and it is preferable to contain the metal conjugate as the organometallic compound, and the metal conjugate has an organic group having a carbon number of 4 or more. .

In the cured adhesive composition for a polarizing film, when the total amount of the active energy ray-curable components is 100 parts by weight, the ratio of the organometallic compound is preferably 0.05 to 9 parts by weight.

In the cured adhesive composition for a polarizing film, the cured product obtained by curing the curable adhesive composition is immersed in pure water at 23 ° C for 24 hours, and the overall water absorption ratio represented by the following formula is preferably 10% by weight or less; {(M2-M1)/M1}×100 (%)

However, M1: the weight of the cured product before impregnation, and M2: the weight of the cured product after the impregnation.

In the cured adhesive composition for a polarizing film, the active energy ray-curable component preferably contains a radical polymerizable compound, and the radical polymerizable compound preferably contains a (meth) acrylamide derivative; The base polymerizable compound preferably contains a polyfunctional compound having at least two radically polymerizable functional groups.

The curable adhesive composition for a polarizing film preferably further contains a photopolymerization initiator, and further preferably contains a compound having a vinyl ether group, and more preferably contains a photoacid generator.

In the cured adhesive composition for a polarizing film, the cured elastic modulus of the cured product obtained by curing the curable adhesive composition at 25 ° C is preferably 1 × 10 ⁷ Pa or more.

Furthermore, the present invention relates to a polarizing film which is provided with a transparent protective film on at least one surface of a polarizer through an adhesive layer, wherein the adhesive layer is one of the claims 1 to 11 The polarizing film is formed of a cured layer of a hardenable adhesive composition. The thickness of the above adhesive layer is preferably 0.1 to 3 μm . Further, after the adhesive layer is immersed in pure water at 23 ° C for 24 hours, the overall water absorption ratio represented by the following formula is preferably 10% by weight or less, and the storage elastic modulus of the above-mentioned adhesive layer at 25 ° C is 1.0 × 10 ⁷ Pa or more is preferred; formula: {(M2-M1)/M1}×100 (%)

However, M1: the weight of the cured product before impregnation, and M2: the weight of the cured product after the impregnation.

Moreover, the present invention relates to a method for producing a polarizing film, which comprises the step of applying a curing adhesive composition for a polarizing film to the aforementioned method. a polarizing member and at least one surface of the transparent protective film; a bonding step of bonding the polarizing member to the transparent protective film; and a step of: adhering the polarizing member and the transparent protective film through an adhesive layer, wherein the adhesive The layer is obtained by curing the active energy ray-curable adhesive composition by irradiating an active energy ray from the surface of the polarizer or the surface of the transparent protective film.

Furthermore, the present invention relates to an optical film characterized in that at least one of the above-described polarizing films is laminated; and the present invention further relates to an image display device characterized in that the polarizing film described above or the optical body described above is used. film.

When the polarizing film in which the transparent protective film is laminated on the polarizer through the adhesive layer is exposed to the dew condensation environment, a mechanism for causing subsequent peeling between the adhesive layer and the polarizing member can be presumed as follows. First, moisture that penetrates the protective film diffuses in the adhesive layer and the moisture diffuses to the polarizer interface side. Here, in the conventional polarizing film, hydrogen bonding and/or ionic bonding contributes a large degree to the adhesion force between the adhesive layer and the polarizing member, but hydrogen is caused at the interface due to moisture diffused to the interface side of the polarizing member. The bond and the ionic bond dissociate, resulting in a low adhesion force between the adhesive layer and the polarizer. Therefore, in the dew condensation environment, there is a case where peeling occurs between the adhesive layer and the polarizing member.

On the other hand, the hardening type adhesive composition for a polarizing film of the present invention contains a viscosity of 15 mPa. Alkoxyalkylene-containing compounds above s. Therefore, even when the moisture penetrates the protective film and the moisture diffuses to the adhesive layer, the alkoxyalkyl group of the compound at the interface between the polarizer and the adhesive layer becomes a stanol group due to the inclusion of moisture, and A functional group such as a hydroxyl group or a carboxyl group present on the surface of the polarizer forms a covalent bond. Further, the alkoxyalkylene group-containing compound used in the present invention maintains fluidity in the pre-polymerization stage of the adhesive composition while polymerizing the binder composition and the alkoxylated alkane in the middle of the polymerization of the composition. The base compound produces moderate incompatibility with a viscosity of 15 mPa. Since s or higher (high molecular weight), the alkoxyalkyl group-containing compound having a low viscosity (low molecular weight) tends to be more likely to be deposited at the interface of the substrate. Therefore, even if the amount of the setting is set to be low, the viscosity is 15 mPa. The alkoxyalkyl group-containing compound above s is biased on the surface side of the polarizer, and more hydrogen bonds are formed between the polarizer and the adhesive layer. And / or ionic bonds, and the formation of covalent bonds, so that the subsequent water resistance between the polarizer and the adhesive layer is dramatically increased.

Further, there is a technique of disposing a decane coupling agent in an adhesive composition for forming an adhesive layer for laminating a liquid crystal cell and a polarizing film, for example, in a hardener-type adhesive composition for a polarizing film according to the present invention. . However, in general, an adhesive composition is applied to a substrate such as a release film to form an adhesive layer, and then transferred to a polarizing film, so that the decane coupling agent is not in the adhesive layer as in the present invention. It is more difficult to think that the decane coupling agent will be biased on the side of the polarizer. Therefore, even if the adhesive layer is disposed in contact with the polarizing member, the adhesion between the polarizing member and the adhesive layer is not so high.

Further, the curable adhesive composition for a polarizing film of the present invention contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal nips, and between the polarizer and the adhesive layer. The subsequent water resistance is particularly leaping. This reason can be estimated as follows. When the binder composition constituting the adhesive layer contains an organometallic compound, the water is diffused in the adhesive layer, and the organometallic compound becomes an active metal species due to inclusion of moisture, and as a result, the organometallic compound and the polarizing member and the binder are formed. The active energy ray-hardening component of the layer interacts strongly. Thereby, even if moisture is present at the interface between the polarizer and the adhesive layer, the solid metal compound strongly interacts with each other, so that the subsequent water resistance between the polarizer and the adhesive layer is particularly drastically improved.

The cured adhesive composition for a polarizing film of the present invention has an overall water absorption of the cured product obtained by curing the curable adhesive composition. The rate is preferably 10% by weight or less. The overall water absorption rate shows that the adhesive layer formed of the hardened adhesive composition for a polarizing film of the present invention has a very low water absorbency when the adhesive layer is formed. Therefore, the polarizing film formed by providing the transparent protective film on the polarizer through the adhesive layer composed of the cured layer has good adhesion between the polarizer and the transparent protective film layer, and can satisfy the high temperature at a higher level. Optical durability in harsh environments under wet conditions.

For example, a polarizing film having a cured layer (adhesive layer) formed using the cured adhesive composition for a polarizing film of the present invention, even in a severe humidifying environment (for example, 85 ° C × 85% RH) Optical durability (humidification durability test) was also good. Therefore, even when the polarizing film of the present invention is placed in the above-described severe humidification environment, the transmittance and the degree of polarization of the polarizing film can be reduced (changed) to be small. Moreover, the polarizing film of the present invention can suppress the decrease in the adhesion force even in a harsh environment in which it is immersed in water, and can be used between the polarizing member and the transparent protective film even under the strict contact with water. The reduction in the adhesion force (between the polarizer and the adhesive layer) is suppressed to be small.

Form for implementing the invention

The composition for a hardening type adhesive for a polarizing film of the present invention comprises an active energy ray curable component and a viscosity of 15 mPa. Alkoxyalkylene-containing compounds above s.

<The viscosity is 15mPa. Alkoxyalkylene-containing compounds above s >

As the viscosity in the present invention is 15mPa. The alkoxyalkylene group-containing compound above s can use a higher molecular weight compound than the alkoxyalkyl group-containing low molecular weight compound, and particularly can be suitably used to contain an alkoxyalkyl group at a side chain and/or a molecular end. A polymer, or oligomer-type alkoxyalkylene-containing compound.

As the polymer containing an alkoxyalkyl group at the side chain and/or the molecular end, a structure in which the main chain is a (meth)acrylic polymer structure can be suitably used. Examples of the (meth)acrylic monomer constituting the acrylic polymer include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate. , (meth)acrylic acid isopropyl, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, (methyl) ) n-Hexyl acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate Dicyclopentyl ester, dodecyl (meth)acrylate, phenyl (meth)acrylate, methyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxy (meth)acrylate Ethyl ester, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearate (meth)acrylate, (A) Acrylic isostearic acid Other (meth) acrylate. In the present invention, the term "(meth)acryl fluorenyl" means acryl fluorenyl and/or methacryl fluorenyl, "(methyl)" The same meaning is as follows.

The viscosity of the polymer containing an alkoxyalkyl group at the side chain and / or molecular end is 15mPa. Above s, preferably 10000 mPa. Above s, more preferably 100000mPa. s above. The upper limit of the viscosity is not particularly limited, and when considering workability, etc., it is 2,000,000 mPa. The following is better.

The oligomer-type alkoxyalkylene group-containing compound may, for example, be a hydrolysis condensate of a low molecular weight alkoxyalkylene group-containing compound. As a hydrolysis condensate of a low molecular weight alkoxyalkyl group-containing compound, a commercially available product can also be used, and, for example, X-41-1059A, X-24-9590, KR- manufactured by Shin-Etsu Chemical Co., Ltd. 516, X-41-1805, KR513, X-40-9296, KR-511, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40- 9227, KR-510, KR-9218, KR-213, etc.

The oligomer-type alkoxyalkyl-containing compound has a viscosity of 15 mPa. Above s, preferably 20 mPa. Above s, more preferably 25mPa. s above. The upper limit of the viscosity is not particularly limited, and when considering workability, etc., it is 100000 mPa. The following is better.

In the present invention, the viscosity is 15 mPa with respect to 100 parts by weight of the total amount of the active energy ray hardening component. The content of the alkoxyalkyl group-containing compound of s or more is preferably in the range of 0.2 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 0.8 to 5 parts by weight. When the amount is more than 15 parts by weight, the storage stability of the adhesive composition is deteriorated, or the ratio of the components to be used in combination with the polarizer and the protective film is relatively insufficient and the adhesion is lowered. Moreover, when it is less than 0.2 part by weight, the effect of water resistance is not followed. The law is fully exploited.

The curable adhesive composition for a polarizing film of the present invention preferably contains an active energy ray-curable component, and further contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal nips. .

<selected from at least one organometallic compound in the group consisting of metal alkoxides and metal nips>

A metal alkoxide is a compound in which at least one or more organic alkoxy groups are bonded to a metal, and the metal conjugate is a compound in which an organic group is bonded or coordinated to a metal through an oxygen atom. As the metal, titanium, aluminum, and zirconium are preferred. Among them, compared with titanium, the reactivity of aluminum and zirconium is relatively rapid, and the pot life of the adhesive composition becomes short, and the effect of improving the water resistance becomes low. Therefore, from the viewpoint of improving the subsequent water resistance of the adhesive layer, titanium is preferable as the metal of the organometallic compound.

When the hardenable adhesive composition for a polarizing film of the present invention contains a metal alkoxide as the organometallic compound, it is preferred to use a metal alkoxide having an organic carbon number of 4 or more, and a carbon number of 6 or more. good. When the carbon number is 3 or less, the pot life of the adhesive composition becomes short, and the effect of improving the water resistance is lowered. As the organic group having 6 or more carbon atoms, for example, an octyloxy group can be suitably used. Examples of suitable metal alkoxides include tetraisopropyl phthalate, tetrabutyl phthalate, butyl phthalate dimer, tetraoctyl phthalate, third amyl citrate, and tetrad. Tributyl phthalate, citric acid tetrastearate, zirconium tetraisopropoxide, tetra-n-butyl zirconia, tetra-octyl zirconia, tetra-butadiene zirconia, tetra-propoxide zirconia, second-butyric acid, Aluminum acetate, aluminum isopropylate, aluminum butyrate, diisopropyl acid-second aluminum butyrate, diisobutyric acid-second butoxide aluminum, and the like. In particular, tetraoctyl phthalate is preferred.

When the hardening type adhesive composition for a polarizing film of the present invention contains a metal tongs as the organometallic compound, it is preferred that the number of carbon atoms of the organic group contained in the metal conjugate is 4 or more. When the carbon number is 3 or less, the pot life of the adhesive composition becomes short, and the effect of improving the water resistance is lowered. Examples of the organic group having 4 or more carbon atoms include an acetoacetate group, an ethyl acetoacetate group, an isostearate group, and an octylene glycolate group. Among these, from the viewpoint of improving the subsequent water resistance of the adhesive layer, an acetoacetate group or an ethyl acetoacetate group is preferably used as the organic group. Examples of suitable metal tongs include, for example, titanium acetylacetonate, titanium octoate, titanium tetraacetone, titanium ethyl acetoacetate, polyhydroxy titanium stearate, and dipropoxy group. - bis(acetonitrile) titanium, bis(octylene glycol) dibutoxide titanium, bis(ethylacetamidineacetic acid) dipropoxide titanium, titanium propoxide, titanium diethanolamine, titanium triethanolamine, double (propanol) titanium dipropoxide, titanium bis(triethanolamine) dipropoxide, bis(triethanolamine) di-n-butoxy titanium, tri-n-butoxytitanium stearate, diisopropyl Oxygen. Bis(ethylacetamidine acetate) titanium, diisopropoxy. Bis(acetate acetate) titanium, diisopropoxy. Bis(acetonitrile) titanium, titanium phosphate compound, titanium ammonium propionate, titanium 1,3-propane dioxybis(ethylacetate), titanium dodecylbenzenesulfonate, amine ethylamine B Keto-titanium, tetraethylguanidinium acetone, zirconium acetonide, zirconium acetonide, zirconium acetonide, zirconium acetate, zirconium acetate, tri-n-butoxyethyl acetoacetate Zirconium, zirconium di-n-butoxy bis(ethylacetamidineacetic acid), zirconium n-butoxy oxyethylene (ethyl acetoacetate), zirconium ruthenium (n-propyl acetonitrile), ruthenium Ethylene acetate) zirconium, lanthanum (ethyl acetoacetate) zirconium, ethyl acetoacetate aluminum, acetoacetate aluminum, bisethyl acetamidine acetate acetoacetate aluminum, diisopropoxyethyl hydrazine Aluminum acetate, aluminum diisopropoxyacetam, aluminum isopropyl bis(ethyl acetonitrile), aluminum isopropyl acetophenone, aluminum ginseng (ethyl ethyl acetonitrile), ginseng (Acetylacetone) aluminum, ethyl acetonide. Bis(ethylacetamidineacetic acid) aluminum. In particular, titanium acetonate or titanium ethyl acetate is preferred.

Examples of the organometallic compound which can be used in the present invention include an organic carboxylic acid metal salt such as zinc octylate, zinc laurate, zinc stearate or tin octylate, zinc acetonitrile citrate, and benzene. A zinc tong compound such as a zinc thioglycolate tongs, a zinc benzoate methane nip, a acetonitrile ethyl acetate, or the like.

In the present invention, the content ratio of the organometallic compound is preferably in the range of 0.05 to 9 parts by weight, preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the total amount of the active energy ray-curable component. 5 parts by weight is more preferred. When the amount is more than 9 parts by weight, there is a possibility that the storage stability of the adhesive composition is deteriorated, or the ratio of the component to be used in combination with the polarizer and the protective film is relatively insufficient and the adhesion is lowered. Moreover, when it is less than 0.05 part by weight, the effect of the subsequent water resistance cannot be sufficiently exhibited.

<hardenable ingredients>

The curable adhesive composition for a polarizing film of the present invention contains an active energy ray-curable component as a curable component.

As the curable component, an active energy ray-curing type such as an electron beam curing type, an ultraviolet curing type, or a visible light curing type can be suitably used. Moreover, an ultraviolet curing type, visible light curing type adhesive composition, The composition can be classified into a radical polymerization hardening type adhesive composition and a cationic polymerization type adhesive composition. In the present invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is described as ultraviolet rays, and an active energy ray having a wavelength range of 380 nm to 800 nm is described as visible light.

<1: Radical polymerization hardening type adhesive composition>

As the curable component, for example, a radical polymerizable compound used in a radical polymerization-curable adhesive composition can be mentioned. The radically polymerizable compound may be a compound having a radical polymerizable functional group having a carbon-carbon double bond such as a (meth)acryl fluorenyl group or a vinyl group. Any of the curable components may be any of a monofunctional radical polymerizable compound or a difunctional or higher polyfunctional radical polymerizable compound. In addition, these radically polymerizable compounds can be used singly or in combination of two or more. As such a radically polymerizable compound, for example, a compound having a (meth) acrylonitrile group is preferred. In the present invention, the term "(meth)acryl fluorenyl group means acryl fluorenyl group and/or methacryl fluorenyl group, and "(meth)" is the same meaning as follows.

Monofunctional free radical polymerizable compound

The monofunctional radically polymerizable compound may, for example, be a (meth) acrylamide derivative having a (meth) acrylamide group. The (meth)acrylamide derivative is preferred in terms of ensuring adhesion to the polarizer and various transparent protective films, and in terms of rapid polymerization rate and excellent productivity. Specific examples of the (meth) acrylamide derivative include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-di. Ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (methyl) propyl N-alkyl-containing (meth) acrylamide derivatives such as decylamine and N-hexyl (meth) acrylamide; N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl ( N-hydroxyalkyl-containing (meth) acrylamide derivative such as methyl acrylamide or N-methylol-N-propane (meth) acrylamide; amine methyl (meth) propylene oxime N-aminoalkyl-containing (meth) acrylamide derivatives such as amines, amine ethyl (meth) acrylamides, etc.; N-methoxymethyl acrylamide, N-ethoxymethyl propylene oxime N-alkoxy-containing (meth) acrylamide derivatives such as amines; N-hydrogen sulfides such as mercaptomethyl (meth) acrylamide, thioethyl (meth) acrylamide A (meth) acrylamide derivative of an alkyl group or the like. In addition, examples of the (meth) acrylamide derivative containing a hetero ring which forms a hetero ring as a nitrogen atom of a (meth) acrylamide group include N-propenyl morpholine and N-propenyl sulfhydryl. Pyridine, N-methylpropenylpiperidine, N-propenylpyrrolidine, and the like.

Among the above (meth) acrylamide derivatives, in terms of adhesion to a polarizer and various transparent protective films, a N-hydroxyalkyl group-containing (meth) acrylamide derivative is preferred. N-hydroxyethyl (meth) acrylamide is preferred.

In addition, examples of the monofunctional radically polymerizable compound include various (meth)acrylic acid derivatives having a (meth)acrylenyloxy group. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and 2-methyl (meth)acrylate. Benzyl-2-nitropropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, (methyl) ) n-amyl acrylate, third amyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-dimethylbutyl (meth)acrylate, n-hexyl (meth)acrylate, ( Methyl)cetyl cetyl ester, n-octyl (meth)acrylate, (A) (meth)acrylic acid (carbon number 1-20) such as 2-ethylhexyl acrylate, 4-methyl-2-propylamyl (meth)acrylate, or n-octadecyl (meth)acrylate Alkyl esters.

In addition, examples of the (meth)acrylic acid derivative include a cycloalkyl (meth)acrylate and a cycloalkyl (meth)acrylate such as cyclopentyl (meth)acrylate; (meth)acrylic acid; Aralkyl ester of (meth)acrylate such as benzyl ester; 2-isodecyl (meth)acrylate, 2-norbornyl (meth)acrylate, 5-northene-2-(meth)acrylate Base-methyl ester, 3-methyl-2-northyl methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (A) Polycyclic (meth) acrylate such as dicyclopentanyl acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylate 2-methoxymethoxyethyl ester, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, alkyl benzene An alkoxy group or a phenoxy group-containing (meth) acrylate such as oxypolyethylene glycol (meth) acrylate.

Further, examples of the (meth)acrylic acid derivative include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxyl (meth) acrylate a hydroxyalkyl (meth) acrylate such as decyl ester or 12-hydroxylauryl (meth)acrylate; [4(hydroxymethyl)cyclohexyl]methyl acrylate, cyclohexanedimethanol mono(meth) acrylate a hydroxyl group-containing (meth) acrylate such as 2-hydroxy-3-phenoxypropyl (meth)acrylate; a glycidyl (meth)acrylate; a 4-hydroxybutyl ester (meth)acrylate epoxy Epoxy-containing (meth) acrylate; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate , hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, etc. (meth) acrylate; alkylaminoalkyl (meth) acrylate such as dimethylaminoethyl methacrylate; 3-oxetanyl methyl (meth) acrylate, (a) 3-methyl-oxetanyl methyl acrylate, 3-ethyl-oxetanyl methyl (meth)acrylate, 3-butyl-oxetan (meth)acrylate An oxetane-containing (meth) acrylate such as an alkyl methyl ester or a 3-hexyl-oxetanyl methyl (meth)acrylate; (tetra) methacrylate (methyl) acrylate (meth) acrylate having a heterocyclic ring such as butyl lactone; and a hydroxytrimethylacetic acid neopentyl glycol (meth)acrylic acid adduct, p-phenylphenol acrylate (meth)acrylate, and the like.

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

Further, examples of the monofunctional radically polymerizable compound include an indoleamine-based vinyl group such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone. Monomer; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, etc. A vinyl monomer such as a ring.

As a monofunctional radically polymerizable compound, it can be used A radically polymerizable compound of an active methylene group. The radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth)acrylonyl group at the terminal or molecule and having an active methylene group. Examples of the active methylene group include an ethyl acetonitrile group, an alkoxy propylene group, or a cyanoethenyl group. The aforementioned active methylene group is preferably an ethyl acetonitrile group. Specific examples of the radically polymerizable compound having an active methylene group include 2-ethyl acetoxyethyl (meth) acrylate and 2-ethyl ethoxy ethoxy propyl (meth) acrylate. Ethyl ethoxide (meth) acrylate such as 2-ethyl acetoxy-1-methylethyl (meth)acrylate; 2-ethoxy propyl (meth) acrylate Ethoxyethyl ester, 2-cyanoethoxyethyl (meth)acrylate, N-(2-cyanoethoxy)ethyl decylamine, N-(2-propenyl hydrazide Oxybutyl) acrylamide, N-(4-acetamethyleneoxymethylbenzyl) acrylamide, N-(2-acetamidoethyl) acrylamide, and the like. The radically polymerizable compound having an active methylene group is preferably acetoxyethyl (meth)acrylate.

Polyfunctional free radical polymerizable compound

In addition, examples of the difunctional or higher polyfunctional radically polymerizable compound include N,N'-methylenebis(meth)acrylamide and tripropylene glycol of a polyfunctional (meth)acrylamide derivative. 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 addition Di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A diglycidyl di(meth) propylene Acid ester, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, cyclic trimethylolpropane methylal (meth) acrylate, dioxane Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Esterified product of (meth)acrylic acid and polyhydric alcohol such as penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified diglycerol tetra(meth)acrylate, 9,9- Bis[4-(2-(methyl)acryloxyethoxyethoxy)phenyl]indole. As a specific example, 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.), and the like are preferred. Further, various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are exemplified as necessary. In addition, since the polyfunctional (meth) acrylamide derivative is not only rapid in polymerization rate but also excellent in productivity, and has excellent crosslinkability when the resin composition is cured, it is contained in curability. The resin composition is preferred.

The radical polymerizable compound is preferably a polyfunctional radical polymerizable compound in terms of controlling the water absorption of the cured product and satisfying the optical durability of the polarizing film in a severe humidifying environment. Among the above polyfunctional radically polymerizable compounds, those having a higher log Pow value to be described later are preferred.

The sin of the hardening type adhesive composition for a polarizing film of the present invention The alcohol/water partition coefficient (hereinafter referred to as the logPow value) is preferably the higher. The logPow value is an index indicating the lipophilicity of a substance and means the logarithm of the partition coefficient of octanol/water. A higher logPow means lipophilicity, which means lower water absorption. The logPow value can also be measured (the flask shake method described in JIS-Z-7260), but can also be calculated by calculation. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridgesoft is used. Further, the logPow value of the adhesive composition can be calculated according to the following formula.

The log composition of the subsequent composition is logPow=Σ(logPowi×Wi)

logPowi: logPow value of each component of the composition

Wi: (the number of moles of the i component) / (the total number of moles of the composition of the adhesive)

The logPow value of the curable adhesive composition of the present invention is 1 or more, preferably 2 or more, and most preferably 3 or more.

Examples of the radically polymerizable compound having a high logPow value include tricyclodecane dimethanol di(meth)acrylate (logPow=3.05) and isodecyl (meth)acrylate (logPow=3.27). Alicyclic (meth) acrylate; long chain fat such as 1,9-nonanediol di(meth)acrylate (logPow=3.68), 1,10-decanediol diacrylate (logPow=4.10) Group (meth) acrylate; hydroxytrimethylacetic acid neopentyl glycol (meth) acrylate adduct (logPow = 3.35), 2-ethyl-2-butyl propylene glycol di (meth) acrylate (logPow =3.92) etc. Multi-branched (meth) acrylate; bisphenol A di(meth) acrylate (logPow = 5.46), bisphenol A ethylene oxide 4 molar addition di(meth) acrylate (logPow=5.15), bisphenol A propylene oxide 2 molar addition di(meth) acrylate (logPow=6.10), bisphenol A propylene oxide 4 molar addition Di(meth)acrylate (logPow=6.43), 9,9-bis[4-(2-(methyl)acryloxyethoxy)phenyl]anthracene (logPow=7.48), (methyl) (A) an aromatic ring-containing (meth) acrylate such as p-phenylphenol ester (logPow=3.98).

From the viewpoint of the adhesion to a polarizer and various transparent protective films and the optical durability in a severe environment, the radically polymerizable compound is a monofunctional radical polymerizable compound and a polyfunctional compound. A radical polymerizable compound is preferred. In general, it is preferably used in an amount of from 3 to 80% by weight of the monofunctional radically polymerizable compound and from 20 to 97% by weight of the polyfunctional radically polymerizable compound, based on 100% by weight of the radically polymerizable compound.

<The aspect of the radical polymerization hardening type binder composition>

When the curable adhesive composition for a polarizing film of the present invention is used as an active energy ray-curable component, an active energy ray-curable adhesive composition can be used. When the active energy ray-curable adhesive composition is an electron beam or the like using an active energy ray, the active energy ray-curable adhesive composition does not need to contain a photopolymerization initiator, but when ultraviolet rays or visible rays are used for the active energy ray, It is preferred to contain a photopolymerization initiator.

Photopolymerization initiator≫

The photopolymerization initiator using a radically polymerizable compound can be appropriately selected in accordance with the active energy ray. When it is hardened by ultraviolet rays or visible rays, a photopolymerization initiator which is cracked by ultraviolet rays or visible rays can be used. Examples of the photopolymerization initiator include diphenylethylenedione (benzil), diphenylketone, benzhydrylbenzoic acid, and 3,3'-dimethyl-4-methoxydiphenyl. a diphenyl ketone compound such as a ketone; 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ketone, α-hydroxy-α,α'-dimethylacetophenone, An aromatic ketone compound such as 2-methyl-2-hydroxypropiophenone or α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, Acetophenone-based compound such as 2,2-diethoxyacetophenone or 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinepropane-1; benzoin a benzoin ether compound such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether or fennel methyl ether; an aromatic ketal compound such as benzyl dimethyl ketal; Aromatic sulfonium chloride compound such as 2-naphthalenesulfonium chloride; photoactive lanthanide compound such as 1-benzophenone-1,1-propanedione-2-(o-ethoxycarbonyl)anthracene; 9-oxygen sulfur (thioxanthone), 2-chloro 9-oxosulfur 2-methylthio group Ketone, 2,4-dimethylthio Ketone, isopropyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur Twelve base 9-oxosulfur 9-oxosulfur a compound; camphorquinone; a halogenated ketone; a fluorenylphosphine oxide; a decylphosphonate. Among the photopolymerization initiators, those having a higher log Pow value are preferred. The logPow value of the photopolymerization initiator is preferably 2 or more, preferably 3 or more, and most preferably 4 or more.

The amount of the photopolymerization initiator to be added is 20 parts by weight or less based on 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The amount of the photopolymerization initiator to be blended is preferably 0.01 to 20 parts by weight, further preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

Moreover, when the composition for a polarizing adhesive for a polarizing film of the present invention is used as a visible light curing type containing a radical polymerizable compound as a curable component, in particular, it is highly sensitive to light of 380 nm or more. A photopolymerization initiator of sensitivity is preferred. A photopolymerization initiator having high sensitivity to light of 380 nm or more is described later.

The photopolymerization initiator is preferably a compound represented by the following formula (1), or a compound represented by the formula (1), and a photopolymerization initiator having high sensitivity to light of 380 nm or more, which will be described later. ,

(wherein R ¹ and R ² represent -H, -CH ₂ CH ₃ , -iPr or Cl, and R ¹ and R ² may be the same or different). When a photopolymerization initiator having a high sensitivity is used alone or in a light source of 380 nm or more, when the compound represented by the formula (1) is used, it has excellent adhesion. Among the compounds represented by the formula (1), diethyl 9-oxosulfuric acid wherein R ¹ and R ² are -CH ₂ CH ₃ It is especially good. The composition ratio of the compound represented by the formula (1) in the composition of the second embodiment is preferably 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, per 100 parts by weight of the total amount of the curable component. It is preferably 0.9 to 3 parts by weight.

Further, it is preferred to add a polymerization initiation aid as necessary. Examples of the polymerization initiation aid include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, and 4-dimethylene. Ethyl methacrylate, isoamyl 4-dimethylaminobenzoate, and the like are particularly preferred as ethyl 4-dimethylaminobenzoate. When a polymerization initiation aid is used, the amount thereof is added in an amount of 100 parts by weight based on the total amount of the curable component, usually 0 to 5 by weight. The portion is preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight.

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

In particular, as the photopolymerization initiator, in addition to the photopolymerization initiator of the formula (1), it is preferred to further use a compound represented by the following formula (2).

(wherein R ³ , R ⁴ and R ⁵ represent -H, -CH3, -CH ₂ CH ₃ , -iPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different). As the compound represented by the formula (2), 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one which is also commercially available can be suitably used (trade name: IRGACURE907 manufacturer: BASF). Further, because 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (trade name: IRGACURE 369: BASF), 2-(dimethylamino)-2 -[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: IRGACURE 379: BASF) is highly sensitive, It is better.

<The radically polymerizable compound (a1) having an active methylene group and a radical polymerization initiator (a2) having a hydrogen extraction action>

In the active energy ray-curable adhesive composition, when a radically polymerizable compound (a1) having an active methylene group is used as the radical polymerizable compound, a radical polymerization initiator having a hydrogen extraction action is used. (a2) It is preferred to use it in combination. When such a configuration is used, in particular, even after being taken out from a high-humidity environment or water (non-dry state), the adhesion of the adhesive layer of the polarizing film is remarkably improved. This reason is not clearly understood and is considered to be the following reason. In other words, the radically polymerizable compound (a1) having an active methylene group is mainly composed of a matrix polymer which is simultaneously polymerized with another radical polymerizable compound constituting the adhesive layer and accommodated in the adhesive layer. The chain and/or side chains form an adhesive layer. In the polymerization process, when a radical polymerization initiator (a2) having a hydrogen extraction action is present, a matrix polymer constituting an adhesive layer is formed, and a hydrogen radical is derived from a radically polymerizable compound having an active methylene group ( A2) is extracted and produces free radicals in the methylene group. Then, a methylene group which generates a radical reacts with a hydroxyl group of a polarizer such as PVA, and a covalent bond is formed between the adhesive layer and the polarizer. The result can be estimated, in particular, even in a non-dry state, the adhesion of the adhesive layer of the polarizing film is remarkably improved.

In the present invention, as the radical polymerization initiator (a2) having a hydrogen extraction action, for example, 9-oxosulfuric acid is exemplified. A radical polymerization initiator, a diphenyl ketone radical polymerization initiator, or the like. The aforementioned radical polymerization initiator (a2) is a 9-oxosulfur A radical polymerization initiator is preferred. 9-oxosulfur The radical polymerization initiator may, for example, be a compound represented by the above formula (1). Specific examples of the compound represented by the formula (1) include, for example, 9-oxosulfur Dimethylthio Ketone, diethyl 9-oxosulfur Isopropyl 9-oxosulfur Chlorine 9-oxosulfur Wait. Among the compounds represented by the formula (1), diethyl 9-oxosulfuric acid wherein R ¹ and R ² are -CH ₂ CH ₃ It is especially good.

When the active energy ray-curable adhesive composition contains a radically polymerizable compound (a1) having an active methylene group and a radical polymerization initiator (a2) having a hydrogen extraction action, the total amount of the curable component is When the amount is 100% by weight, the radical polymerizable compound (a1) having the active methylene group and the total amount of the curable component are contained in an amount of from 0.1 to 10% by weight in an amount of from 0.1 to 10% by weight. The part by weight of the radical polymerization initiator (a2) is preferred.

As described above, in the present invention, the methylene group of the radically polymerizable compound (a1) having an active methylene group generates a radical in the presence of a radical polymerization initiator (a2) having a hydrogen extraction action. Such a methylene group reacts with a hydroxyl group of a polarizer such as PVA to form a covalent bond. Therefore, when the methylene group of the radically polymerizable compound (a1) having an active methylene group generates a radical and sufficiently forms such a covalent bond, when the total amount of the curable component is 100% by weight, the content is contained. The radically polymerizable compound (a1) having an active methylene group is preferably from 1 to 50% by weight, and more preferably from 3 to 30% by weight. In order to sufficiently improve the water resistance and improve the adhesion in a non-dry state, the radically polymerizable compound (a1) having an active methylene group is set to 1% by weight. It is better. On the other hand, when it is more than 50% by weight, there is a case where the adhesive layer is hardened. In addition, the radical polymerization initiator (a2) having a hydrogen extraction action is preferably contained in an amount of 0.1 to 10 parts by weight, and further preferably 0.3 to 9 parts by weight, based on 100 parts by weight of the total amount of the curable component. In order to sufficiently carry out the hydrogen extraction reaction, it is preferred to use 0.1 part by weight or more of the radical polymerization initiator (a2). On the other hand, when it is more than 10 parts by weight, there is a case where it is not completely dissolved in the composition.

<2: Cationic polymerization hardening type adhesive composition>

The cationically polymerizable compound used in the cationically polymerizable resin composition can be classified into a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule, and having two or more cations in the molecule. A polyfunctional cationically polymerizable compound having a polymerizable functional group. Since the monofunctional cationically polymerizable compound has a low liquid viscosity, the liquid viscosity of the resin composition can be lowered by containing the resin composition. In addition, the monofunctional cationically polymerizable compound has a functional group which exhibits various functions, and the resin composition contains a monofunctional cationically polymerizable compound, and the cured product of the resin composition and/or the resin composition can exhibit various functions. . Since the polyfunctional cationically polymerizable compound can crosslink the cured product of the resin composition three-dimensionally, it is preferred that the resin composition contains a polyfunctional cationically polymerizable compound. The ratio of the monofunctional cationically polymerizable compound to the polyfunctional cationically polymerizable compound is preferably from 10 parts by weight to 1000 parts by weight based on 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 the epoxy group-containing compound include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound, and the cationically polymerizable resin composition of the present invention has excellent curability and then It is particularly preferred to contain an alicyclic epoxy compound. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxycyclohexylmethyl-3,4-. The caprolactone modified product of the epoxycyclohexane carboxylate, the trimethyl caprolactone modified product, the valerolactone modified product, and the like, 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 Japan Co., Ltd.). The compound having an oxetane group has an effect of improving the curability of the cationically polymerizable resin composition of the present invention or lowering the liquid viscosity of the composition to contain an oxetane group. The compound is preferred. Examples of the compound having an oxetane group include 3-ethyl-3-hydroxymethyloxetane and 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 novolac oxetane, and the like, 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.), and the like. A compound having a vinyl ether group has a cationic polymerization curable resin which improves the present invention The curability of the composition or the effect of lowering the liquid viscosity of the composition is preferable so that the compound having a vinyl ether group is contained. Examples of the compound having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and triethylene glycol divinyl ether. , cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl vinyl ether, neopentyl Alcohol type tetravinyl ether and the like.

<Photocationic polymerization initiator>

The cationically polymerizable resin composition contains at least one compound selected from the group consisting of a compound having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group, which are described above as a curable component. Any of these will be hardened by cationic polymerization, so that a photocationic polymerization initiator can be formulated. The photocationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with an active energy ray such as visible light, ultraviolet rays, X-rays, or electron beams, and starts polymerization of an epoxy group and an oxetane group. As the photocationic polymerization initiator, a photoacid generator to be described later can be suitably used. Further, when the curable resin composition used in the present invention is used in the visible light curability, it is preferable to use a photocationic polymerization initiator having high sensitivity to light of 380 nm or more, because photocationic polymerization is initiated. The agent system usually exhibits a greatly absorbed compound at or near the wavelength of 300 nm, so the longer wavelength region is compared by blending, specifically, the light absorption at the longer wavelength of 380 nm shows the absorption of the maximum absorption. The agent is capable of inducing light at the nearby wavelength to promote the generation of a cationic species or acid from the photocationic polymerization initiator. As a photosensitizer, For example, an anthracene compound, a ruthenium compound, a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo, a diazo compound, a halogen compound, a photoreducible dye, etc. may be mentioned, and these two types may be mixed. Use above. The antimony compound is particularly preferable because it has an excellent photosensitizing effect, and specific examples thereof include ANTHRACURE UVS-1331 and ANTHRACURE UVS-1221 (manufactured by Kawasaki Kasei Co., Ltd.). The content of the photosensitizer is preferably from 0.1% by weight to 5% by weight, more preferably from 0.5% by weight to 3% by weight.

<Other ingredients>

The hardening type adhesive composition of the present invention preferably contains the following components.

<Acrylic oligomer (A)>

The active energy ray-curable adhesive composition of the present invention may contain an acrylic oligomer obtained by polymerizing a (meth)acryl oxime monomer in addition to the curable component of the radical polymerizable compound. A). By including the component (A) in the active energy ray-curable adhesive composition, it is possible to reduce the curing energy by curing the composition by irradiating the active energy ray, and to reduce the adhesion and the polarizer, the transparent protective film, and the like. The interface stress of the adherend. As a result, it is possible to suppress the adhesion of the adhesive layer and the adherend to be lowered. In order to sufficiently suppress the occurrence of hardening shrinkage of the cured layer (adhesive layer), the content of the acrylic oligomer (A) is preferably 20 parts by weight or less, based on 100 parts by weight of the total amount of the curable component, and is 15 parts by weight. The following are preferred. When the content of the acrylic oligomer (A) in the subsequent composition is too large, the reaction rate when the active energy ray is applied to the composition is drastically lowered and the curing failure is caused. On the other hand, the total amount of 100 weight relative to the hardenable component The acrylic oligomer (A) is preferably contained in an amount of 3 parts by weight or more, preferably 5 parts by weight or more.

When the workability and uniformity at the time of coating are considered, the active energy ray-curable adhesive composition is preferably a low-viscosity, so that an acrylic oligomer obtained by polymerizing a (meth) acrylonitrile-based monomer ( A) It is also preferred to have a low viscosity. The acrylic oligomer having a low viscosity and capable of preventing the adhesive layer from undergoing curing shrinkage is preferably a weight average molecular weight (Mw) of 15,000 or less, more preferably 10,000 or less, and most preferably 5,000 or less. 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 (A) is preferably 500 or more, more preferably 1,000 or more. More than 1500 is especially good. Specific examples of the (meth)acryl fluorenyl monomer constituting the acrylic oligomer (A) include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). N-propyl acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S -butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, third amyl (meth) acrylate, 3-pentyl (meth) acrylate, ( 2,2-dimethylbutyl methacrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethyl methacrylate a (meth)acrylic acid (carbon number 1-20) alkyl ester such as an ester, 4-methyl-2-propylamyl (meth)acrylate or N-octadecyl (meth)acrylate; and Cycloalkyl (meth) acrylate (for example, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, etc.), aryl (meth) acrylate (for example, benzyl (meth) acrylate) Etc., polycyclic (meth) acrylate (for example, 2-isodecyl (meth) acrylate, (a ) 2-norbornyl methyl acrylate, 5-northene-2-yl-methyl (meth) acrylate, 3-methyl-2-northyl methyl (meth) acrylate, etc.), hydroxyl group-containing (Meth) acrylates (for example, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropylmethyl-butyl (methyl) methyl Acrylate, etc., alkoxy or phenoxy-containing (meth) acrylate (2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (A) 2-methoxymethoxyethyl acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, etc. ) an epoxy group-containing (meth) acrylate (for example, glycidyl (meth) acrylate) or a halogen-containing (meth) acrylate (for example, (meth)acrylic acid 2, 2 , 2-trifluoroethyl ester, 2,2,2-trifluoroethyl ethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, (methyl) Octafluoropentyl acrylate, heptadecafluoro(meth)acrylate, etc.), alkylaminoalkyl (meth) acrylate (eg, methyl methacrylate) Ethyl ester, etc.). These (meth) acrylates can be used alone or in combination of two or more. Specific examples of the acrylic oligomer (A) include "ARUFON" manufactured by Toagosei Co., Ltd., "ACT FLOW" manufactured by Amika Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Japan Co., Ltd., and the like. Among the acrylic oligomers (A) obtained by polymerizing a (meth)acrylonitrile monomer, a higher logPow value is preferred. The log Pow value of the acrylic oligomer (A) obtained by polymerizing the (meth)acrylonitrile monomer is preferably 2 or more, preferably 3 or more, and most preferably 4 or more.

<Photoacid generator (B)>

The active energy ray-curable adhesive composition can contain a photoacid generator (B). The active energy ray-curable resin composition contains photoacid When the agent is produced, the water resistance and durability of the adhesive layer can be drastically improved as compared with the case where the photoacid generator is not contained. The photoacid generator (B) can be represented by the following general formula (3).

General formula (3) [Chemical 3] L ⁺ X ^-

(wherein, L+ represents an arbitrary phosphonium cation. Further, X-system represents a group selected from PF ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , SbCl ₆ ^- , BiCl ₅ ^- , SnCl ₆ ^- , ClO ₄ ^- , thiamine carboxylate anion, SCN ^- the counter anion of the group) configuration.

Among the above-mentioned exemplary anions, as the relative anion X ^- in the formula (3), particularly preferred examples of the anion include PF ₆ ^- , SbF ₆ ^- and AsF ₆ ^- , and PF ₆ ^- , SbF ₆ ^- It is especially good.

Therefore, specific examples of the preferred sulfonium salt constituting the photoacid generator (B) of the present invention include "Cyracure-UVI-6992" and "Cyracure-UVI-6974" (above, manufactured by DOW CHEMICAL Japan Co., Ltd.) ), "ADEKA OPTOMER SP150", "ADEKA OPTOMER SP152", "ADEKA OPTOMER SP170", "ADEKA OPTOMER SP172" (above, ADEKA company), "IRGACURE250" (manufactured by CIBA.SPECIALTY.CHEMICALS), "CI- 5102", "CI-2855" (above, manufactured by Japan's Soda Corporation), "SANEIDO SI-60L", "SANEIDO SI-80L", "SANEIDO SI-100L", "SANEIDO SI-110L", "SANEIDO SI-180L" (above, Sanshin Chemical Co., Ltd.), "CPI-100P", "CPI-100A" (above, manufactured by SAN-APRO Co., Ltd.), "WPI-069", "WPI-113", "WPI-116", "WPI-041", "WPI-044", "WPI-054", "WPI-055", "WPAG-281", "WPAG" -567" and "WPAG-596" (above, Wako Pure Chemical Industries, Ltd.) are preferred examples of the photoacid generator (B) of the present invention.

The content of the photoacid generator (B) is 10 parts by weight or less based on 100 parts by weight of the total amount of the curable component, preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and preferably 0.1 to 0.1 part by weight. 3 parts by weight is particularly good.

<Compound (C) containing either an alkoxy group or an epoxy group>

In the active energy ray-curable adhesive composition, a photoacid generator (B) and a compound containing an alkoxy group or an epoxy group can be used in combination in the active energy ray-curable adhesive composition. ).

(epoxy group-containing compound and polymer) (C)

When 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 is used, it may be used in combination with two or more epoxy groups in the molecule. A compound having a reactive functional group. Here, the functional group reactive with an epoxy group may, for example, be a carboxyl group, a phenolic hydroxyl group, a thiol group, or a 1 or 2 aromatic amine group. In view of three-dimensional hardenability, it is particularly preferable to have two or more in one molecule.

Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, and bisphenol F and epichlorohydrin. Alcohol-derived bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F phenolic Varnish type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydrogen Polyfunctional epoxy resin, epoxy acrylate, epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, fluorene epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, etc. Alkyl ester type epoxy resin, epoxy propylamine type epoxy resin, hydantoin type epoxy resin, isomeric cyanate type epoxy resin, aliphatic chain epoxy resin, etc., such rings The oxy resin can also be halogenated or hydrogenated. As a commercially available epoxy resin product, JER COAT828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, DIC Corporation, manufactured by Japan Epoxy Resins Co., Ltd., may be mentioned. Epiclon 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series made by the company ADEKA, CELLOXIDE series (2021, 2021P, 2083, 2085, 3000, etc.) made by DAICEL Chemical Co., Ltd., EPOLEAD series, EHPE series, YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyhydroxy polyether synthesized from bisphenols and epichlorohydrin and having epoxy groups at both ends; NP series) manufactured by Nippon Steel Chemical Co., Ltd. In addition, the DENACOL series manufactured by NAGASE CHEMTEX Co., Ltd. and the Epolite series manufactured by Kyoritsu Chemical Co., Ltd. are not limited. These epoxy resins may be used in combination of two or more kinds. Further, when the glass transition temperature Tg of the adhesive layer was calculated, the compound having an epoxy group and the polymer (C) were not included in the calculation.

(a compound having an alkoxy group and a polymer)

The compound having an alkoxy group in the (C) molecule is not particularly limited as long as it has one or more alkoxy groups in the molecule, and a known one can be used. Examples of such a compound include a melamine compound, an amine resin, a decane coupling agent, and the like. Also, in calculating the adhesive layer When the glass transition temperature Tg is calculated, the compound having an alkoxy group and the polymer (C) are not included in the calculation.

The compound (C) containing the alkoxy group and the epoxy group is contained in an amount of usually 30 parts by weight or less based on 100 parts by weight of the total amount of the curable component, and the amount of the compound (C) in the composition is too large. For a long time, the adhesion is low and the resistance to the drop test is deteriorated. The content of the compound (C) in the composition is preferably 20 parts by weight or less. On the other hand, in terms of water resistance, the compound (C) is preferably contained in an amount of 2 parts by weight or more, and preferably 5 parts by weight or more.

<decane coupling agent (D)>

The hardening type adhesive composition for a polarizing film of the present invention is characterized in that it has a viscosity of 15 mPa. The alkoxyalkylalkyl group-containing compound above s, the alkoxyalkyl group-containing compound is equivalent to a higher molecular weight compound. Moreover, in the present invention, it is also possible to adjust the specific viscosity of the adhesive composition to 15 mPa. a lower molecular weight decane coupling agent (D) having an alkoxyalkylene group above s. When the curable adhesive composition for a polarizing film of the present invention is an active energy ray-curable curing type, the decane coupling agent (D) is preferably an active energy ray-curable compound, but it is not active energy ray hardening property. Can impart the same water resistance.

Specific examples of the decane coupling agent (D) of the low molecular weight alkoxyalkylene group-containing compound include vinyl trichloromethane, vinyl trimethoxy decane, and vinyl as the active energy ray-curable compound. Triethoxy decane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldi Ethoxy Decane, 3-glycidoxypropyltriethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropene oxime Oxypropyltrimethoxydecane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropane Trimethoxy decane and the like.

Preferred are 3-methacryloxypropyltrimethoxydecane and 3-propenyloxypropyltrimethoxydecane.

As a specific example of the active energy ray-curable decane coupling agent, a decane coupling agent (D1) having an amine group is preferred. Specific examples of the decane coupling agent (D1) having an amine group include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and γ-aminopropyltriisopropoxydecane. , γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxydecane, γ-(2-aminoethyl)aminepropyltrimethoxydecane, γ-(2-amine Ethyl)aminopropylmethyldimethoxydecane, γ-(2-aminoethyl)aminepropyltriethoxydecane, γ-(2-aminoethyl)aminepropylmethyldiethoxy Decane, γ-(2-aminoethyl)aminopropyltriisopropoxydecane, γ-(2-(2-aminoethyl)amineethyl)aminepropyltrimethoxydecane, γ-(6- Aminohexyl)aminopropyltrimethoxydecane, 3-(N-ethylamino)-2-methylpropyltrimethoxydecane, γ-ureidopropyltrimethoxydecane, γ-ureidopropyltriethoxy Baseline, N-phenyl-γ-aminopropyltrimethoxydecane, N-benzyl-γ-aminopropyltrimethoxydecane, N-vinylbenzyl-γ-aminopropyltriethoxydecane , N-cyclohexylamine methyl triethoxy decane, N-cyclohexylamine methyl diethoxymethyl decane, N-phenylamine methyl trimethoxy decane, (2-aminoethyl) amine Base three An amine group-containing decane such as methoxy decane or N,N'-bis[3-(trimethoxydecyl)propyl]ethylenediamine; N-(1,3-dimethyl amide) A ketimine type decane such as butyl)-3-(triethoxydecyl)-1-propanamine.

The decane coupling agent (D1) having an amine group may be used singly or in combination of plural kinds. Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxydecane, γ-(2-aminoethyl)aminopropyltrimethoxydecane, γ-(2-aminoethyl) Aminopropylmethyldimethoxydecane, γ-(2-aminoethyl)aminepropyltriethoxydecane, γ-(2-aminoethyl)aminepropylmethyldiethoxydecane, N -(1,3-Dimethylbutylene)-3-(triethoxydecyl)-1-propanamine is preferred.

The blending amount of the decane coupling agent (D) is preferably 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, and 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the curable component. Better. When the amount is more than 20 parts by weight, the storage stability of the adhesive composition is deteriorated, and when it is less than 0.1 part by weight, the effect of the subsequent water resistance cannot be sufficiently exhibited. Further, when the glass transition temperature Tg of the adhesive layer was calculated, the decane coupling agent (D) was not included in the calculation.

Specific examples of the decane coupling agent other than the above-described active energy ray-curable exemplifying agent include 3-ureidopropyltriethoxy decane, 3-chloropropyltrimethoxydecane, and 3-hydrothiopropylmethyl. Dimethoxy decane, 3-hydrothiopropyltrimethoxy decane, bis(triethoxydecylpropyl)tetrasulfide, 3-isocyanate propyl triethoxy decane, imidazolium, and the like.

<Compound (E) with vinyl ether group>

The cured adhesive composition for a polarizing film of the present invention contains the vinyl ether group-containing compound (E) because of the subsequent water resistance of the polarizer and the adhesive layer. Improvement is better. The reason why such an effect is obtained is not clearly understood, and it is presumed that the vinyl ether group of the compound (E) interacts with the polarizer to improve the adhesion of the polarizer and the adhesive layer. In order to further improve the subsequent water resistance of the polarizer and the adhesive layer, the compound (E) is preferably a radical polymerizable compound having a vinyl ether group. Further, the content of the compound (E) is preferably 0.1 to 19 parts by weight based on 100 parts by weight of the total amount of the curable component.

<Compound (F) which produces keto-enol tautomerism>

The curable adhesive composition for a polarizing film of the present invention can contain a compound which produces keto-enol tautomerism. For example, in the case of an adhesive composition containing a crosslinking agent or an adhesive composition which can be used in the preparation of a crosslinking agent, a form containing a compound which produces the above-described keto-enol tautomerism can be suitably used. Thereby, it is possible to suppress the excessive increase in the viscosity of the adhesive composition after the preparation of the organometallic compound, gelation, and suppression of the formation of the microgel, thereby realizing the effect of prolonging the pot life of the composition.

As the compound (F) which produces the above keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include acetamidine acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane-2. Β-diketones such as 4-dione and 2,6-dimethylheptane-3,5-dione; methyl acetate, ethyl acetate, isopropyl acetate, acetamidine Acetyl acetate such as tert-butyl acetate; propyl mercapto acetate such as ethyl acetoacetate, ethyl acetoacetate, isopropyl propyl acetate, and tributyl propyl decyl acetate And isobutyl decyl acetate such as isobutyl decyl ethyl acetate, isobutyl decyl isopropyl acetate, and isobutyl decyl phthalic acid; A malonic ester such as methyl malonate or ethyl malonate. In particular, as a suitable compound, acetamidineacetone and acetamidine acetate are mentioned. The compound (F) which produces the keto-enol tautomerism may be used singly or in combination of two or more.

The amount of the compound which produces keto-enol tautomerism can be, for example, 0.05 parts by weight to 10 parts by weight, preferably 0.2 parts by weight to 3 parts by weight, based on 1 part by weight of the organometallic compound (for example, 0.3). Parts by weight to 2 parts by weight). When the amount of the above compound is less than 0.05 part by weight based on 1 part by weight of the organometallic compound, it is difficult to exhibit a sufficient use effect. On the other hand, when the amount of the compound is more than 10 parts by weight based on 1 part by weight of the organometallic compound, the interaction proceeds excessively in the organometallic compound and the target water resistance is not easily exhibited.

<Additives other than the above>

Further, the curable adhesive composition for a polarizing film of the present invention can be formulated with various additives as other optional components without impairing the object and effect of the present invention. Examples of such an additive include an epoxy resin, a polyamide, a polyamidamine, a polyurethane, a polybutadiene, a polychloroprene, a polyether, a polyester, and a styrene-butylene. a polymer or oligomer of a diene block copolymer, a petroleum resin, a xylene resin, a ketone resin, a cellulose resin, a fluorine-based oligomer, an anthrone-based oligomer, or a polythioether-based oligomer; Polymerization inhibitors such as phenothiazine, 2,6-di-tert-butyl-4-methylphenol; polymerization initiation aid; leveling agent; wettability improver; surfactant; plasticizer; Inorganic fillers; pigments; dyes, and the like. Among the various additives, the higher the logPow value is preferred. The logPow value of various additives It is preferably 2 or more, preferably 3 or more, and most preferably 4 or more.

The additive is usually 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component.

<Adhesive composition viscosity>

The curable adhesive composition for a polarizing film of the present invention contains the curable component, and the adhesiveness of the adhesive composition is preferably 100 cp or less at 25 ° C from the viewpoint of coatability. On the other hand, when the curable adhesive composition for a polarizing film of the present invention is more than 100 cp at 25 ° C, the temperature of the adhesive composition can be controlled at the time of coating, and it can be adjusted to 100 cp or less. The preferred range of viscosity is 1 to 80 cp, and most preferably 10 to 50 cp. The viscosity can be measured using an E-type viscometer TVE22LT manufactured by Toki Sangyo Co., Ltd.

Further, from the viewpoint of safety, the curable adhesive composition for a polarizing film of the present invention is preferably a material having a low skin irritation as the curable component. Skin irritation can be judged by the P.I.I index. P.I.I is widely used as a degree of skin disorder and can be measured using the Draize method. The measured value is expressed in the range of 0 to 8. The smaller the numerical value, the lower the irritancy can be judged, but since the error of the measured value is large, it is considered to be preferable by the reference value. P.I.I is preferably 4 or less, preferably 3 or less, and most preferably 2 or less.

<Overall water absorption rate>

In the cured adhesive composition for a polarizing film of the present invention, it is preferred that the cured product obtained by curing the curable adhesive composition is immersed in pure water at 23 ° C for 24 hours, and then the overall water absorption ratio described above is 10% by weight or less. . Polarized When the film is placed in a severe high temperature and high humidity (85 ° C / 85% RH, etc.) environment, the moisture passing through the transparent protective film and the adhesive layer invades the polarizing member, and the alignment of the two color pigments is caused by the hydrolysis of the crosslinked structure and is transmitted. The rate is increased, and the optical durability such as a low degree of polarization is deteriorated. By setting the total water absorption rate of the adhesive layer to 10% by weight or less, it is possible to prevent the water from moving toward the polarizer when the polarizing film is placed in a severe high-temperature and high-humidity environment, and the transmittance of the polarizer can be increased to suppress the decrease in the degree of polarization. The adhesive layer of the polarizing film is preferably 5% by weight or less, more preferably 3% by weight or less, from the viewpoint of further improving the optical durability in a severe environment at a high temperature. 1% by weight or less is optimal. On the other hand, when the polarizer is bonded to the transparent protective film, the polarizer retains a certain amount of moisture, and when the cured adhesive composition comes into contact with the moisture contained in the polarizer, shrinkage spots, bubbles, and the like are generated. Poor appearance. In order to suppress the appearance defect, the hardening type adhesive composition is preferably capable of absorbing a certain amount of moisture. More specifically, the overall water absorption rate is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more. The overall water absorption rate is specifically measured by the water absorption rate test method described in JIS K 7209.

<hardening shrinkage rate>

Further, since the curable adhesive composition for a polarizing film of the present invention has a curable component, when the curable adhesive composition is cured, curing shrinkage usually occurs. The hardening shrinkage ratio is an index showing the ratio of hardening shrinkage from the hardenable adhesive composition for a polarizing film to the formation of an adhesive layer. When the curing shrinkage ratio of the subsequent layer is increased, when the adhesive film composition for a polarizing film is cured to form an adhesive layer, the interface is suppressed. It is not good in terms of strain and subsequent failure. From the above viewpoints, the cured shrinkage ratio of the cured product obtained by curing the cured adhesive composition of the polarizing film of the present invention is preferably 10% or less. The hardening shrinkage ratio is preferably small, and the hardening shrinkage ratio is preferably 8% or less, and more preferably 5% or less. The hardening shrinkage ratio can be measured by the method described in JP-A-2013-104869, and specifically, it can be measured by a method using a SECTECH company to cure a shrinkage sensor.

<Polarized film>

In the polarizing film of the present invention, a transparent protective film is bonded to at least one surface of the polarizer through an adhesive layer formed by the cured layer of the cured adhesive composition for a polarizing film. The adhesive layer of the cured layer is as described above, and the overall water absorption is preferably 10% by weight or less.

<Binder layer>

The thickness of the adhesive layer formed by the above-mentioned hardening type adhesive composition is preferably controlled to be 0.1 to 3 μm . The thickness of the subsequent layer is preferably 0.3 to 2 μm, more preferably 0.5 to 1.5 μm . In order to suppress occurrence of adhesion defects due to cohesive force of the adhesive layer and appearance defects (bubbles) at the time of lamination, it is preferable to set the thickness of the adhesive layer to 0.1 μm or more. On the other hand, when the adhesive layer is thicker than 3 μm , the polarizing film may not satisfy the durability.

Further, the curable adhesive composition is preferably selected such that the Tg of the adhesive layer formed is 60 ° C or higher, more preferably 70 ° C or higher, more preferably 75 ° C or higher, more preferably 100 ° C or higher, and 120 ° C. The above is even better. On the other hand, when the Tg of the adhesive layer is too high, the flexibility of the polarizing film is low, so the Tg of the adhesive layer is preferably 300 ° C or lower, and further preferably 240 ° C or lower, and More preferably below 180 °C. Tg <glass transition temperature> The measurement was carried out under the following measurement conditions using a dynamic viscoelasticity measuring apparatus RSAIII manufactured by TA Instruments.

Sample size: width 10mm, length 30mm, Clamp distance is 20mm, Measurement mode: stretching, frequency: 1 Hz, temperature rising rate: dynamic viscoelasticity was measured at 5 ° C / min, and peak top temperature of tan δ was used as Tg.

Further, the cured adhesive composition preferably has a storage elastic modulus of the adhesive layer formed at 1.0 ° 10 ⁷ Pa or more at 25 ° C, preferably 1.0 × 10 ⁸ Pa or more. Further, the storage elastic modulus of the adhesive layer is 1.0 × 10 ³ Pa to 1.0 × 10 ⁶ Pa, which is different from the storage elastic modulus of the adhesive layer. The storage elastic modulus of the subsequent layer affects the cracking of the polarizer when the polarizing film is subjected to thermal cycling (-40 ° C to 80 ° C, etc.), and when the storage elastic modulus is low, the crack of the polarizer is likely to occur. . The temperature region having a high storage elastic modulus is preferably 80 ° C or less, and preferably 90 ° C or less. The storage elastic modulus can be measured under the same measurement conditions using TAG <glass transition temperature> while using a dynamic viscoelasticity measuring device RSAIII manufactured by TA Instruments. The dynamic viscoelasticity was measured and the value of the storage elastic modulus (E') was used.

The polarizing film of the present invention can be produced by a manufacturing method comprising the steps of: coating a polarizing film with a hardening type adhesive composition on at least one side of a polarizing member and a transparent protective film; a step of bonding the polarizing member and the transparent protective film; and, in the following step, passing the polarizer through the adhesive layer And a transparent protective film, wherein the adhesive layer is obtained by curing the active energy ray-curable adhesive composition by irradiating an active energy ray from the surface of the polarizer or the surface of the transparent protective film. In the manufacturing method, the moisture content of the polarizing member in the bonding step is preferably 8 to 19%.

The polarizing member and the transparent protective film may be subjected to surface modification treatment before applying the hardening type adhesive composition. Specific treatments include treatment by corona treatment, plasma treatment, and saponification treatment.

The coating method of the hardening type adhesive composition can be appropriately selected in accordance with the viscosity of the composition and the target thickness. Examples of the coating method include a reverse roll coater, a gravure coater (straight roll, reverse roll, and compensation), a bar reverse roll coater, a roll coater, a die coater, and a bar coat. Cloth, stick coating machine, etc. Further, the coating system can suitably use a method such as a dipping method.

The polarizing member is bonded to the transparent protective film through the hardened adhesive composition coated as described above. The bonding of the polarizer and the transparent protective film can be carried out using a roll bonding machine or the like.

<hardening of the composition of the adhesive>

The hardenable adhesive composition for a polarizing film of the present invention can be used as an active energy ray-curable adhesive composition. The active energy ray-curable adhesive composition can be used in the form of an electron beam curing type, an ultraviolet curing type, or a visible light curing type. From the viewpoint of productivity, the aspect of the above-mentioned hardening type adhesive composition is preferably a visible light curing type adhesive composition.

≪Active energy line hardening type ≫

In the active energy ray-curable adhesive composition, after the polarizer and the transparent protective film are bonded together, the active energy ray (electron ray, ultraviolet ray, visible light, etc.) is irradiated and the active energy ray-curable adhesive composition is hardened. An adhesive layer is formed. The irradiation direction of the active energy ray (electron ray, ultraviolet ray, visible ray, etc.) can be irradiated from any appropriate direction. It is preferred to illuminate from the side of the transparent protective film. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron rays, ultraviolet rays, visible rays, etc.).

≪electron ray hardening type ≫

In the electron beam curing type, the irradiation condition of the electron beam can be any suitable condition as long as the active energy ray-curable adhesive composition can be cured. For example, when the electron beam is irradiated, the acceleration voltage is preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. When the accelerating voltage is less than 5 kV, the electron beam cannot reach the adhesive and there is a possibility of insufficient hardening. When the accelerating voltage is greater than 300 kV, the penetration force of the sample is too strong to cause damage to the transparent protective film and the polarizing member. In terms of the amount of illumination, it is 5 to 100 kGy, more preferably 10 to 75 kGy. When the amount of irradiation line is less than 5 kGy, the adhesive hardening is insufficient, and when it is more than 100 kGy, damage to the transparent protective film and the polarizing member is caused, mechanical strength is lowered, yellowing is caused, and predetermined optical characteristics are not obtained.

The electron beam irradiation system is usually irradiated in an inert gas, and if necessary, in the atmosphere and with a little introduction of oxygen. Also depending on the material of the transparent protective film, by appropriately introducing oxygen, the surface of the transparent protective film irradiated by the first electron beam intentionally causes oxygen to block, and It is possible to prevent damage to the transparent protective film and to efficiently irradiate the electron beam to the adhesive.

≪UV hardening type, visible light hardening type ≫

In the method for producing a polarizing film field of the present invention, as the active energy ray, a visible light having a wavelength range of 380 nm to 450 nm is included, and in particular, an active energy ray having the highest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm is preferably used. In the ultraviolet curing type and the visible light curing type, when a transparent protective film (ultraviolet-opaque transparent protective film) which imparts ultraviolet absorbing ability is used, since light having a shorter wavelength than about 380 nm is absorbed, wavelengths shorter than 380 nm are used. The light system did not reach the active energy ray-curable adhesive composition, but did not contribute to its polymerization. Moreover, the light having a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, so that the transparent protective film itself generates heat and becomes a polarizing film to cause curling. Bad causes such as wrinkles. Therefore, when the ultraviolet curable type and the visible light curable type of the present invention are used, it is preferable to use a device that does not emit light having a shorter wavelength than 380 nm as the active energy ray generating device, more specifically, the gamma 440 to 440 nm cumulative. The ratio of the illuminance to the cumulative illumination of the wavelength range of 250 to 370 nm is preferably 100:0 to 100:50, and preferably 100:0 to 100:40. The active energy ray of the present invention is preferably an LED light source in which a halogenated metal lamp is enclosed in gallium and light having a wavelength in the range of 380 to 440 nm is emitted. Or can use low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, white hot electric ball, xenon lamp, halogen lamp, carbon arc lamp, halogen metal lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight A light source containing ultraviolet and visible light; a bandpass filter can also be used. Ultraviolet rays having a shorter wavelength than 380 nm were used for blocking. In order to improve the adhesion performance of the adhesive layer between the polarizer and the transparent protective film while preventing the polarizing film from being curled, a gallium-passed metal halide lamp is used to pass through a band pass filter capable of blocking light of a shorter wavelength than 380 nm. The obtained active energy ray or an active energy ray having a wavelength of 405 nm obtained using an LED light source is preferred.

In the ultraviolet curing type or the visible light curing type, it is preferable to heat the active energy ray-curable adhesive composition (warming before irradiation) before irradiating ultraviolet rays or visible rays, and at this time, it is heated to 40 ° C. The above is preferred, and heating to 50 ° C or higher is preferred. Further, after irradiating ultraviolet rays or visible rays, it is also preferable to heat the active energy ray-curable adhesive composition (warming after irradiation), and it is preferably heated to 40 ° C or higher to heat to 50 ° C. The above is preferred.

The active energy ray-curable adhesive composition of the present invention can be suitably used in the case where a transparent protective film for forming a polarizing member and a light transmittance of 365 nm at a wavelength of less than 5% is formed. Here, the active energy ray-curable adhesive composition of the present invention is capable of irradiating ultraviolet rays and making an adhesive layer over a transparent protective film having a UV absorbing ability by containing a photopolymerization initiator of the above formula (1). Hardened to form. Therefore, even if a polarizing film having a transparent protective film having a UV absorbing ability is laminated on both surfaces of the polarizing member, the adhesive layer can be cured. However, it goes without saying that the polarizing film in which a transparent protective film having no UV absorbing ability is laminated can also harden the adhesive layer. Moreover, the so-called transparent protective film with UV absorption means the transmittance of light at 380 nm. Less than 10% transparent protective film.

The method of imparting UV absorbing ability to the transparent protective film includes a method of including an ultraviolet absorber in the transparent protective film, and a method of laminating a surface treatment layer containing the ultraviolet absorber on the surface of the transparent protective film.

Specific examples of the ultraviolet absorber include a hydroxydiphenylketone compound, a benzotriazole compound, a salicylate compound, a diphenylketone compound, and a cyanoacrylate compound, which are well known in the prior art. A nickel salt-based compound, a triazine-based compound, or the like.

After bonding the polarizer to the transparent protective film, the active energy ray-curable adhesive composition is cured by irradiation with an active energy ray (electron ray, ultraviolet ray, visible light, or the like) to form an adhesive layer. The irradiation direction of the active energy ray (electron ray, ultraviolet ray, visible ray, etc.) can be irradiated from any appropriate direction. It is preferred to illuminate from the side of the transparent protective film. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron rays, ultraviolet rays, visible rays, etc.).

When the polarizing film of the present invention is produced by a continuous production line, the production line speed depends on the hardening time of the adhesive composition, preferably from 1 to 500 m/min, preferably from 5 to 300 m/min, more preferably from 10 to 100 m/min. . The line speed is too small, lacks productivity, or damages the transparent protective film too much, and it is impossible to manufacture a polarizing film that can withstand durability tests and the like. When the line speed is too large, the hardening of the adhesive composition becomes insufficient, and there is a case where the target adhesion cannot be obtained.

Moreover, the polarizing film of the present invention transmits the above active energy ray The adhesive layer formed of the cured layer of the cured adhesive composition bonds the polarizer to the transparent protective film, but an easy adhesion layer can also be provided between the transparent protective film and the adhesive layer. The easy-adhesion layer can be, for example, a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, an anthrone, a polyamine skeleton, a polyimine skeleton, a polyvinyl alcohol skeleton, or the like. The resin is formed. These polymer resins can be used singly or in combination of two or more. Further, other additives may be added to the formation of the easy-to-adhere layer. Specifically, a stabilizer such as an adhesion-imparting agent, an ultraviolet absorber, an antioxidant, a heat-resistant stabilizer, or the like can be further used.

The easy-adhesion layer is usually provided in advance on the transparent protective film, and the easy-adhesion layer side of the transparent protective film is bonded to the polarizing member by an adhesive layer. The formation of the easy-adhesion layer can be carried out by applying a formation of an easy-adhesion layer on a transparent protective film and drying it using a well-known technique. The formation of the easy-adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying, the smoothness of coating, and the like. The thickness of the layer which is easily dried is preferably from 0.01 to 5 μm , more preferably from 0.02 to 2 μm , still more preferably from 0.05 to 1 μm . Further, the plurality of layers can be provided in the easy-to-attach layer. In this case, it is preferable that the total thickness of the easily-adhesive layer is in the above range.

<polarizer>

The polarizer is not particularly limited, and various materials can be used. Examples of the polarizer include a polyvinyl alcohol-based film, a partially methylalized polyvinyl alcohol-based film, and ethylene. A hydrophilic polymer film such as a partially saponified film of a vinyl acetate copolymer is adsorbed by a dichroic material such as iodine or a dichroic dye, and is uniaxially stretched; a dehydrated material of polyvinyl alcohol or a polyvinyl chloride A polyene-based alignment film or the like such as a hydrochloric acid-treated product. Among these, a polarizing member composed of a polyvinyl alcohol-based film and a dichroic material such as iodine is preferred. The thickness of the polarizers is not particularly limited, and is usually about 80 μm or less.

A polarizing material obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine and dyeing it to extend 3 to 7 times the original length. It is also possible to immerse in an aqueous solution of boric acid, potassium iodide or the like as necessary. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. When the polyvinyl alcohol-based film is washed with water, it is possible to prevent contamination of the surface of the polyvinyl alcohol-based film and the anti-adhesive agent, and also to prevent unevenness in dyeing unevenness due to swelling of the polyvinyl alcohol-based film. . The extension system may be carried out after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. It can also be extended in an aqueous solution of boric acid, potassium iodide, etc., and in a water bath.

In addition, when a thin polarizer having a thickness of 10 μm or less is used as the polarizing material of the present invention, the effect can be remarkably exhibited (accepting the optical durability in a severe environment under high temperature and high humidity) . Compared with a polarizer having a thickness of more than 10 μm, the polarizer having a thickness of 10 μm or less has a relatively large influence on moisture, and is less likely to cause insufficient optical durability in an environment of high temperature and high humidity. The transmittance increases and the degree of polarization is low. Therefore, a cured product composed of a cured adhesive composition for a polarizing film of the present invention containing at least one organometallic compound selected from the group consisting of metal alkoxides and metal tongs is used. When the agent layer or even the above-mentioned 10 μm or less of the polarizer is laminated on the adhesive layer having a total water absorption of 10% by weight or less, the movement of the water to the polarizer can be suppressed in a harsh environment of high temperature and high humidity, so that the polarized light is polarized. The transmittance of the film is increased, and the deterioration of optical durability such as a decrease in the degree of polarization can be remarkably suppressed. From the viewpoint of thinning, the thickness of the polarizer is preferably 1 to 7 μm . Such a thin polarizer is preferred because it has a small thickness unevenness and excellent visibility, and has a small dimensional change, and can also be made thinner as the thickness of the polarizing film.

As a thin type of polarizing material, the specification is exemplified in JP-A-51-069644, JP-A-2000-338329, WO2010/100917, PCT/JP2010/001460, or JP-A-2010-269002. The thin polarizing film described in the specification of Japanese Patent Application No. 2010-263692. The thin polarizing film can be obtained by a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) layer and a resin substrate for stretching, and a dyeing step, in a state in which the laminate is contained. . In this method, even if the PVA-based resin layer is thin and supported by the resin substrate for stretching, it is possible to extend without causing defects such as breakage due to stretching.

In the method of forming the thin polarizing film, which is carried out in a state in which the layered body is stretched and a dyeing step, the film can be extended to a high magnification and the polarizing performance is improved, by a booklet such as WO2010/100917. It is preferable to obtain the method of the step of extending in an aqueous solution of boric acid described in the specification of PCT/JP2010/001460, or the specification of Japanese Patent Application No. 2010-269002 and the specification of Japanese Patent Application No. 2010-263692, especially by Special offer 2010-269002 specification and special wish It is preferred that the method of assisting the step of extending in the air before extending in a boric acid aqueous solution described in the specification of 2010-263692 is preferred.

<Transparent protective film>

The material for forming the transparent protective film provided on one or both sides of the polarizer is preferably a material having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, and the like. For example, a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate; a cellulose-based polymer such as cellulose diacetate or cellulose triacetate; and polymethyl methacrylic acid; Acrylic polymer such as ester; polystyrene, acrylonitrile. A styrene polymer such as a styrene copolymer (AS resin); a polycarbonate polymer or the like. Further, examples thereof include polyethylene, polypropylene, and a polyolefin having a ring system or a norbornene structure, such as ethylene. A polyolefin polymer such as a propylene copolymer, a vinyl chloride polymer, a phthalimide polymer such as nylon or an aromatic polyamide, a quinone imine polymer, a fluorene polymer, or a polyether fluorene system Polymer, polyetheretherketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate A polymer, a polyoxymethylene polymer, an epoxy polymer, or a blend of the above polymers is exemplified as a polymer forming the transparent protective film. The transparent protective film may contain any appropriate additive of one or more types. Examples of the additive include an ultraviolet absorber, an antioxidant, a slip agent, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a colorant, and the like. The content of the above thermoplastic resin in the transparent protective film is preferably from 50 to 100% by weight, preferably from 50 to 99% by weight. More preferably, it is 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, the high transparency and the like which the thermoplastic resin originally has may not be sufficiently exhibited.

Further, as the transparent protective film, a polymer film described in JP-A-2001-343529 (WO01/37007), for example, a resin composition containing (A) having a substitution and/or an unsubstituted in a side chain, may be mentioned. a thermoplastic resin having a quinone imine group; and (B) a thermoplastic resin having a substituted and/or unsubstituted phenyl group and a nitrile group in a side chain. Specific examples thereof include a film of a resin composition containing: an alternating copolymer composed of isobutylene and N-methylbutyleneimine; and acrylonitrile. Styrene copolymer. As the film, a film composed of a mixed extruded product of a resin composition or the like can be used. Since these film types have a small phase difference and a small photoelastic modulus, the strain of the polarizing film can be prevented from being uneven, and the moisture permeability is small, so that it has excellent humidifying durability.

In the polarizing film, the transparent protective film preferably has a moisture permeability of 150 g/m ² /24 h or less. With such a configuration, moisture in the air does not easily enter the polarizing film, and variation in the moisture content of the polarizing film itself can be suppressed. As a result, it is possible to suppress curling and dimensional change of the polarizing film due to the storage environment.

The material for forming the transparent protective film provided on one or both sides of the polarizing member is preferably a material having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc., particularly The humidity is preferably 150 g/m ² /24 h or less, particularly preferably 140 g/m ² /24 h or less, and more preferably 120 g/m ² /24 h or less. The moisture permeability was determined by the method described in the examples.

As a material for forming the transparent protective film having low moisture permeability, for example, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; an aromatic ester resin; and a nylon can be used. A quinone imine resin such as aromatic polyamine; such as polyethylene, polypropylene, ethylene. A polyolefin-based polymer of a propylene copolymer, a cyclic olefin-based resin having a ring-based or norbornene structure, a (meth)acrylic resin, or a mixture thereof. Among the above resins, a polycarbonate resin, a cyclic polyolefin resin, and a (meth)acrylic resin are preferred, and a cyclic polyolefin resin or a (meth)acrylic resin is particularly preferred.

The thickness of the transparent protective film can be appropriately determined, and is usually about 1 to 100 μm in terms of workability such as strength and workability, and thinness. In particular, it is preferably 1 to 80 μm, and preferably 3 to 60 μm .

Further, when the transparent protective film is provided on both surfaces of the polarizing member, a transparent protective film made of the same polymer material may be used on the front and back sides, and a transparent protective film composed of a different polymer material or the like may be used.

A functional layer such as a hard coat layer, an antireflection layer, an anti-adhesion layer, a diffusion layer or an anti-glare layer can be provided on the surface of the transparent protective film which is not attached to the polarizing member. Further, the functional layer such as the hard coat layer, the antireflection layer, the anti-adhesion layer, the diffusion layer, and the anti-glare layer may be provided separately from the transparent protective film itself, or may be provided as a separate transparent protective film. object.

<Optical film>

The polarizing film of the present invention can be used as other light when it is practical. The optical film laminated by the students. The optical layer system is not particularly limited, and for example, a liquid crystal display device or the like which forms a reflector, a semi-transmissive plate, a retardation plate (including a wavelength plate of 1/2, 1/4, etc.), a viewing angle compensation film, or the like can be used. The optical layer is one layer or two or more layers. In particular, the polarizing film of the present invention further comprises a reflective polarizing film or a transflective polarizing film formed by laminating a reflecting plate or a transflective sheet, and an elliptically polarizing film or a circle formed by further laminating a phase difference plate in the polarizing film. The polarizing film, the wide viewing angle polarizing film in which the viewing angle compensation film is further laminated on the polarizing film, or the polarizing film in which the brightness increasing film is further laminated on the polarizing film is preferable.

The optical film in which the optical layer is laminated on the polarizing film can be formed by sequentially laminating in a manufacturing process such as a liquid crystal display device. However, it is an optical film that is laminated in advance and has excellent quality stability. The utility model has the advantages of being able to improve the manufacturing steps of the liquid crystal display device or the like. The layering system can use an appropriate bonding means such as an adhesive layer. When the above-described polarizing film and other optical films are followed, the optical axis systems can be set to an appropriate arrangement angle in accordance with the target phase difference characteristics and the like.

In the above-mentioned polarizing film and the optical film in which at least one polarizing film is laminated, an adhesive layer can be provided for connection with other members such as liquid crystal cells. The adhesive to form the adhesive layer is not particularly limited, and for example, an acrylic polymer, an anthrone polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine, a rubber, or the like can be appropriately selected. The polymer is used as a matrix polymer. In particular, it is an acrylic adhesive which has excellent optical transparency and exhibits appropriate wettability, cohesiveness and adhesion. Adhesive properties, excellent weather resistance, heat resistance, etc., can be suitably used.

The adhesive layer can also be provided as an overlapping layer of different compositions or types, and provided on one or both sides of the polarizing film and the optical film. Further, when it is provided on both sides, an adhesive layer having a different composition, type, thickness, or the like can be provided on the front and back of the polarizing film and the optical film. The thickness of the adhesive layer can be appropriately determined depending on the purpose of use, the adhesion, and the like, and is usually 1 to 500 μm , preferably 1 to 200 μm, and particularly preferably 1 to 100 μm .

During the period of practical use, in order to prevent contamination or the like, the exposed surface of the adhesive layer may be temporarily adhered to cover the separator. Thereby, it is possible to prevent contact with the adhesive layer in a normal operation state. As the separator, in addition to the above-described thickness conditions, for example, a suitable thin material such as a plastic film, a rubber sheet, a paper, a cloth, a nonwoven fabric, a mesh, a foamed sheet, a metal foil, or the like can be used. The coating process is carried out using an appropriate release agent such as an anthrone or a long-chain alkyl group, a fluorine-based or a molybdenum sulfide, and the like.

<Image display device>

The polarizing film or the optical film of the present invention can be suitably used in various devices and the like for forming a liquid crystal display device or the like. The formation of the liquid crystal display device can be performed in accordance with the prior art. In other words, the liquid crystal display device can be formed by appropriately assembling a liquid crystal cell, a polarizing film or an optical film, and a constituent component such as a necessary illumination system, and incorporating the driving circuit. Other than the point of inventing the polarizing film or the optical film, it is not particularly limited and can be used in accordance with the prior art. For the liquid crystal cell, it is also Any type such as a TN type, an STN type, or a 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 disposed on one side or both sides of a liquid crystal cell, and a liquid crystal display device in which a backlight or a reflecting plate is used in an illumination system. At this time, the polarizing film or the optical film according to the present invention can be disposed on one side or both sides of the liquid crystal cell. When the polarizing film or the optical film is disposed on both sides, the same may be the same or different. Further, when forming a liquid crystal display device, for example, one or two or more diffusion plates, an anti-glare layer, an anti-reflection film, a protective plate, a tantalum array, a lens array sheet, a light diffusing plate, and a backlight can be disposed at appropriate positions. Suitable parts such as boards.

Example

Hereinafter, the examples of the present invention are described, but the embodiments of the present invention are not limited thereto.

<Manufacture of polarizer>

A polyvinyl alcohol film having an average degree of polymerization of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water of 30 ° C for 60 seconds to swell. Next, the film was immersed in an aqueous solution of 0.3% by weight of iodine/potassium iodide (weight ratio = 0.5/8), and the film was dyed while being extended to 3.5 times. Subsequently, the aqueous solution of boric acid ester at 65 ° C was extended so that the total stretching ratio was 6 times. After stretching, it was dried in an oven at 40 ° C for 3 minutes to obtain a PVA-based polarizer X (thickness: 23 μm ).

<Transparent protective film>

Transparent protective film 1: Corona treatment was applied to a cellulose acetate resin having a thickness of 60 μm (described as TAC in Table 1).

Transparent protective film 2: A (meth)acrylic resin (water vapor transmission rate: 96 g/m ² /24 h) having a lactone ring structure having a thickness of 40 μm (referred to as an acrylic resin in Table 1) was used.

<Transparency of transparent protective film>

The measurement of the moisture permeability is measured in accordance with the moisture permeability test (cup method) of JIS Z0208. The sample cut into a diameter of 60 mm was placed in a moisture permeable cup to which about 15 g of calcium chloride was added, and placed in a thermostat having a temperature of 40 ° C and a humidity of 90% RH, and it was measured by placing it for 24 hours. The weight of calcium chloride is increased to obtain moisture permeability (g/m ² /24h).

<Storage Elastic Modulus>

The storage elastic modulus was measured using the dynamic viscoelasticity measuring apparatus RSAIII manufactured by TA Instruments under the following measurement conditions.

Sample size: width 10mm, length 30mm, clamp distance 20mm, measurement mode: stretching, frequency: 1 Hz, heating rate: 5 ° C / minute

The dynamic viscoelasticity was measured and set as the measured value of the storage elastic modulus at 25 °C.

<Overall water absorption rate>

The cured film for a polarizing film used in each example was sandwiched between two sheets of glass provided with a spacer of 100 μm , and hardened under the same active energy conditions as in the examples to prepare a thickness of 100 μm . Then the agent layer (hardened). This was taken as a sample. The weight of the sample was set to (M1)g. The sample M1g was immersed in pure water at 23 ° C for 24 hours. Subsequently, after rubbing off with a cloth taken out from pure water and dried, the weight (M2) g of the sample was measured again within 1 minute. From these results, the overall water absorption rate was calculated according to the following formula: {(M2-M1)/M1}×100 (%).

<active energy line>

As the active energy ray, a visible light ray (a gallium-sealed metal halide lamp) irradiation device is used: Light HAMMER ¹ 0 valve manufactured by Fusion UV Systems, Inc.: V valve peak illuminance: 1600 mW/cm 2 , cumulative irradiation amount 1000/mJ/cm 2 ( Wavelength 380~440nm). Further, the illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.

Examples 1 to 4 and Comparative Examples 1 to 4

(modulation of active energy ray-curable adhesive)

According to the preparation table described in Table 1, each component was mixed, and KAYACURE-DETX-S (2,4-diethyl 9-oxosulfide) was added to 100 g of the total of the radically polymerizable compound. , manufactured by Nippon Kayaku Co., Ltd., and IRGACURE 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one; manufactured by BASF), each adding 1.5 g and 3 g The active energy ray-curable adhesive compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were obtained by stirring.

(Manufacture of polarizing film)

The active energy ray-curable adhesives of Examples 1 to 4 or Comparative Examples 1 to 4 were subjected to an MCD coater (manufactured by Fuji Machinery Co., Ltd.) (groove shape: honeycomb shape, number of gravure rolls: 1000 pieces/inch, rotation) The speed of 140% / the line speed) was applied to the transparent protective film so as to have a thickness of 0.7 μm , and was bonded to both faces of the polarizing member X by using a roll machine. Subsequently, the active light ray-curable adhesive of Example 1 and Comparative Example 1 was cured by irradiating the visible light rays on both sides of the transparent protective film side (both sides) after bonding. The film was dried by hot air at 70 ° C for 3 minutes to obtain a polarizing film having a transparent protective film on both sides of the polarizing member. The line speed of the lamination was carried out at 25 m/min.

The following evaluations were performed on the polarizing films obtained in the above examples and comparative examples. The evaluation results are shown in Table 1.

<Adhesion force after water immersion (water resistance evaluation)>

The polarizing film was cut into a size of 200 mm parallel to the extending direction of the polarizing member and 15 mm in the orthogonal direction, and the polarizing film was immersed in water at 23 ° C for 18 hours, and taken out within 30 minutes (in a non-dry state). The polarizing film was attached to a glass plate. Then, a slit is cut into the slit between the transparent protective film (acrylic resin or TAC) and the polarizing member, and the protective film and the polarizing member are peeled off at a peeling speed of 1000 mm/min in a 90-degree direction by a universal tensile tester (TENSILON) at a peeling speed of 1000 mm/min. To determine the peel strength (N/15 mm). When the peel strength was 0.15 N/15 mm or more, it was judged as ○, and when it was less than 0.15 N/15 mm, it was judged as ×.

In Table 1, the radical polymerizable single system is represented by HEAA: hydroxyethyl acrylamide, manufactured by Xingren Co., Ltd.; ACMO: acryloyl morpholine, manufactured by Xingren Co., Ltd.; 1,9-NDA: 1,9 壬Diacrylate, manufactured by Kyoeisha Chemical Co., Ltd.

The alkoxyalkyl group-containing compound is represented by TA Polymer SA100S: main chain (meth)acrylic polymer type, manufactured by Kaneka Co., Ltd.

X-MAP SA110S: Main chain (meth)acrylic polymer type, manufactured by Kaneka Corporation

X-40-9225: an oligo-type alkoxyalkylene group-containing compound, a product of the sulfonate company, KR-213: an oligo-type alkoxyalkyl group-containing compound, manufactured by Shin-Etsu Chemical Co., Ltd., KC-89S: A low molecular weight alkoxyalkylene group-containing compound, a product manufactured by Shin-Etsuenone Co., Ltd., KBM403: a low molecular weight alkoxyalkylene group-containing compound, and a Shinozolone company.

The metal alkoxide system is represented by D-20: butadiene titanium oxide (carbon number of organic group 4), and is manufactured by Shin-Etsu Chemical Co., Ltd.

The vinyl ether compound is VEEA: 2-(2-vinyloxyethoxy)ethyl acrylate, manufactured by Nippon Shokubai Co., Ltd. The photoacid generator is CPI-100P, manufactured by SAN-APRO.

Claims (22)

The invention relates to a hardening type adhesive composition for a polarizing film, which is used for the transparent protective film to be followed by at least one side of the polarizing member, characterized in that the active energy ray hardening component and the viscosity are 15 mPa. Alkoxyalkylene-containing compounds above s. The hardened adhesive composition for a polarizing film according to claim 1, wherein the main chain of the alkoxyalkyl group-containing compound is an acrylic polymer structure. The hardened adhesive composition for a polarizing film according to claim 1 or 2, further comprising at least one organometallic compound selected from the group consisting of metal alkoxides and metal nips. The hardening type adhesive composition for a polarizing film according to claim 3, wherein the metal of the organometallic compound is titanium. The hardened adhesive composition for a polarizing film according to claim 3 or 4, which contains the metal alkoxide as the organometallic compound, and the metal alkoxide has an organic group having 4 or more carbon atoms. The curable adhesive composition for a polarizing film according to claim 3 or 4, which comprises the metal conjugate as the organometallic compound, and the metal conjugate has an organic group having a carbon number of 4 or more. The curable adhesive composition for a polarizing film according to any one of claims 3 to 6, wherein the ratio of the organometallic compound is 0.05 to 9 when the total amount of the active energy ray-curable component is 100 parts by weight. Parts by weight. The hardened adhesive composition for a polarizing film according to any one of claims 1 to 7, wherein the cured product obtained by hardening the hardened adhesive composition is immersed in pure water at 23 ° C for 24 hours, and the overall water absorption represented by the following formula The ratio is 10% by weight or less; and the formula: {(M2-M1)/M1}×100 (%): M1: the weight of the cured product before impregnation, and M2: the weight of the cured product after the immersion. The curable adhesive composition for a polarizing film according to any one of claims 1 to 8, wherein the active energy ray-curable component contains a radical polymerizable compound. The hardenable adhesive composition for a polarizing film according to claim 9, wherein the radically polymerizable compound contains a (meth) acrylamide derivative. The hardenable adhesive composition for a polarizing film according to claim 9 or 10, wherein the radically polymerizable compound contains a polyfunctional compound having at least two radically polymerizable functional groups. The hardenable adhesive composition for a polarizing film according to any one of claims 1 to 11, which further contains a photopolymerization initiator. The hardenable adhesive composition for a polarizing film according to any one of claims 1 to 12, which further comprises a compound having a vinyl ether group. The hardenable adhesive composition for a polarizing film according to any one of claims 1 to 13, which further comprises a photoacid generator. The hardenable adhesive composition for a polarizing film according to any one of claims 1 to 14, wherein the cured product obtained by curing the hardened adhesive composition has a storage elastic modulus of 1.0 × 10 ⁷ Pa at 25 °C. A polarizing film which is provided with a transparent protective film on at least one surface of a polarizing member through an adhesive layer, wherein the adhesive layer is a hardening type adhesive for a polarizing film according to any one of claims 1 to 15. A cured layer of the composition is formed. The polarizing film of claim 16, wherein the thickness of the adhesive layer is 0.1 to 3 μm . The polarizing film of claim 16 or 17, wherein the adhesive layer is immersed in pure water at 23 ° C for 24 hours, and the overall water absorption ratio represented by the following formula is 10% by weight or less; and: {(M2-M1)/M1} ×100 (%): M1: weight of cured product before immersion, M2: weight of cured product after immersion. The polarizing film according to any one of claims 16 to 18, wherein the adhesive layer has a storage elastic modulus at 25 ° C of 1.0 × 10 ⁷ Pa or more. A method of producing a polarizing film according to any one of claims 16 to 19, characterized by comprising the step of coating a step of coating the polarizing film with a hardening type adhesive composition At least one surface of the polarizing member and the transparent protective film; a bonding step of bonding the polarizing member to the transparent protective film; and a step of: subsequently adhering the polarizing member and the transparent protective film through an adhesive layer, wherein the bonding The agent layer is obtained by curing the active energy ray-curable adhesive composition by irradiating an active energy ray from the surface of the polarizer or the surface of the transparent protective film. An optical thin film characterized in that at least one optical film according to any one of claims 16 to 19 is laminated. An image display device characterized by using the polarizing film of any one of claims 16 to 19 or the optical film of claim 21.