TW201512348A - Adhesive agent composition, adhesive agent composition for polarizing plate, adhesive agent for polarizing plate, and polarizing plate manufactured using said adhesive agent - Google Patents

Abstract

An adhesive agent composition which is an adhesive agent having excellent adhesion strength, is suitable for the bonding of any one of various protective films for polarizing plates to a polarizer, particularly the bonding of a protective film other than TAC to a polarizer, has excellent production efficiency, and also has excellent color fading resistance. In order to produce the adhesive agent composition, an adhesive agent composition is provided, which comprises (A) a metal or semimetal compound capable of forming a chelate and (B) a photopolymerizable compound having a functional group capable of forming a chelate in conjunction with the metal or semimetal, or which comprises (A-B) a chelate compound formed from (A) a metal or semimetal compound capable of forming a chelate and (B) a photopolymerizable compound having a functional group capable of forming a chelate in conjunction with the metal or semimetal.

Description

Adhesive composition, adhesive composition for polarizing plate, adhesive for polarizing plate, and polarizing plate using the same

The present invention relates to an adhesive composition, an adhesive composition for a polarizing plate, an adhesive for a polarizing plate, and a polarizing plate produced using the same, and more particularly to a liquid crystal display device or the like which is suitable for bonding. An adhesive composition used in an active energy ray-curable acrylic adhesive of a polarizer of a polarizing plate and a protective film.

Liquid crystal display devices are widely used as image display devices such as liquid crystal televisions, computer monitors, mobile phones, and digital phase machines. In the liquid crystal display device, a polarizing plate is laminated on both sides of a glass substrate in which liquid crystal is sealed, and various optical functional films such as a phase difference plate are laminated thereon as needed.

Conventionally, the polarizing plate is used in a structure in which at least one of the polarizers made of a polyvinyl alcohol-based film is bonded to both surfaces with a protective film. Here, in the polarizer, a PVA film formed by using a polyvinyl alcohol-based resin having a high degree of saponification (hereinafter, a polyvinyl alcohol is abbreviated as "PVA") is widely used to disperse and adsorb iodine or the like. The dichroic material is preferably a uniaxially stretched PVA film which is further crosslinked by a crosslinking agent such as boric acid. Since such a polarizer is a uniaxially stretched PVA film and is easily contracted at a high humidity, a protective film is attached to the polarizer in order to reinforce moisture resistance or strength.

As the protective film, transparency, mechanical strength, thermal stability, and moisture barrier properties of a thermoplastic resin such as a cellulose resin, a polycarbonate resin, a cyclic polyolefin resin, a (meth)acrylic resin, and a polyester resin are considered. It is excellent in isotropic properties, and the like, and a protective film made of a triethylenesulfonyl cellulose (TAC) resin is widely used.

Further, these protective films are bonded together by a bonding agent and a polarizer. As the adhesive, it is preferable to use a PVA-based resin aqueous solution from the viewpoint of adhesion to a polarizer having a hydrophilic surface, especially The PVA-based resin aqueous solution mainly composed of a PVA-based resin having a similarly high degree of saponification is preferred.

In recent years, the polarizing plate has been required to be thinned. In place of the TAC film which has been used most recently as a protective film, an acrylic film or a cyclic polyolefin resin film has been used. However, the protective film of the TAC film cannot be used. The conventional PVA-based adhesive and the polarizer are firmly bonded. Therefore, as an alternative to the PVA-based adhesive, various adhesives suitable for bonding a protective film such as an acrylic film or a cyclic polyolefin-based resin film have been developed.

Further, the PVA-based adhesive is used as a solution or a dispersion after using water, so that the water is dried when the adhesive is hardened, the drying of the water takes a long time, and the drying property is poor, which causes the production efficiency of the polarizing plate to decrease. For this point, it is also required to improve.

For example, Patent Document 1 proposes an adhesive comprising a composition containing an epoxy resin containing no aromatic ring as a main component and containing a photocationic polymerization initiator, and describes that the adhesive is a cation caused by irradiation with active energy rays. Since it is hardened by polymerization, even if the resin film with low moisture permeability is used as a protective film, it has sufficient adhesive strength, and does not cause a problem of a poor appearance, etc. It can provide the polarizing board which bonded the protective film on the single surface or both surfaces of a polarizer. .

Further, Patent Document 2 proposes an active energy ray-curable adhesive composition containing three kinds of radically polymerizable compounds having different SP値 as a curing component, and is excellent in adhesion between a polarizer and a protective film, and has durability. An excellent adhesive for water resistance.

Further, Patent Document 3 proposes a radical polymerizable adhesive composition for forming a polarizing plate, which comprises 4-butyl hydroxyacrylate: 20 to 90% by weight, ω-carboxypolycaprolactone acrylate: 1 to 70 by weight %, other radical polymerizable compound: 0 to 15% by weight, photopolymerization initiator: 0.01 to 20% by weight, decane coupling agent: 0 to 10% by weight, and the glass transition temperature after hardening is -80 ～0°C, a PVA-based polarizer and a hard-to-contact protective film represented by an acrylic film or a cycloolefin film are used as a constituent layer, and the force is large, and excellent durability can be formed. A polarizing plate of a small piece of a polarizing plate, and a polarizing plate excellent in press workability can be obtained.

Further, Patent Document 4 proposes an ultraviolet curable composition comprising a (meth)acrylamide compound having no hydroxyl group, an alkyl (meth)acrylate compound having a hydroxyl group, boric acid, and a photopolymerization initiator. By using the adhesive composition, not only a wide variety of protective films but also an ultraviolet curable composition having excellent adhesion strength to the acrylic resin film can be obtained. [Prior Art Literature] [Patent Literature]

Japanese Unexamined Patent Publication No. Publication No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No.

(The subject to be solved by the invention)

However, the adhesive agent of the above-mentioned Patent Document 1 uses a cationically polymerizable ultraviolet curable adhesive instead of the water-based adhesive. However, since the cationically polymerizable ultraviolet-curable adhesive has a dark reaction after ultraviolet irradiation, it is elongated. When the object is rolled into a roll shape, there is a problem that a winding mark is likely to occur during storage. Further, the cationically polymerizable ultraviolet curable adhesive is likely to be affected by the humidity at the time of curing, and there is a problem that the hardened state is likely to be uneven.

In the radically polymerizable ultraviolet curable adhesive of Patent Document 2, since the adhesive layer is relatively hard, the adhesive force is lowered as time passes, and the press-resistant workability or durability is not satisfied.

In the radically polymerizable adhesive composition of the above-mentioned Patent Document 3, when the (meth)acrylic monomer is cured, it is accompanied by hardening and shrinkage, so that the initial stability is lowered, and the subsequent force is insufficient.

The ultraviolet curable composition of Patent Document 4 exhibits an adhesive force with respect to the acrylic resin film, but the adhesion to the polarizer is insufficient, and the discoloration resistance is also weak.

Therefore, the above-mentioned active energy ray-curing type adhesive agent does not require a drying step, and the production efficiency is improved as compared with the PVA-based adhesive used in the form of an aqueous solution, but the protective film for various polarizing plates and the polarizer are sufficiently followed. There are difficulties and further improvements are required.

Moreover, in recent years, when the polarizing plate is left standing under high temperature and high humidity for a long time, there is a problem of discoloration (fading), and it is necessary, for example, that although it is a more severe evaluation, even if it is immersed in warm water, it is not A polarizing plate in which discoloration or a degree of discoloration occurs. In order to obtain such a polarizing plate excellent in discoloration resistance, the adhesives of the above-mentioned Patent Documents 1 to 4 cannot be obtained in the case where the improvement of the adhesive for bonding the polarizer and the protective film is also sought. Decolorization.

In view of the above, an object of the present invention is to provide an adhesive which is excellent in adhesion, and is also suitable for various protective films for polarizing plates and polarizers, in particular, a protective film other than TAC and a polarizer. Further, an adhesive composition which is excellent in production efficiency and excellent in discoloration resistance, particularly an adhesive composition for a polarizing plate. (method of solving the problem)

In view of the circumstances, the inventors of the present invention have found that a metal or semimetal chelate compound exists in the adhesive composition for an active energy ray-curable polarizing plate in the preparation of an adhesive. Further, the polarizer is excellent in adhesion to the protective film, and the discoloration resistance of the polarizing plate is also excellent, and the present invention has been completed.

That is, the gist of the present invention relates to a photopolymerizable compound (B) comprising a metal or semimetal compound (A) capable of forming a chelate and a functional group capable of forming a chelate with the metal or semimetal. The resulting adhesive composition, further relates to a photopolymerizable compound comprising a metal or semimetal compound (A) capable of forming a chelate compound, and a functional group capable of forming a chelate compound with the metal or semimetal ( B) An adhesive composition of the formed chelate compound (AB).

Moreover, the present invention provides an adhesive composition for a polarizing plate using the above-described adhesive composition, an adhesive for polarizing plate obtained by curing the composition, and a polarizer interposed between the polarizing plate and the adhesive. A polarizing plate in which a protective film is bonded.

Here, in the present invention, the presence of a chelate compound of a metal or a semimetal is important, and it is presumed that the hydroxyl group on the surface of the PVA forming the polarizer forms a chemical bond with the functional group capable of forming a chelate in the adhesive, and The adhesion strength between the polarizer and the protective film is increased, and the discoloration resistance of the polarizing plate is improved because the iodine diffusion in the polarizer is prevented. (Effect of the invention)

The adhesive composition of the present invention, particularly the adhesive composition for a polarizing plate, has high production efficiency of a polarizing plate, and can be used for a protective film for various polarizing plates and a polarizer, especially an acrylic film or a cyclic polyolefin resin. The protective film other than the TAC such as a film and the polarizer are sufficiently adhered to obtain a polarizing plate which is excellent in discoloration resistance because the polarizing plate is immersed in high temperature and high humidity or in warm water.

The present invention will be described in detail below, but these are examples of preferred embodiments. Further, in the present invention, the (meth)acrylic group means an acrylic group or a methacryl group, the (meth)acryloyl group means an acryl group or a methacryl group, and the (meth)acrylate means an acrylic group. Ester or methacrylate. Further, the acrylic single system refers to a monomer having at least one of an acrylonitrile group and a methacryl group, and the acrylic resin refers to a resin obtained by polymerizing a polymerization component containing at least one type of acrylic monomer. .

(Binder composition) The adhesive composition of the present invention, characterized in that: [I] comprises a metal or semimetal compound (A) capable of forming a chelate compound, and contains a chelate compound capable of forming a chelate with the metal or semimetal And a functional group of the photopolymerizable compound (B); further characterized in that: [II] comprises a metal or semimetal compound (A) capable of forming a chelate compound, and a material capable of forming a metal or a semimetal The chelate compound (AB) formed by the photopolymerizable compound (B) having a functional group of a chelate compound.

<Metal or semimetal compound (A) capable of forming a chelate compound> The metal or semimetal compound (A) capable of forming a chelate compound used in the present invention is capable of forming a chelate with a photopolymerizable compound (B) described later. The compound may be, for example, an alkoxide selected from a metal or a semimetal, a hydrolyzate of the alkoxide, a condensate of the alkoxide, a chelate compound of an alkoxide, a partial alkoxide of the chelate compound. At least one of the group of compounds, and metal or semi-metal tellurides, particularly a metal or semi-metal alkoxide, a chelate compound of the alkoxide, is preferred, and is represented by the following formula (1). A metal or semimetal alkoxide or a chelate compound of the alkoxide is preferred. In addition, as the metal or semimetal compound (A) which can form a chelate compound, one type of the above-mentioned compounds may be used alone or two or more types may be used in combination.

[Chemical 1]

(wherein M represents a metal or a semimetal atom, R ¹ represents a monovalent organic group having the same or different carbon number of 1 to 10, and R ² represents a hydrogen which may be the same or different or an alkane having a carbon number of 1 to 5 A group or a phenyl group having 1 to 6 carbon atoms or a phenyl group, m and n each represent an integer of 0 or more, and m+n represents an atomic price of M.)

In the above formula (1), M represents a metal or a semimetal atom, for example, a transition element metal, a Group 2, Group 12, Group 13, Group 14 metal or semimetal element, especially boron, lanthanum, aluminum, zirconium, Titanium, magnesium, chromium, cobalt, copper, iron, nickel, vanadium, zinc, indium, calcium, manganese, tin are ideal, more preferably boron, antimony, aluminum, titanium, chromium, copper, iron, nickel, zinc, indium . Further, in general, a 2 to 4 valent metal or a semimetal is used, and particularly boron, ruthenium, aluminum, titanium, or zirconium is preferable. Further, the state of the alkoxide or the telluride is a liquid, and boron and bismuth are most preferable from the viewpoint of handling convenience. Moreover, even if it is a solid state, it is good as the photopolymerizable compound (C) is easy to be soluble.

In the above formula (1), the monovalent organic group having 1 to 10 carbon atoms represented by R ¹ , when the formula (1) is a metal or a semimetal alkoxide, for example, a methyl group or an ethyl group; An alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-hexyl, n-heptyl, n-octyl or 2-ethylhexyl; a fluorenyl group such as propyl fluorenyl, butyl fluorenyl, pentamidine, benzhydryl, toluoyl; vinyl, allyl, cyclohexyl, phenyl, epoxypropyl, (meth)acrylic acid Examples of the oxy group, the ureido group, the decylamino group, the fluoroacetamido group, and the isocyanate group include substituted derivatives of the above groups. As the substituent in the substituted derivative, for example, a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, or a (meth)acrylic acid Alkoxy group, ureido group, ammonium salt group, and the like. However, the number of carbon atoms of R ¹ composed of the substituted derivatives is 10 or less including the carbon atoms in the substituent.

Further, when the above formula (1) is a metal or a semimetal halide, R ¹ may, for example, be an ethoxycarbonyl group, a propenyloxy group, a butoxy group, a pentyloxy group or a benzamidine group. A methoxy group such as tolylmethoxy group. Further, in the above formula (1), when two or more R ¹ are present, they may be the same or different, but are preferably the same.

In the above formula (1), the alkyl group having 1 to 5 carbon atoms represented by R ² is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or tert-butyl. Examples of the fluorenyl group having a carbon number of 1 to 6, such as an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like. Further, R ² may also represent hydrogen. Further, in the above formula (1), when a plurality of R ² are present, they may be the same or different, and are preferably the same.

In the present invention, the hydrolyzate of the metal or semimetal alkoxide is hydrolyzed by the OR ² group contained in the above metal or semimetal alkoxide, but does not require the full hydrolysis of the OR ² contained in the metal or semimetal alkoxide. For example, only one of them may be hydrolyzed, two or more of them may be hydrolyzed, or a mixture thereof.

In the present invention, the condensate of the metal or semimetal alkoxide refers to a structure in which the hydrolyzate of the above metal or semimetal alkoxide is condensed to have a structure of MOM, but the present invention does not require the condensation of the hydroxyl group of the hydrolyzate. The concept includes a mixture of only a part of the hydroxyl group, a mixture of different degrees of condensation, and the like.

In the present invention, a chelate compound of a metal or semimetal alkoxide refers to a compound having a structure in which at least one of the ligands of a metal or a semimetal alkoxide is chelated and bonded. The chelate compound of the metal or semimetal alkoxide is preferably a metal or semimetal alkoxide, and is selected from the group consisting of β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylic acid salts, hydroxycarboxylic acid esters, The reaction of at least one of the keto alcohol and the amino alcohol is preferably obtained.

Among these compounds, β-diketones or β-ketoesters are preferably used, and specific examples thereof include ethyl acetoacetate, ethyl acetoacetate, ethyl acetate and ethyl acetate. Propyl ester, isopropyl acetate, n-butyl acetate, n-butyl acetate, tert-butyl acetate, 2,4-hexanedione, 2,4-heptanedione, 3 , 5-heptanedione, 2,4-octanedione, 2,4-nonanedione, 5-methyl-hexanedione, and the like. Among these, it is preferred to use ethyl acetonylacetate or ethyl acetonitrile.

In the present invention, the hydrolyzate of the chelating compound and the hydrolyzate of the above metal or semimetal alkoxide are not required to be all hydrolyzed by the OR ² group contained in the chelating compound, and for example, only one of the hydrolyzed ones or two or more may be used. Hydrolyzed, or a mixture of such.

In the present invention, the metal or semimetal telluride means that at least one of the ligands of the above metal or semimetal alkoxide is a decyloxy group.

Among the metal or semimetal compound (A) capable of forming a chelate compound, specific examples of the chelate compound of a metal or a semimetal alkoxide and a metal or a semimetal alkoxide include: [1] boric acid, boric acid Trimethyl ester, triethyl borate, tributyl borate (including normal-, iso-, tertiary-, secondary-), tripropyl borate, triisopropyl borate, trimethyl carbitol borate Equal boron compound;

[2] Aluminium Hydroxide, Triethoxy Aluminium, Diethoxy, Ethyl Acetone, Aluminum, Ethoxy, Bis(acetyl)pyruvate, Aluminum, Ethyltriacetate, Tripropyl Aluminium oxy-aluminum, dipropoxy-ethyl acetonate, aluminum, propoxy, bis(acetyl)pyruvate, aluminum tributoxide, dibutoxy, aluminum acetonate, butoxy Bis(acetylthiopyruvate) aluminum, diethoxyethyl ethylacetate aluminum, ethoxy, bis(ethylacetamidineacetic acid) aluminum, ginseng (ethyl acetoacetate) aluminum, dipropoxy・Aluminum compounds such as ethyl acetoacetate aluminum, propoxy bis, ethyl acetoacetate, aluminum dibutoxide, ethyl acetoacetate, butanoxy, bis(ethyl acetonitrile) aluminum ;

[3] Titanium hydroxide, titanium tetraethoxide, titanium triethoxy, titanium acetonate, titanium diethoxy, bis(acetylthiopyruvate), ethoxy, ginseng (acetylthiopyruvate) Titanium, lanthanum (ethionylpyruvate) titanium, tetrapropoxy titanium, tripropoxy acetyl acetonate, titanium dipropoxy bis(acetyl thiopyruvate), propoxy oxy (acetyl acetylpyruvate) titanium, titanium tetrabutoxide, titanium tributoxide, titanium acetonate, titanium dibutoxide, bis(acetylthiopyruvate), butoxy; ginseng Pyruvic acid) titanium, triethoxy, ethyl acetoacetate, titanium, diethoxy, bis(ethyl acetonitrile) titanium, ethoxy, ginseng (ethyl acetoacetate) titanium, strontium (ethyl Ethyleneacetate) titanium, tripropoxy, ethyl acetoacetate, titanium, dipropoxy. Bis(ethylacetamidineacetic acid) titanium, propoxy, ginseng (ethyl acetoacetate) titanium, tributoxy, ethyl acetoacetate, titanium, dibutoxy bis (ethyl acetonitrile) titanium a titanium compound such as butoxy or ginseng (ethyl ethyl acetonitrile) titanium;

[4] cerium (methoxy) zirconium, cerium (ethoxy) zirconium, cerium (propoxy) zirconium, cerium (isopropoxy) zirconium, cerium (butoxy) zirconium, cerium (isobutoxy) Zirconium, lanthanum (2nd butoxy) zirconium, cerium (3, butoxy) zirconium, cerium (pentyloxy) zirconium, cerium (3 pentyloxy) zirconium, cerium [2-(2-methoxy) Ethyl]zirconium, iridium [2-(1-methyl-2-methoxy)propoxy]zirconium, ruthenium [2-(2-methoxy)propoxy]zirconium, ruthenium [2] -(dimethylamino)ethoxy]zirconium, ruthenium [2-(2-dimethylamino-1-methyl)propoxy]zirconium, anthracene [2-(2-dimethylamino)propoxy Zirconium, bis(2-propoxy)bis[2-(2-dimethylamino-1-methyl)propoxy]zirconium, bis(t-butoxy)bis[2-(2- Dimethylamino-1-methyl)propoxy]zirconium, bis(t-butoxy)bis[2-(2-dimethylamino)propoxy]zirconium, (3th butoxy) ginseng [2-(2-Dimethylamino-1-methyl)propoxy]zirconium, ginseng (3rd butoxy) [2-(2-dimethylamino-1-methyl)propoxy] Zirconium alkoxide zirconium compound; cerium (dimethylamino) zirconium, cerium (diethylamino) zirconium, cerium (ethyl methylamino) zirconium, cerium (dipropyl) zirconium, cerium (dibutylamine) Zirconium, bis(dimethylamino)bis(diethylamino)zirconium, bis(diethylamino)bis(ethylmethylamino)zirconium, (diethyl) Ginseng (methylmethylamino) zirconium or the like, or bis(methoxy)bis(dimethylamino)zirconium, bis(methoxy)bis(diethylamino)zirconium, bis(methoxy) Bis(ethylmethylamino)zirconium, bis(ethoxy)bis(dimethylamino)zirconium, bis(ethoxy)bis(diethylamino)zirconium, bis(ethoxy)bis(ethyl) Methylamino)zirconium, bis(2-propoxy)bis(diethylamino)zirconium, bis(butylene)bis(diethylamino)zirconium, bis(butylene)bis(ethyl) An aminozirconium compound such as zirconium, zirconium, (t-butyl) ginseng (ethylmethyl) zirconium, or decyl acetonate, acenaphthyl acetate, hexane-2, 4-diketonate, indole-5-methylhexane-2,4-dione acid ester, heptane-2,4-dione acid ester, indole-2-methylheptane-3,5 -diketoester, indole-5-methylheptane-2,4-dione acid ester, indole-6-methylheptane-2,4-dione acid ester, indole-2,2-dimethyl Hepeptane-3,5-diketonate, indole-2,6-dimethylheptane-3,5-dione ester, indole-2,2,6-trimethylheptane-3, 5-diketonate, 肆-2,2,6,6-tetramethylheptane-3,5-dione ester, 肆-octane-2,4-dione ester, 肆-2, 2,6-trimethyloctane-3,5-diketonate, indole-2,6-dimethyloctane-3,5-diketonic acid Ester, indole-2-methyl-6-ethylnonane-3,5-dione ester, indole-2,2-dimethyl-6-ethyldecane-3,5-dione ester Equivalent alkyl substituted β-diketonate, 肆-1,1,1-trifluoropentane-2,4-dione ester, 肆-1,1,1-trifluoro-5,5-di Methyl hexane-2,4-dione ester, 肆-1,1,1,5,5,5-hexafluoropentane-2,4-dione ester, 肆-1,3-two Fluorine-substituted alkyl β-diketone esters such as fluorohexylpropane-1,3-dione ester, 肆-1,1,5,5-tetramethyl-1-methoxyhexane-2,4 -Diketonate, 肆-2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, 肆-2,2,6,6-tetramethyl a β-diketone zirconium compound such as a β-diketonate ester substituted with an ether such as 1-(2-methoxyethoxy)heptane-3,5-dione acid ester;

[5] Zinc hydroxide, zinc diethoxy zinc, zinc ethoxylate, zinc bis(ethylmercaptopyruvate), zinc dipropoxide, zinc propoxide, zinc acetophenone, two Zinc butoxide, zinc butoxide, zinc acetophenone, zinc ethoxylate, ethyl acetoacetate, zinc bis(ethyl acetonitrile), propoxy, zinc ethyl acetoacetate, butoxy a zinc compound such as zinc ethyl acetoacetate, zinc bis(ethyl acetylacetonate) or zinc di(ethyl acetoacetate);

[6] Tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxydecane, tetraisobutoxydecane, tetra-butoxydecane And a tetraalkoxydecane such as tetrabutyloxydecane, and a hydrazine compound such as a compound obtained by hydrolyzing (condensing) the same.

Among these metal or semimetal alkoxides and the chelating compound, preferred are boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, aluminum hydroxide, and triethyl ethane. Aluminium oxyaluminum, aluminum tripropoxide, aluminum tributoxide, aluminum dipropoxide, ethyl acetoacetate, aluminum ginseng (ethyl acetoacetate), aluminum ginseng (acetyl acetonate), hydrogen peroxide Titanium, dibutoxy, bis(acetylthiopyruvate) titanium, dipropoxy, bis(acetylthiopyruvate) titanium, diethoxy bis(acetylthiopyruvate) titanium, dibutoxy Base, bis(ethyl acetonitrile) titanium, dipropoxy bis (ethyl acetonitrile) titanium, diethoxy bis (ethyl acetonitrile) titanium, zinc hydroxide, bis (ethyl hydrazine) Zinc pyruvate zinc, di(ethylacetylacetic acid) zinc, particularly desirable compounds are boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, aluminum hydroxide, tripropoxy Aluminium, ginseng (acetoxypyruvate) aluminum, dibutoxy, bis(acetylthiopyruvate) titanium, bis(acetylthiopyruvate) zinc, and the like. Further, boric acid, trimethyl borate, and boric acid are considered from the viewpoints of ease of operation in a liquid state at room temperature, solubility in a photopolymerizable compound (C), or reactivity with a hydroxyl group of a PVA resin forming a polarizer. Triethyl esters such as triethyl ester, tripropyl borate and tributyl borate having a C 1 to 5 alkyl group, particularly tributyl borate, are most preferred.

Further, specific examples of the metal or semimetal telluride include dihydroxy, titanium dibutyrate, diisopropoxy titanium, titanium diacetate, diisopropoxy titanium diisopropylate, and diisopropoxy group. Titanium dimalate, titanium diisopropoxide, titanium dibenzoate, zirconium di-n-butoxy, zirconium diacetate, aluminum diisopropylaluminate, etc., and particularly preferred compounds are dihydroxy-titanium dibutyrate. A titanium compound such as diisopropoxy or titanium diacetate.

<Photopolymerizable compound (B) containing a functional group capable of forming a chelate with the metal or semimetal> Further, photopolymerization containing a functional group capable of forming a chelate with the above metal or semimetal as the present invention The compound (B) may be any compound having such a functional group and an ethylenically unsaturated group.

a functional group capable of forming a chelate with the above metal or semimetal, for example, a β-diketone structure having a β-diketone structure, a malonate or the like, but considering a general use The viewpoint of reactivity, convenience, and reactivity with a hydroxyl group is preferred.

In the present invention, the photopolymerizable compound (B) containing a functional group capable of forming a chelate compound with a metal or a semimetal is in the case of an ethylenically unsaturated compound (b1) containing an ethylidene group, for example, as follows Method of manufacturing.

(I) reacting a functional group-containing ethylenically unsaturated compound (i) with diketene. The functional group may, for example, be a hydroxyl group, a guanamine group, a carbamate group, an amine group, a carboxyl group or the like. The desired functional group-containing ethylenically unsaturated compound (i) is a fat having an alkyl group having 1 to 10 carbon atoms. The family contains an alkyl (meth) acrylate compound, particularly preferably 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate. And (meth) acrylate having a hydroxyalkyl group having 1 to 5 carbon atoms, such as 2-hydroxy-3-chloropropyl (meth)acrylate.

(II) The above-mentioned functional group-containing ethylenically unsaturated compound (i) is subjected to transesterification with acetamidine acetate.

The reaction of diketene in the case of the above (I) may be carried out without a catalyst, or may be a tertiary amine, an acid (sulfuric acid or the like), a basic salt (sodium acetate or the like), or an organometallic compound (lauric acid). It is carried out in the presence of a catalyst such as dibutyltin. The reaction of the above (II) acetamidine acetate is preferably carried out in the presence of a transesterification catalyst such as calcium acetate, zinc acetate or lead oxide. Among the functional group-containing ethylenically unsaturated compound (i), it is preferred to use a hydroxyalkyl group-containing (meth) acrylate from the viewpoints of versatility, convenience, stability at the time of production or storage, and the like. .

<Photopolymerizable Compound (C)> In the present invention, the photopolymerizable compound (C) is further contained (except that the photopolymerizable compound (B) is excluded) from the viewpoints of coatability, curability, and adhesion. ideal. The photopolymerizable compound (C) used in the present invention is preferably one selected from the group consisting of an ethylenically unsaturated compound (c1) having one ethylenically unsaturated group, and two or more of the photopolymerizable compound (B). At least one of the group of ethylenically unsaturated ethylenically unsaturated compounds (c2) is preferred.

An ethylenically unsaturated compound having one ethylenically unsaturated group (hereinafter sometimes referred to simply as "monofunctional monomer") (c1), for example, styrene, vinyl toluene, chlorostyrene, α-methyl Styrene, methyl (meth)acrylate, ethyl (meth)acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (A) 2-hydroxybutyl acrylate, phenoxyethyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate Propyl propyl ester, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, (methyl) Cyclohexyl acrylate, isodecyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ( Dicyclopentyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, Ethyl (meth) acrylate, Isodecyl (meth)acrylate, dodecyl (meth)acrylate, n-stearyl (meth)acrylate, benzyl (meth)acrylate, phenol ethylene oxide modified (n=2) (A Acrylate, nonylphenol propylene oxide modified (n=2.5) (meth) acrylate, 2-(meth) propylene methoxyethyl phosphate, 2-(methyl) propylene hydride Semi-(meth) acrylate of phthalic acid derivatives such as oxy-2-hydroxypropyl phthalate, decyl (meth) acrylate, carbitol (meth) acrylate, (a) Benzyl acrylate, butoxyethyl (meth)acrylate, allyl (meth) acrylate, propylene fluorenyl Porphyrin, dimethyl methacrylamide, 2-hydroxyethyl acrylamide, N-methylol (meth) acrylamide, N-vinyl pyrrolidone, 2-vinyl pyridine, polyoxyethylene 2 grade alkyl ether Acrylate and the like.

Further, in addition to this, a Michael addition of acrylic acid or a mono-ethyl propylene oxyethyl dicarboxylate may be used in combination, and as a Michael addition of acrylic acid, an acrylic acid dimer or methacrylic acid may be mentioned. Dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, and the like. Further, as the 2-propenylmethoxyethyl dicarboxylic acid monoester, a carboxylic acid having a specific substituent such as 2-propenyloxyethyl succinic acid monoester or 2-methylpropenyl oxyethyl ester Succinic acid monoester, 2-propenyloxyethyl phthalate monoester, 2-methylpropenyloxyethyl phthalate monoester, 2-propenyl methoxyethyl hexahydrophthalic acid Monoester, 2-methylpropenyloxyethylhexahydrophthalic acid monoester, and the like. Further, other oligoester acrylates may also be mentioned.

In addition, examples of the ethylenically unsaturated compound having two or more ethylenically unsaturated groups (hereinafter sometimes simply referred to as "polyfunctional monomer") (c2) include a bifunctional monomer and a trifunctional or higher monomer.

A bifunctional monomer such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(methyl) Acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol II ( Methyl) acrylate, neopentyl glycol di(meth) acrylate, ethylene oxide modified bisphenol A type di(meth) acrylate, propylene oxide modified bisphenol A type di(methyl) Acrylate, cyclohexanedimethanol di(meth)acrylate, ethoxylated cyclohexanedimethanol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, three Cyclodecane dimethanol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(meth) acrylate, ethylene glycol Diglycidyl di(meth) acrylate, diethylene glycol diglycidyl di(meth) acrylate, diglycidyl phthalate di(meth) acrylate, hydroxy trimethyl Modified acetic acid Pentandiol di(meth)acrylate, isocyanuric acid ethylene oxide modified diacrylate, and the like.

a trifunctional or higher monomer such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth) acrylate, tris(meth) propylene methoxy ethoxy trimethylol propane, glycerol polyglycidyl ether poly(meth) acrylate, isocyanuric acid oxirane Modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, Caprolactone modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide Modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, ethoxylated glycerin triacrylate, and the like. The photopolymerizable compound (C) may be used alone or in combination of two or more.

In summary, the present invention is: [I] a photopolymerizable compound (B) comprising a metal or semimetal compound (A) capable of forming a chelate and a functional group capable of forming a chelate with the metal or semimetal. Further, it further comprises an adhesive composition in which another photopolymerizable compound (C) (except that the photopolymerizable compound (B) is excluded), and [II] contains a metal or a semimetal compound capable of forming a chelate compound ( A) a chelate compound (AB) formed of a photopolymerizable compound (B) containing a functional group capable of forming a chelate with the metal or a semimetal, preferably further comprising another photopolymerizable compound (C) ( The binder composition obtained by excluding the photopolymerizable compound (B) is excluded.

Regarding the blending ratio of (A) and (B), (A)/(B) is preferably 1/99 to 50/50 by weight, particularly 5/95 to 40/60, more preferably 10 by weight. /90~30/70. If the enthalpy of (A)/(B) is too small, the adhesion between the polarizer and the protective film may be lowered or the discoloration resistance may be lowered, and if it is too large, the durability at the time of the warm water test may be lowered. .

In the case of the above [I], (A) to (C) may be appropriately blended to form an adhesive composition. The ratio of each of (A) to (C) is (A) is 0.1 to 30% by weight, (B) is 0.9 to 40% by weight, and (C) is 30, based on the total of (A) to (C). Preferably, it is from 99 to 20% by weight, (A) is from 0.5 to 20% by weight, (B) is from 1.5 to 30% by weight, (C) is preferably from 50 to 98% by weight, and more preferably (A) is from 1 to 15%. The weight %, (B) is 5 to 20% by weight, and (C) is 65 to 94% by weight. If the content of the (A) is too small, the adhesion between the polarizer and the protective film may be lowered, or the decolorization resistance may be lowered. If there is too much, the durability may be lowered during the warm water resistance test, or the polarizer may be The tendency of the adhesion of the protective film to decrease. If the content of the component (B) is too small, the adhesion between the polarizer and the protective film tends to decrease, and if it is too much, the durability against the warm water test tends to decrease. If the content of the component (C) is too small, the durability against the warm water test tends to be lowered, and if there is too much, the adhesion between the polarizer and the protective film tends to decrease.

In the present invention, the adhesive composition containing (A) and (B), preferably further containing (C), is applied to a substrate such as a polarizer, and is usually 50 to 200 ° C, particularly preferably 60 °. Drying at 150 ° C can form a chelate compound (AB). Further, after the composition of the adhesive containing (A) and (B), preferably further containing (C), usually at 50 to 120 ° C, particularly preferably 60 to 90 ° C, (A) and (B) The reaction can form a chelate compound (AB).

Further, in the case of [II], the chelating compound (AB) formed of (A) and (B) may be contained, and it is preferable to further contain (C), but it may also contain (A), (B), The chelate compound (AB) formed of (A) and (B), and preferably contains (C).

The content of the chelating compound (A-B) is preferably from 0.5 to 50% by weight, particularly preferably from 1 to 40% by weight, more preferably from 5 to 30% by weight. If the content is too small, the adhesion between the polarizer and the protective film is lowered, and the discoloration resistance tends to be lowered. If there is too much, the durability in the warm water resistance test may be lowered, or the polarizer and the protective film may be used. Then the tendency of the force to decrease.

When the chelate compound (A-B) is formed, it is usually mixed at 20 to 120 ° C, especially at 30 to 80 ° C.

In the present invention, by the presence of the above-mentioned metal or semimetal chelate compound, the effect of excellent discoloration resistance of the polarizing plate can be exhibited.

The adhesive composition of the present invention may be blended with a polymerization initiator, a decane coupling agent, an antistatic agent, other acrylic binders, other binders, and amines, within the range not impairing the effects of the present invention. Adhesive-imparting agent such as an acid ester resin, a rosin, a rosin ester, a hydrogenated rosin ester, a phenol resin, an aromatic modified terpene resin, an aliphatic petroleum resin, an alicyclic petroleum resin, a styrene resin, or a xylene resin a conventionally known additive such as a plasticizer such as a polyhydric alcohol, a coloring agent, a filler, an anti-aging agent, an ultraviolet absorber, or a functional dye, or a compound which may be colored or discolored by ultraviolet rays or radiation, and the like. The blending amount is preferably 30% by weight or less based on the entire composition, and particularly preferably 20% by weight or less.

In addition to the above additives, impurities and the like contained in the raw material of the constituents of the constituents of the adhesive composition may be contained in a small amount.

<Polymerization initiator (D)> In the present invention, it is preferred to further contain the above polymerization initiator (D) and to cure the adhesive composition. As the polymerization initiator (D), for example, various polymerization initiators such as a photopolymerization initiator (d1) and a thermal polymerization initiator (d2) can be used, but in particular, a photopolymerization initiator (d1) can be used. It is preferable to use the active energy irradiation hardening such as ultraviolet rays for a short period of time.

Further, when the photopolymerization initiator (d1) is used, the adhesive composition is cured by active energy ray irradiation, and when the thermal polymerization initiator (d2) is used, the adhesive composition is cured by heating. It is also desirable to use both.

The above photopolymerization initiator (d1), for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4-( 2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Oxo (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenones such as phenylphenyl)butanone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone oligomer; benzoin and benzoin Methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin; diphenyl ketone, methyl o-benzoyl benzoate, 4-phenyl diphenyl ketone , 4-benzylidene-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetrakis(t-butoxycarbonyl)diphenyl ketone, 2,4,6-three Methyldiphenyl ketone, 4-benzylidene-N,N-dimethyl-N-[2-(1-o-oxy-2-propenyloxy)ethyl]benzylammonium bromide, Diphenyl ketones such as (4-benzylidenebenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthene Ketone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H- Thioxanthone such as thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)- a fluorenylphosphine oxide such as 2,4,4-trimethyl-pentylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; In addition, these photopolymerization initiators (d1) may be used alone or in combination of two or more.

Further, as such an auxiliary agent, triethanolamine, triisopropanolamine, 4,4'-dimethylaminodiphenyl ketone (milaxone), 4,4'-diethylamino group may be used in combination. Phenyl ketone, 2-dimethylaminoethyl benzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylamino benzene Isoamyl formate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzhydryl isopropyl ether, 4-(2-hydroxyethoxy)-phenyl (2-hydroxy-2- Propyl)ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one is preferred.

Further, the above thermal polymerization initiator (d2), for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetonitrile acetate peroxide, ethyl acetonitrile Acid ester peroxide, 1,1-bis(Third-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(trihexylperoxy)-cyclohexane, 1 , 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1, 1-bis(t-butylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethyl Butyl hydrogen peroxide, cumene hydroperoxide, third hexyl hydroperoxide, tert-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, diiso Propyl phenyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, tert-butyl cumyl peroxide, di-tert-butyl peroxide , 2,5-dimethyl-2,5-bis (t-butyl) 3-hexyne, peroxide isobutyl sulfonium, 3,5,5-trimethylhexyl decyl peroxide, octyl peroxide, oxidized laurel, stearyl peroxide, amber Acid peroxide, m-toluamyl benzhydryl peroxide, benzammonium peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, diperoxydicarbonate Tert-butylcyclohexyl ester), di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxyperoxydicarbonate Butyl ester, di-5-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, α,α'-bis(neonyl peroxide) Diisopropylbenzene, cumene peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate Ester, perhexyl peroxy neodecanoate, tert-butyl peroxy neodecanoate, trihexyl peroxydiacetate, tert-butyl peroxytrimethylacetate, 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexanoate , 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, third hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate Ester, third hexyl isopropyl isopropyl monocarbonate, tert-butyl isobutyrate, third butyl maleate, peroxy-3,5,5-trimethylhexanoic acid Butyl ester, tributyl butyl laurate, tert-butyl isopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxyacetate, peroxidation Tert-butyl tolylbenzylbenzoate, tert-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis ( Meta-toluidine-based peroxy)hexane, benzoyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzylammonium peroxy)hexane, peroxyallyl Tert-butyl carbonate, tributyltrimethyldecane peroxide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, 2,3-dimethyl- Organic peroxide-based initiator such as 2,3-diphenylbutane; 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano) -1-methylethyl)azo]mercaptoamine, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile) , 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine) Hydrogen chloride, 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrogen chloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropane脒] Dihydrogen chloride, 2,2'-azobis[N-(4-hydrophenyl)-2-methylpropanthene]hydrogen dichloride, 2,2'-azobis[2-methyl-N- (phenylmethyl)propanoid]hydrogen dichloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propene]hydrogen dichloride, 2,2'-azobis[N -(2-hydroxyethyl)-2-methylpropanthene]hydrogen dichloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrogen, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]hydrogen dichloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H) -1,3-diazepine-2-yl)propane]hydrogen dichloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]hydrogen dichloride , 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]hydrogen dichloride, 2,2'-azobis[2-[ 1-(2-hydroxyethyl)-2- Oxazolin-2-yl]propane]hydrogen dichloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl- N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxyl) Ethyl]propanolamine], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide], 2,2'-azobis(2-methyl) Propionamide, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 2,2-azo Di(2-methylpropionic acid) dimethyl ester, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(hydroxymethyl)propanenitrile], etc. An azo initiator; In addition, these thermal polymerization initiators (d2) may be used alone or in combination of two or more.

The content of the polymerization initiator (D) is preferably 0.5 in terms of the total of the above (A) and (B) (in the case of (C), the total of (A) to (C)). It is preferably from 20 parts by weight, particularly preferably from 0.8 to 15 parts by weight, more preferably from 1 to 10 parts by weight. When the content of the polymerization initiator (D) is too small, the curing property is insufficient, and the physical properties tend to be unstable. If too much, the low molecular weight component is increased, the crosslinking density is lowered, and the water resistance or heat resistance is lowered. Propensity.

In the present invention, in addition to the above components, a urethane (meth) acrylate compound (E), a polymer (F), an acid group-containing monomer (G), and a photobase generator (H) are appropriately contained. As a blending agent, it is preferable to consider the viewpoints of coatability, hardenability, and adhesion. These may be used alone or in combination of two or more. Among the above compounds, it is preferred to blend the urethane (meth) acrylate compound (E), especially the urethane (meth) acrylate compound (E) and the polymer (F). The system is more ideal.

<A urethane (meth) acrylate type compound (E)> The urethane (meth) acrylate type compound (E) is a hydroxyl group-containing (meth) acrylate type compound ( E1), a polyisocyanate compound (e2) and a polyol compound (e3) are reacted (E1), or a hydroxyl group-containing (meth)acrylate compound (e1) or a polyvalent isocyanate compound (e2) The reaction is made (E2). Among them, a urethane (meth) acrylate system obtained by reacting a hydroxyl group-containing (meth) acrylate compound (e1), a polyvalent isocyanate compound (e2), and a polyol compound (e3) is particularly preferable. Compound (E1).

The weight average molecular weight of the urethane (meth) acrylate compound (E) used in the present invention is preferably from 500 to 50,000, more preferably from 1,000 to 30,000. If the weight average molecular weight is too small, the hardening shrinkage becomes large, and the force tends to decrease. If it is too large, the water resistance tends to decrease.

In addition, the weight average molecular weight is a weight average molecular weight converted from a standard polystyrene molecular weight, and is used in a high-speed liquid chromatograph ("Shodex GPC system-11 type" manufactured by Showa Denko Co., Ltd.) in series with three columns: Shodex GPC KF-806L (excluding the limit molecular weight: 2 × 10 ⁷ , separation range: 100 ~ 2 × 10 ⁷ , theoretical number of layers: 10,000 layers / support, filler material: styrene-divinylbenzene copolymer, filler The particle size: 10 μm) was measured.

The viscosity of the above urethane (meth)acrylate compound (E) at 60 ° C is preferably 500 to 150,000 mPa ‧ , more preferably 500 to 120,000 mPa s, and still more preferably 1000 ~100,000 mPa‧s. When the viscosity is outside the above range, the coating property tends to be lowered. Further, the viscosity measurement method was carried out using an E-type viscometer.

As the hydroxyl group-containing (meth)acrylate compound (e1), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate Hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate or 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-(methyl) propylene hydride Oxyethyl-2-hydroxypropyl phthalate, caprolactone modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth) acrylate, fatty acid modified (meth) acrylate Glycidyl propyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-(methyl) propylene methoxy propyl (meth) acrylate, Glycerol di(meth)acrylate, 2-hydroxy-3-propenyloxypropyl methacrylate, pentaerythritol tri(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, ring Oxyethane modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol Penta(meth)acrylate and the like.

Among these, a hydroxy (meth) acrylate type compound having one ethylenically unsaturated group is preferred because it can alleviate the hardening shrinkage when forming a coating film, and more preferably (meth)acrylic acid. 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. In the case of using a hydroxyalkyl (meth) acrylate, in particular, when 2-hydroxyethyl (meth) acrylate is used, it is preferable from the viewpoint of excellent reactivity and general versatility. In addition, one type or a combination of two or more types may be used.

As the polyvalent isocyanate compound (e2), for example, methylphenyl diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl Aromatic polyisocyanates such as xylene diisocyanate, phenyl diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diazonic acid diisocyanate, and isocyanuric acid triisocyanate Aliphatic polyisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, etc. Ring-type polyisocyanate, or a 3-mer compound or a polymer compound of such a polyisocyanate, an allophanate type polyisocyanate, a diurea type polyisocyanate, a water-dispersible polyisocyanate (for example, a Japanese polyamine) "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc. manufactured by the formic acid ester company.

Among these, in view of the fact that yellowing is small, it is preferable to use an aliphatic diisocyanate such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate or diazonic acid diisocyanate, or hydrogenated diphenylmethane diisocyanate. An alicyclic diisocyanate such as hydrogenated xylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate or 1,3-bis(isocyanatemethyl)cyclohexane is preferred, and it is particularly preferred to consider hardening. From the viewpoint of reduction, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylene diisocyanate are preferably used. Further, in view of excellent reactivity and general versatility, isophorone diisocyanate is preferably used.

Examples of the polyol compound (e3) include a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, a polybutadiene polyol, and a (meth)acrylic resin. Polyol, polyoxyalkylene polyol, and the like.

The polyether polyol, for example, a polyether polyol containing an alkylene group structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol, or polyhexamethylene glycol, Or such random or block copolymers of polyalkylene glycols.

The polyester-based polyol, for example, a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); and a component obtained from three components of a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester Reaction product, etc.

The aforementioned polyol, for example: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene glycol, 1,3-tetramethylene glycol, 2- Methyl-1,3-triethyl glycol, 1,5-pentamethylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 3-methyl-1,5- Pentaethylene glycol, 2,4-diethyl-1,5-pentamethylene glycol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediol (1, 4-cyclohexanediol or the like), bisphenols (such as bisphenol A), sugar alcohols (xylitol, sorbitol, etc.), and the like.

As the polyvalent carboxylic acid, for example, malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc. Group of dicarboxylic acids; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, benzoic acid An aromatic dicarboxylic acid such as a dicarboxylic acid or a trimellitic acid.

Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

Examples of the polycarbonate-based polyol include a reaction product of a polyol and phosgene; a ring-opening polymer of a cyclic carbonate (such as a alkyl carbonate).

Examples of the polyhydric alcohol include a polyhydric alcohol exemplified in the description of the polyester-based polyol, and the alkylene carbonate, for example, ethyl carbonate, propylene carbonate, butyl carbonate, hexyl carbonate, and the like. .

Further, the polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and a terminal hydroxyl group, and may have both a carbonate bond and an ester bond.

The polyolefin-based polyol may, for example, be a homopolymer or a copolymer of ethylene, propylene, butylene or the like as a saturated hydrocarbon skeleton and having a hydroxyl group at its molecular terminal.

Examples of the polybutadiene-based polyol include a copolymer having butadiene as a hydrocarbon skeleton and a hydroxyl group at a molecular terminal thereof. The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol obtained by hydrogenating all or a part of the ethylenically unsaturated group contained in the structure.

The (meth)acrylic polyol may, for example, be a (meth) acrylate having at least two hydroxyl groups in the molecule of the polymer or copolymer, for example, (meth)acrylic acid ester, for example, (meth)acrylic acid. Methyl ester, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-(meth)acrylate An alkyl (meth)acrylate such as ethylhexyl ester, decyl (meth)acrylate, dodecyl (meth)acrylate or octadecyl (meth)acrylate.

The polyoxyalkylene-based polyol is, for example, a dimethylpolydecane polyol or a methylphenyl polyoxane polyol.

Among these, a polyester-based polyol or a polyether-based polyol is preferable, and in particular, a polyester-based polyol is preferably used from the viewpoint of excellent mechanical properties such as flexibility at the time of curing.

The weight average molecular weight of the polyol compound (e3) is preferably from 500 to 8,000, more preferably from 550 to 5,000, still more preferably from 600 to 3,000. When the molecular weight of the polyol compound (e3) is too large, the strength tends to decrease, and if it is too small, the water resistance tends to decrease.

In the present invention, the urethane (meth) acrylate compound (E) can be produced in the following manner. The following description is directed to a urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound (e1), a polyvalent isocyanate compound (e2), and a polyol compound (e3). Although the compound (E1) is described, a urethane (methyl) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (e1) and a polyvalent isocyanate compound (e2) may be produced according to the method. Acrylate compound (E2).

In the method for producing a urethane (meth) acrylate compound (E1), the hydroxyl group-containing (meth) acrylate compound (e1), the polyvalent isocyanate compound (e2), and the polyol compound ( E3) It may be added to the reactor in whole or in a single reaction, but a hydroxyl group-containing (methyl group) is added to the reaction product obtained by previously reacting the polyol compound (e3) with the polyvalent isocyanate compound (e2). When the acrylate-based compound (e1) is allowed to react, it is useful from the viewpoint of reaction stability or reduction of by-products.

A known reaction method can be used for the reaction of the polyol compound (e3) with the polyvalent isocyanate compound (e2). In this case, for example, the molar ratio of the hydroxyl group in the isocyanate group:polyol compound (e3) in the polyvalent isocyanate compound (e2) is usually about 2n:(2n-2) (n is 2 or more) In the integer), after the terminal isocyanate group-containing urethane (meth) acrylate type compound having an isocyanate group is obtained, an addition reaction with the hydroxyl group-containing (meth) acrylate type compound (e1) can be carried out.

The addition reaction of the reaction product obtained by previously reacting the polyol compound (e3) with the polyvalent isocyanate compound (e2) and the hydroxyl group-containing (meth) acrylate compound (e1) may be a known reaction. method.

Reaction molar ratio of reaction product to hydroxyl group-containing (meth) acrylate compound (e1), for example, two isocyanate groups of polyisocyanate compound (e2), hydroxyl group-containing (meth) acrylate compound When there is one hydroxyl group (e1), the reaction product: the hydroxyl group-containing (meth)acrylate compound (e1) is about 1:2, and the polyisocyanate compound (e2) has three isocyanate groups, and the hydroxyl group is contained. When the hydroxyl group of the (meth) acrylate type compound (e1) has one, the reaction product: the hydroxyl group-containing (meth) acrylate type compound (e1) is about 1:3.

When the reaction product and the hydroxyl group-containing (meth) acrylate-based compound (e1) are subjected to an addition reaction, the residual isocyanate group content of the reaction system is 0.5% by weight or less, and the reaction is completed, whereby a uric acid can be obtained. An ester (meth) acrylate compound (E).

In order to promote the reaction of the polyol compound (e3) with the polyvalent isocyanate compound (e2), and further promote the reaction in the reaction of the reaction product with the hydroxyl group-containing (meth) acrylate compound (e1), Using a catalyst, the catalyst, for example, an organic metal compound such as dibutyltin dilaurate, trimethyltin hydroxide or tetra-n-butyltin, zinc octoate, tin octylate, cobalt naphthenate, tin (II) chloride, chlorine a metal salt such as tin (IV), triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4, 0] undecene, N, N, N', N'-tetramethyl-1,3-butanediamine, N-ethyl An amine-based catalyst such as porphyrin, cerium nitrate, cerium bromide, cerium iodide, cerium sulfide, etc., or an organic cerium compound such as dibutyl guanidine dilaurate or dioctyl guanidine laurate or 2-ethyl group. Barium caproate salt, barium naphthenate salt, barium isononium salt, barium neodecanoate salt, barium laurate salt, barium maleate salt, barium stearate salt, barium oleate salt, barium linoleate salt , strontium acetate, bismuth bismuth citrate, bismuth sub salicylate, bismuth bismuth citrate, and the like, and the bismuth-based catalyst of the organic acid strontium salt, among which dibutyltin dilaurate, 1,8 is preferred. -Diazabicyclo[5,4,0]undecene.

Further, in the reaction of the polyol compound (e3) with the polyvalent isocyanate compound (e2), and further, the reaction product and the hydroxyl group-containing (meth) acrylate compound (e1) may be used without isocyanate group. An organic solvent which reacts with a functional group, for example, an ester such as ethyl acetate or butyl acetate; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; or an organic solvent such as an aromatic compound such as toluene or xylene.

Further, the reaction temperature is usually from 30 to 90 ° C, preferably from 40 to 80 ° C, and the reaction time is usually from 2 to 10 hours, preferably from 3 to 8 hours.

The number of unsaturated groups of the urethane (meth) acrylate type compound (E) used in the present invention, from the viewpoint of hardening shrinkage, is preferably from 2 to 6, more preferably from 2 to 4, and 2 Better.

When the urethane (meth) acrylate type compound (E) is used, it is made up of: [I'] comprising: a metal or semimetal compound (A) capable of forming a chelate compound, containing a metal or a half The photopolymerizable compound (B) which forms a functional group of a chelate compound, and the urethane (meth) acrylate type compound (E) preferably further contain other photopolymerizable compound (C) (except for exclusion) The photopolymerizable compound (B) is an adhesive composition which is further prepared by: [II'] comprising: a metal or a semimetal compound (A) capable of forming a chelate compound and containing a metal capable of The chelating compound (AB) and the urethane (meth) acrylate compound (E) formed by the photopolymerizable compound (B) having a functional group of a semimetal to form a chelate preferably further comprise An adhesive composition of a photopolymerizable compound (C (except for the photopolymerizable compound (B)).

In the case of the above [I'], the adhesive composition can be prepared by appropriately blending (A) to (C) and (E). The ratio of each of (A) to (C) and (E) is (A) to (C) and (E), (A) is 0.1 to 30% by weight, and (B) is 0.01 to 30. The weight %, (C) is 30 to 99% by weight, and (E) is preferably 0.5 to 50% by weight, particularly (A) is 0.5 to 20% by weight, (B) is 0.05 to 20% by weight, and (C) is 50 to 98% by weight, (E) is preferably 1 to 40% by weight, (A) is 1 to 15% by weight, (B) is 0.1 to 10% by weight, and (C) is 65 to 94% by weight, (E) ) is preferably 4 to 30% by weight.

If the content of the (A) is too small, the adhesion between the polarizer and the protective film is lowered, and the discoloration resistance tends to be lowered. If too much, the durability during the warm water resistance test is lowered, and the polarizer is The tendency of the adhesion of the protective film to decrease. If the content of the component (B) is too small, the adhesion between the polarizer and the protective film tends to decrease, and if it is too large, the durability during the warm water resistance test tends to decrease. If the content of the component (C) is too small, the durability at the time of the warm water test tends to be lowered. If the content is too high, the adhesion between the polarizer and the protective film tends to decrease. If the content of the (E) is too small, the water resistance or the adhesion strength tends to decrease, and if it is too much, the adhesion tends to decrease.

The above-mentioned composition containing (A) and (B), preferably further containing (C) and (E), may be applied to a polarizer, and is usually 50 to 200 ° C, particularly preferably 60 °. Drying was carried out at 150 ° C to form a chelate compound (AB). Further, after the composition of the adhesive containing (A) and (B), preferably further containing (C) and (E), it is usually 50 to 120 ° C, preferably 60 to 90 ° C (A). ) reacts with (B) to form a chelate compound (AB).

Further, in the case of [II'], the chelating compounds (AB) and (E) formed by (A) and (B) are contained, preferably (C), but may also contain (A), B), (E), and a chelate compound (AB) formed of (A) and (B) preferably contain (C).

The content of the chelating compound (A-B) is preferably from 0.1 to 40% by weight, more preferably from 0.5 to 30% by weight, still more preferably from 1 to 20% by weight. If the content is too small, the adhesion between the polarizer and the protective film is lowered, and the discoloration resistance tends to be lowered. If too much, the durability in the warm water resistance test is lowered, and the polarizer and the protective film are followed. The tendency to reduce the force.

As described above, by containing the urethane (meth) acrylate-based compound (E), the curing shrinkage can be alleviated, and it is presumed that the degree of crosslinking can be improved by the polyfunctionality, and the bonding strength can be improved. Water resistance is improved. It is presumed that it is considered that the above-mentioned urethane (meth) acrylate type compound (E) is polyfunctional and has a polymer site (having a certain molecular weight due to the repeating structure of the polyol moiety), Therefore, the degree of crosslinking can be improved while reducing the hardening shrinkage.

<Polymer (F)> Next, the polymer (F) which is the aforementioned admixture will be described. Further, in the above polymer (F) used in the present invention, the solubility parameter (SP値) of the polymer is from 8 to 25, preferably from 9 to 20. If the SP is too low, the mutual solubility tends to decrease, and if it is too high, the mutual solubility tends to decrease.

The above solubility parameter (SP値) is based on the algorithm of Fedors [refer to "PoIymer Eng. & Sci.", Vol. 14, No. 2 (1974), pp. 148-154]. Determination.

The weight average molecular weight for the polymer (F) is usually from 10,000 to 1,500,000, preferably from 30,000 to 1,000,000, and particularly preferably from 40,000 to 500,000. If the weight average molecular weight is too low, the adhesion tends to decrease, and if it is too high, the mutual solubility is lowered and the stability as an adhesive composition tends to be lowered.

The weight average molecular weight is obtained by converting the molecular weight of the standard polystyrene into three columns: a high-speed liquid chromatograph ("Waters 2695 (main body)" and "Waters 2414 (detector)" manufactured by Waters, Japan): Shodex GPC KF-806L (excluding the limit molecular weight: 2 × 10 ⁷ , separation range: 100 ~ 2 × 10 ⁷ , theoretical number of layers: 10,000 layers / support, filler material: styrene-divinylbenzene copolymer, filler Measured by particle size: 10 μm).

The glass transition temperature (Tg) of the polymer (F) is usually -20 to 120 ° C, preferably -10 to 110 ° C, and more preferably -5 to 100 ° C. If the glass transition temperature is too low, the water resistance tends to decrease, and if it is too high, the adhesion tends to decrease.

Further, the Tg of the polymer (F) was measured by DSC using the difference in heat between the measurement sample and the change in the heat balance with the phase transfer and the melting of the standard sample.

Further, when the polymer (F) has an unsaturated group, it contributes to a photoreaction, which is preferable.

In the present invention, the polymer (F) is, for example, a polyethylene resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polylactic acid resin, a polypropylene resin, a polycarbonate resin, or a polytetrafluoroethylene. a resin, a polyurethane resin, a polystyrene resin, an ABS resin, an acrylic resin, a polyacetal resin, a polyester resin, a polyamide resin, a polyalkylene oxide resin, or the like. Among them, it is preferred to use at least one of an acrylic resin (f1) and a polymer (f2) containing a polyoxyalkylene chain. These may be used alone or in combination of two or more.

In the present invention, the acrylic resin (f1) is obtained by polymerizing a monomer component containing a (meth)acrylic monomer. The acrylic resin (f1) may be used alone or in combination of two or more.

The acrylic resin (f1) preferably contains a (meth) acrylate monomer (f1-1) as a main component in the polymerization component, and may also contain a functional group-containing monomer (f1). 2) Other copolymerizable monomers (f1-3) are used as a copolymerization component. The (meth) acrylate monomer (f1-1), for example, an aliphatic (meth) acrylate monomer such as an alkyl (meth) acrylate or an aromatic compound such as phenyl (meth) acrylate ( Methyl) acrylate monomer.

For the alkyl (meth)acrylate, the carbon number of the alkyl group is usually from 1 to 12, particularly from 1 to 8, more preferably from 4 to 8. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate. (Methyl) n-propyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, (methyl) ) Lauryl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, and the like. Further, examples of the phenyl (meth)acrylate include benzyl (meth)acrylate and phenoxyethyl (meth)acrylate. Examples of the other (meth) acrylate-based monomer include tetrahydrofurfuryl (meth) acrylate. These may be used alone or in combination of two or more.

Among the (meth) acrylate-based monomers (f1-1), methyl (meth) acrylate or (methyl) is used from the viewpoints of copolymerizability, physical properties, ease of handling, and ease of obtaining raw materials. N-butyl acrylate and 2-ethylhexyl (meth)acrylate are preferred.

a functional group-containing monomer (f1-2), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an alkoxy group- or phenoxy group-containing monomer, a guanamine group-containing monomer, and an amine group-containing monomer The monomer, the nitrogen-containing monomer, the epoxy group-containing monomer, the phosphate group-containing monomer, the sulfonic acid group-containing monomer, and the like may be used alone or in combination of two or more.

The above hydroxyl group-containing monomer, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyl (meth)acrylate Hydroxyl (meth) acrylate such as hexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate Caprolactone-modified monomer such as 2-hydroxyethyl (meth)acrylate, 2-propenyloxyethyl-2-hydroxyethylphthalic acid, N-hydroxymethyl ( a methyl group-containing monomer such as methacrylamide or N-hydroxyethyl (meth) acrylamide; 2-hydroxypropyl (meth)acrylate; 2-hydroxybutyl (meth)acrylate; 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. 2 a hydroxyl group-containing monomer; a 3-hydroxy group-containing monomer such as 2,2-dimethyl-2-hydroxyethyl (meth)acrylate.

Further, a polyethylene glycol derivative such as diethylene glycol mono(meth)acrylate or polyethylene glycol mono(meth)acrylate or a polypropylene glycol derivative such as polypropylene glycol mono(meth)acrylate may be used. , polyethylene glycol-polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol - tetramethylene glycol) single An alkylene-modified monomer such as (meth) acrylate.

The above carboxyl group-containing monomer, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, (methyl) Michael addition of acrylic acid (for example: acrylic acid dimer, methacrylic acid dimer, acrylic acid terpolymer, methacrylic acid terpolymer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2- (Methyl) propylene oxiranyl ethyl dicarboxylic acid monoester (for example: 2-propenyloxyethyl succinic acid monoester, 2-methyl propylene oxyethyl succinic acid monoester, 2-propene oxime) Monoethyl phthalate monoester, 2-methylpropenyl oxiranyl phthalate monoester, 2-propenyl methoxyethyl hexahydrophthalic acid monoester, 2-methyl propylene oxime Ethyl hexahydrophthalic acid monoester, etc.). Further, the carboxyl group-containing monomer may be used as it is in the form of an acid, or may be used in the form of a salt neutralized to form a salt.

The alkoxy group-containing monomer is, for example, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-butoxydiethylenedi(meth)acrylate, methoxydiethylene (meth)acrylate, methoxytriethylene glycol (A) Acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, octyloxy polyethylene Aliphatic groups such as diol-polypropylene glycol-mono(meth)acrylate, lauryloxy polyethylene glycol mono(meth)acrylate, stearyloxy polyethylene glycol mono(meth)acrylate ( Methyl) acrylate or the like; phenoxy group-containing monomer, for example: 2-phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxy polyethyl b An acrylate such as an aromatic (meth) acrylate such as a diol-polypropylene glycol-(meth) acrylate or a nonyl phenol ethylene oxide adduct (meth) acrylate.

The above-mentioned amidino group-containing monomer, for example, acrylamide, methacrylamide, N-(n-butoxyalkyl)propenylamine, N-(n-butoxyalkyl)methacrylamide , N,N-Dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, propylene Indole-3-methylbutylmethylamine, dimethylaminoalkyl acrylamide, dimethylaminoalkylmethacrylamide, and the like.

The above-mentioned amino group-containing monomer is, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate or a tertiary compound thereof. The above nitrogen-containing monomer, for example, acrylonitrile Porphyrin and the like.

The above-mentioned epoxy group-containing monomer is, for example, glycidyl (meth)acrylate or allyl epoxidized ether.

The phosphoric acid group-containing monomer is, for example, 2-(meth)acryloxyethyl acid phosphate or bis(2-(methyl)acryloxyethyl) acid phosphate.

The above sulfonic acid group-containing monomer, for example, an olefin sulfonic acid such as ethylenesulfonic acid, allylsulfonic acid or methallylsulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid or benzene Ethylene sulfonic acid or a salt thereof. These functional group-containing monomers (f1-2) may be used alone or in combination of two or more.

Other copolymerizable monomers (f1-3), for example, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, Vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, acrylonitrile, methyl vinyl ketone, A monomer such as N-propylene guanamine methyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, or dimethyl allyl vinyl ketone.

Further, when polymerizing, it is also possible to use ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, or polyethylene glycol in combination. A compound having two or more ethylenically unsaturated groups such as an alcohol di(meth)acrylate, propylene glycol di(meth)acrylate or divinylbenzene.

In the acrylic resin (f1), the content ratio of the (meth)acrylate monomer (f1-1), the functional group-containing monomer (f1-2), and other copolymerizable monomer (f1-3) The (meth) acrylate monomer (f1-1) is preferably 10 to 100% by weight, particularly preferably 20 to 95% by weight, and the functional group-containing monomer (f1-2) is preferably 0 to 90% by weight. It is preferably from 5 to 80% by weight, and the other copolymerizable monomer (f1-3) is preferably from 0 to 50% by weight, particularly preferably from 5 to 40% by weight.

In the present invention, as the acrylic resin (f1), from the viewpoint of water resistance and adhesion, a polymer having a methyl (meth) acrylate as a polymerization component is preferred, and in particular, methyl methacrylate is polymerized. The polymer of the component is preferably, more preferably polymethyl methacrylate.

In the present invention, the acrylic resin (f1) is produced by polymerizing the monomer components of the above (f1-1) to (f1-3), and the polymerization can be carried out by solution radical polymerization, suspension polymerization, bulk polymerization, A conventionally known method such as emulsion polymerization is carried out. For example, the above (meth) acrylate monomer (f1-1), functional group-containing monomer (f1-2), and other copolymerizable monomer (f1-3) are mixed or added dropwise in an organic solvent. The polymerization monomer, the polymerization initiator (azobisisobutyronitrile, azobisisovaleronitrile, benzammonium peroxide, etc.) are polymerized in a reflux state or at 50 to 90 ° C for 2 to 20 hours.

Further, as the polymer (f2) containing a polyoxyalkylene chain, it is also preferably an allyl epoxidized ether copolymer containing a polyoxyalkylene chain, more preferably ethylene oxide ‧ propylene oxide The allyl epoxidized ether copolymer is particularly preferably a random copolymer or a block copolymer.

In the case of using the polymer (F), it is made up of: [I''] comprising: a metal or semimetal compound (A) capable of forming a chelate, and a functional group capable of forming a chelate with the metal or semimetal The photopolymerizable compound (B) and the polymer (F) are preferably an adhesive composition further comprising another photopolymerizable compound (C) (except that the photopolymerizable compound (B) is excluded), , [I''] comprises: a metal or semimetal compound (A) capable of forming a chelate and a photopolymerizable compound containing a functional group capable of forming a chelate with the metal or semimetal (B) The chelate compound (AB) and the polymer (F) to be formed preferably further comprise an additional binder composition of the other photopolymerizable compound (C) (except that the photopolymerizable compound (B) is excluded).

For the blending ratio of (A) and (F), (A)/(F) is preferably 50/50 to 95/5 by weight ratio, more preferably 55/45 to 90/10, more preferably It is 60/40~80/20. If the (A)/(F) is too small, the force tends to decrease. If it is too large, the force tends to decrease.

In the case of the above [I''], (A) to (C) and (F) may be appropriately blended to form an adhesive composition. The ratio of each of (A) to (C) and (F) is preferably 0.1 to 30% by weight and (B) is 0.5% based on the total of (A) to (C) and (F). 40% by weight, (C) is 30 to 99% by weight, and (F) is preferably 0.01 to 20% by weight, particularly (A) is 0.5 to 20% by weight, and (B) is 1 to 30% by weight, (C) ) is preferably 50 to 98% by weight, (F) is preferably 0,05 to 10% by weight, more preferably (A) is 1 to 15% by weight, (B) is 4 to 20% by weight, and (C) is 65 to 94% by weight and (F) is 0.1 to 8% by weight. If the content of the (A) is too small, the adhesion between the polarizer and the protective film is lowered, or the discoloration resistance tends to be lowered. If too much, the durability during the warm water resistance test is lowered, or the polarizer is The tendency of the adhesion of the protective film to decrease. If the content of the component (B) is too small, the adhesion between the polarizer and the protective film tends to decrease, and if the temperature is too high, the durability tends to decrease. If the content of the component (C) is too small, the durability in the case of the warm water resistance test tends to be lowered, and if the excessive force of the polarizer and the protective film is too small, the adhesive force tends to decrease. If the content of the component (F) is too small, the adhesion tends to decrease, and if it is too large, the mutual solubility decreases and the adhesive force tends to decrease.

In the above, as the (A) and (B), it is preferable to further apply the adhesive composition containing (C) and (F) to a polarizer, usually at 50 to 200 ° C, particularly preferably 60. Drying at ~150 ° C forms a chelate compound (AB). Further, after the composition of the adhesive containing (A) and (B), preferably further containing (C) and (F), it is usually 50 to 120 ° C, preferably 60 to 90 ° C (A). In reaction with (B), a chelate compound (AB) can be formed.

Further, in the case of [II''], the chelate compound (AB) and the polymer (F) formed of (A) and (B) are contained, and it is preferable to further contain (C), but sometimes The chelating compound (AB) containing (A), (B), (F) and (A) and (B) is preferably further contained in (C).

The content of the chelating compound (A-B) is preferably from 0.1 to 40% by weight, particularly preferably from 0.5 to 30% by weight, more preferably from 1 to 20% by weight. If the content is too small, the adhesion between the polarizer and the protective film is lowered, and the discoloration resistance tends to be lowered. If too much, the durability in the warm water resistance test is lowered, and the polarizer and the protective film are followed. The tendency to reduce the force.

As described above, it is presumed that by having the polymer (F), the polymer chain is incorporated into the polymer network structure upon ultraviolet curing, whereby the hardening shrinkage can be alleviated, and the bonding strength can be further improved to achieve an improvement in water resistance.

<Acid Group-Containing Monomer (G)> Next, it is explained with respect to the acid group-containing monomer (G) which is the said admixture. In the present invention, the acid group-containing monomer (G), for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, A Michael addition of cinnamic acid or (meth)acrylic acid (for example: acrylic acid dimer, methacrylic acid dimer, acrylic acid terpolymer, methacrylic acid terpolymer, acrylic acid tetramer, methacrylic acid tetra Polymer, etc.), 2-(methyl) propylene oxiranyl ethyl dicarboxylic acid monoester (for example: 2-propenyloxyethyl succinate monoester, 2-methyl propylene oxyethyl succinate mono Ester, 2-propenyloxyethyl phthalate monoester, 2-methylpropenyloxyethyl phthalate monoester, 2-propenyloxyethyl hexahydrophthalic acid monoester, 2-methylpropenyloxyethylhexahydrophthalic acid monoester, etc.), carboxyethyl acrylate, etc., among which (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. The carboxyl group preferably contains an ethylenically unsaturated compound, and particularly preferably (meth)acrylic acid or carboxyethyl acrylate. These may be used alone or in combination of two or more.

When the acid group-containing monomer (G) is used, it is made up of: [I'''] comprising: a metal or semimetal compound (A) capable of forming a chelate compound, which is capable of forming a chelate with the metal or semimetal The photopolymerizable compound (B) having a functional group and the acid group-containing monomer (G) preferably further comprise another photopolymerizable compound (C) (except that the photopolymerizable compound (B) is excluded). The composition of the adhesive, in addition, is made up of: [II'''] comprising: a metal or semimetal compound (A) capable of forming a chelate and a functional group capable of forming a chelate with the metal or semimetal The chelating compound (AB) formed by the photopolymerizable compound (B), the acid group-containing monomer (G), and preferably further containing other photopolymerizable compound (C) (except that the photopolymerizable compound is excluded) B). The resulting adhesive composition.

For the blending ratio of (A) and (G), (A) / (G) is preferably 50/50 to 95/5 by weight, more preferably 55/45 to 90/10, 60/ 40~80/20 is better. If the (A)/(G) is too small, the water resistance tends to decrease, and if it is too large, the adhesion tends to decrease.

In the case of the above [I'''], (A) to (C) and (G) may be appropriately blended to form an adhesive composition. The ratio of each of (A) to (C) and (G) is preferably 0.1 to 30% by weight and (B) is 0.5% based on the total of (A) to (C) and (G). 40% by weight, (C) is 30 to 99% by weight, and (G) is preferably 0.01 to 20% by weight, particularly (A) is 0.5 to 20% by weight, and (B) is 1 to 30% by weight, (C) It is preferably 50 to 98% by weight, and (G) is 0.05 to 10% by weight, more preferably (A) is 1 to 15% by weight, (B) is 4 to 20% by weight, and (C) is 65 to 94%. The weight % and (G) are 0.1 to 8% by weight. When the content of the (A) is too small, the adhesion between the polarizer and the protective film is lowered, and the discoloration resistance tends to be lowered. If the content is too large, the durability in the warm water resistance test is lowered, and the polarizer and the polarizer are The tendency of the adhesion of the protective film to decrease. If the content of the component (B) is too small, the adhesion between the polarizer and the protective film tends to decrease, and if it is too large, the durability at the time of the warm water test tends to be lowered. If the content of the component (C) is too small, the durability during the warm water resistance test tends to be lowered. If the content is too high, the adhesion between the polarizer and the protective film tends to decrease. If the content of the (G) is too small, the adhesive strength tends to decrease, and if it is too much, the water resistance tends to decrease.

In the above, as the (A), (B) and (G), it is preferable to further contain the composition of the adhesive (C), which is usually applied at 50 to 200 ° C, preferably at 50 to 200 ° C. Drying at 60 to 150 ° C can form a chelate compound (AB). Further, after the composition containing (A), (B) and (G), preferably further containing (C), it is usually 50 to 120 ° C, preferably 60 to 90 ° C (A) In reaction with (B), a chelate compound (AB) can be formed.

Further, in the case of [II'''], the chelate compound (AB) formed of (A) and (B) and the acid group-containing monomer (G) are contained, and it is preferable to further contain (C). However, it may contain (A), (B), (G), a chelate compound (AB) formed from (A) and (B), and preferably (C).

The content of the chelating compound (A-B) is preferably from 0.1 to 40% by weight, more preferably from 0.5 to 30% by weight, still more preferably from 1 to 20% by weight. If the content is too small, the adhesion between the polarizer and the protective film is lowered, and the discoloration resistance tends to be lowered. If too much, the durability in the warm water resistance test is lowered, and the polarizer and the protective film are lowered. Then the tendency to reduce the force.

As described above, by having the acid group-containing monomer (G), it is presumed that the mutual variability (ketone oxime) of the photopolymerizable compound (B) containing a functional group capable of forming a chelate with the metal or the semimetal is promoted. The enolization of the enol is an increase in adhesion. In particular, it is considered that when the component (B) is an ethylenically unsaturated compound (b1) containing an ethyl oxime group, a plurality of hydroxyl groups which are effective for the adhesion force are formed by blending the acid group-containing monomer.

<Photobase generator (H)> Next, it is explained with respect to the photobase generator (H) which is the aforementioned admixture. In the present invention, the photobase generator (H) is a compound which generates one or more kinds of basic substances by utilizing light irradiation such as ultraviolet rays or visible light to cause molecular structure change or molecular cracking to function as a curing catalyst. The basic substance is, for example, a secondary amine or a tertiary amine.

As the photobase generator, a photobase generator known from the prior art, and a preferred photobase generator can be used, and examples thereof include compounds represented by the following formulas (2) to (7). These may be used alone or in combination of two or more.

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemistry 7]

Among the above, the compounds represented by the above formulas (2) and (3) are preferred.

The above photobase generator (H) is usually preferred to have a maximum molar absorption coefficient below 405 nm.

When a photobase generator (H) is used, it is made up of: [I''''] comprising: a metal or semimetal compound (A) capable of forming a chelate, containing a chelate compound capable of forming a chelate with the metal or semimetal The photopolymerizable compound (B) and the photobase generator (H) having a functional group preferably further comprise another photopolymerizable compound (C) (except that the photopolymerizable compound (B) is excluded). The composition, in addition, is made up of: [II''''] comprising: a metal or semimetal compound (A) capable of forming a chelate and a functional group capable of forming a chelate with the metal or semimetal The chelate compound (AB) and the photobase generator (H) which are formed of the photopolymerizable compound (B) preferably contain another photopolymerizable compound (C) (except that the photopolymerizable compound (B) is excluded). Adhesive composition.

For the blending ratio of (A) and (H), (A)/(H) is preferably 99.1/0.1 to 70/30 by weight, particularly preferably 99/1 to 80/20, more preferably Good for 95/5~85/15. If the (A)/(H) is too small, the water resistance tends to decrease, and if it is too large, the water resistance tends to decrease.

In the case of the above [I'''''', the (A) to (C) and (H) may be appropriately blended to form an adhesive composition. The ratio of each of (A) to (C) and (H) is preferably 0.1 to 30% by weight and (B) is 0.5% based on the total of (A) to (C) and (H). 40% by weight, (C) is 30 to 99% by weight, and (H) is preferably 0.1 to 20% by weight, particularly (A) is 0.5 to 20% by weight, and (B) is 1 to 30% by weight, (C) It is preferably 50 to 98% by weight, (H) is preferably 0.5 to 15% by weight, more preferably (A) is 1 to 15% by weight, (B) is 4 to 20% by weight, and (C) is 65~. 94% by weight and (H) are 1 to 10% by weight. If the content of the (A) is too small, the adhesion between the polarizer and the protective film is lowered, and the discoloration resistance tends to be lowered. If too much, the durability of the warm water test is lowered, and the polarizer and the protection are protected. The tendency of the film's adhesion to decrease. If the content of the component (B) is too small, the adhesion between the polarizer and the protective film tends to decrease, and if it is too large, the durability at the time of the warm water test tends to be lowered. If the content of the component (C) is too small, the durability during the warm water resistance test tends to be lowered. If the content is too high, the adhesion between the polarizer and the protective film tends to decrease. If the content of the (H) is too small, the water resistance tends to decrease, and if too much, the water resistance tends to decrease.

In the above, as the adhesive composition containing (A), (B) and (H), preferably further containing (C), it is preferably applied at a temperature of 50 to 200 ° C by applying it to a polarizer. The chelating compound (AB) can be formed by drying at 60 to 150 °C. Further, after the composition containing (A), (B) and (H), preferably further containing (C), it is usually at 50 to 120 ° C, preferably 60 to 90 ° C (A) In reaction with (B), a chelate compound (AB) can be formed.

Further, in the case of [II''''], the chelate compound (AB) and the photobase generator (H) formed of (A) and (B) are contained, and it is preferable to further contain (C). However, the chelating compound (AB) formed of (A), (B), (H), and (A) and (B) may be contained, and it is preferable to further contain (C).

The content of the chelating compound (A-B) is preferably from 0.5 to 50% by weight, more preferably from 1 to 40% by weight, still more preferably from 5 to 30% by weight. If the content is too small, the adhesion between the polarizer and the protective film is lowered, and the discoloration resistance tends to be lowered. If too much, the durability in the warm water resistance test is lowered, and the polarizer and the protective film are followed. The tendency to reduce the force.

As described above, it is presumed that by having a photobase generator (H), the acidity of the photopolymerizable compound (B) containing a functional group capable of forming a chelate with the metal or the semimetal is neutralized, in particular The acidity of the ethylenically unsaturated compound (b1) containing the ethyl acetonitrile group is neutralized, the reactivity of the component (B) is improved, and the water resistance is improved. In particular, when the photobase generator is irradiated with ultraviolet rays or the like to generate an alkali component and the anion of the double bond is hardened, the weak acidity of the component (B) may have a poor influence on water resistance, so it is considered that by blending the photobase The generator also has the meaning of neutralization.

In summary, the adhesive composition of the present invention is obtained. The adhesive composition of the present invention is preferably cured by active energy ray irradiation, and is suitable as an adhesive for use as an adhesive for a polarizing plate for adhering a polarizer and a protective film.

Further, the adhesive composition of the present invention may be used in the form of a solvent-free composition, but it is preferably used in the form of a solvent-free composition from the viewpoint of excellent adhesion performance.

(Polarizer) The polarizer is not particularly limited, and a known one can be used. For example, (i) a dichroic material such as iodine or a dichroic dye is adsorbed to a PVA film, a partially formalized PVA film, or a vinyl alcohol resin film such as an ethylene vinyl alcohol resin film, and is uniaxially stretched. (i) The above (i), wherein the vinyl alcohol resin film has both a dichroic material and a liquid crystal property, as described in (i) above. (for example, refer to Japanese Laid-Open Patent Publication No. 2007-72203); (iii) uniaxially extending a thermoplastic norbornene-based resin film containing a dichroic material (for example, refer to JP-A-2001-356213) (iv) a polyene-based film obtained by dehydrating or deacetating a PVA-based resin or an ethylene-vinyl alcohol-based resin to introduce a continuous polyene structure and extending the same (for example, refer to JP-A-2007- Bulletin No. 17845). Among them, in view of the excellent polarization characteristics, it is preferred that the PVA film has a uniaxially stretched film having iodine adsorption.

The thickness of the polarizer is usually 0.1 to 100 μm, particularly preferably 0.5 to 80 μm, more preferably 1 to 60 μm.

(Protective film) The protective film is insufficient in durability under high humidity by being bonded to at least one of the polarizers, preferably bonded to both surfaces, and capable of reinforcing the problem of the polarizer. In addition, the properties required for the protective film used in the present invention include transparency, mechanical strength, thermal stability, moisture barrier properties, and optical isotropic properties.

As a material of the protective film, a cellulose ester resin, a cyclic olefin resin, or a (meth)acrylic resin is preferably used from the viewpoint of optical properties, durability, and the like. Moreover, as another material, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, a polystyrene resin such as polystyrene or acrylonitrile styrene copolymer, or the like may be mentioned. Polyolefin resin such as polyethylene or polypropylene, polyarylate resin, polycarbonate resin, vinyl chloride resin, melamine resin such as nylon or aromatic polyamide, or fluorine-containing polyimide A resin, a polyetheretherketone resin, a polyphenylene sulfide resin, a vinylidene chloride resin, a polyvinyl acetal resin such as polyvinyl butyral, a polyacetal resin, an epoxy resin, or the like. These may be used alone or in combination of two or more.

The cellulose ester-based resin used in the cellulose ester-based resin film is represented by triethyl fluorenyl cellulose or diethyl hydrazino cellulose, and further, a lower fatty acid ester of cellulose or cellulose acetate C can be used. A mixed fatty acid ester such as an acid ester or a cellulose acetate butyrate.

The cyclic olefin-based resin used as the cyclic olefin-based resin film is a norbornene-based resin. The norbornene-based resin includes, for example, a ring-opening (co)polymer of a norbornene-based monomer, a resin obtained by addition polymerization of a norbornene monomer, and a norbornene-based monomer and ethylene or an α-olefin. A resin obtained by addition-polymerization of an olefin-based monomer or the like.

Specific examples of the norbornene-based monomer include dimers such as norbornene and norbornadiene; terpolymers such as dicyclopentadiene and dihydroxypentadiene; and tetracyclopentadiene and the like. a ring; an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; an alkenyl group such as a vinyl group; an alkylene group such as an ethylidene group; an aryl group such as a phenyl group, a tolyl group or a naphthyl group; a substituent; further having such an ester group, an ether group, a cyano group, a halogen, an alkoxycarbonyl group, a pyridyl group, a hydroxyl group, a carboxylic acid group, an amine group, a hydroxyl group, a decyl group, an epoxy group, an acryl group And a substituent such as a group containing an element other than carbon or hydrogen such as a methacrylinyl group.

As a commercial product of the cyclic olefin resin film, "ARTON" manufactured by JSR Corporation, "ZEONOR" manufactured by Japan Zeon Co., Ltd., "ZEONEX", "OPTOREZ" manufactured by Hitachi Chemical Co., Ltd., and "APEL" manufactured by Mitsui Chemicals Co., Ltd., and the like are exemplified.

The (meth)acrylic resin used as the (meth)acrylic resin film may, for example, be a poly(meth)acrylate such as polymethyl methacrylate or a copolymer of methyl methacrylate-(meth)acrylic acid. , methyl methacrylate-(meth) acrylate copolymer, methyl methacrylate-acrylate-(meth)acrylic acid copolymer, methyl (meth) acrylate-styrene copolymer, having an alicyclic ring a hydrocarbon-based polymer (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-methyl (meth) acrylate), intramolecular crosslinking, intramolecular A (meth)acrylic resin having a high glass transition temperature obtained by a cyclization reaction, a rubber-acrylic graft type core-shell polymer, or the like.

The commercially available product of the (meth)acrylic resin film is "ACRYPET VRL20A" manufactured by Mitsubishi Rayon Co., Ltd., "ACRYPET IRD-70", and "MUX-60" manufactured by UMGABS Co., Ltd., and the like.

In addition, the protective film may be subjected to a saponification treatment to apply a lye to a film made of a cellulose ester-based resin or a corona discharge treatment to a film made of a cyclic olefin-based resin. Surface hydrophilization treatment such as plasma treatment.

Further, in order to improve the affinity between the surface of the protective film and the adhesive, various surface treatments other than hydrophilization may be carried out, and a (meth)acrylate emulsion or a styrene latex may be contained on the surface of the protective film. An easy-adhesion layer or a tackifying coating layer such as a polyethyleneimine or a polyurethane/polyester copolymer, or a surface treatment using a coupling agent such as a decane coupling agent or a titanium coupling agent. Further, various surface treatment methods described above may be used in combination. Further, it is also preferred to apply an antistatic agent to the surface of the protective film or to include an antistatic agent in the film.

The thickness of the protective film is not particularly limited. Usually, the polarizer is thicker than the polarizer, and the substrate of the polarizer has a function of imparting strength, and is usually 10 to 100 μm, preferably 20 to 80 μm.

Further, the protective film may be provided with a hard coat layer on a surface on which the polarizer is not laminated, or may be subjected to various treatments such as stacking, anti-reflection, and anti-glare. Further, various optical functional films such as a phase difference plate or a viewing angle expansion film may be laminated.

(Polarizing Plate) The polarizing plate of the present invention is obtained by laminating the above-mentioned polarizer and protective film with an adhesive for a polarizing plate. More specifically, the protective film is bonded to at least one of the polarizers, preferably on both sides, using the adhesive for the polarizing plate of the present invention, and the liquid adhesive composition is usually uniformly coated. After the polarizer or the protective film, or both, the two are bonded and pressure-bonded, and subjected to active energy ray irradiation to form a polarizing plate.

When the adhesive composition is coated on a polarizer or a protective film, for example, a reverse coater, a gravure coater (direct, reverse or indirect), a reverse coating bar, a roll coater can be used. Coating with a die coater, a coating bar, a coating bar, or the like, or by dip coating.

For the bonding and crimping, for example, a laminating roller or the like can be used, and the pressure can be selected from the range of 0.1 to 10 MPa.

The active energy ray irradiation can use electromagnetic waves such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X-rays, gamma rays, and the like, and an electron beam, a proton beam, a neutron beam, or the like can be used, and the curing speed and the irradiation device can be easily obtained. From the viewpoints of sex and price, it is advantageous to use hardening by ultraviolet irradiation. Further, when electron beam irradiation is performed, the photopolymerization initiator (d1) can be used without being cured.

As the light source when the ultraviolet ray is irradiated, a high pressure mercury lamp, an electrodeless lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black lamp, an LED, or the like can be used. The ultraviolet irradiation is carried out under the conditions of 2 to 3000 mJ/cm ² , preferably 10 to 2000 m J/cm ² .

In particular, the above-described high-pressure mercury lamp is, for example, carried out under conditions of 5 to 3000 mJ/cm ² , preferably 50 to 2000 m J/cm ² . Further, in the case of the above-described electrodeless lamp, for example, it is carried out under conditions of 2 to 2000 m J/cm ² , preferably 10 to 1000 m J/cm ² .

Further, the irradiation time varies depending on the type of the light source, the distance between the light source and the coated surface, the coating thickness, and other conditions, and is usually from several seconds to several tens of seconds, and may be a fraction. Further, in the case of the above-described electron beam irradiation, for example, an electron beam having an energy in the range of 50 to 1000 keV can be used, and an irradiation amount of 2 to 50 Mrad can be used.

The irradiation direction of the active energy ray (electron beam, ultraviolet light, or the like) can be irradiated from any appropriate direction, but it is preferable to irradiate from the side of the transparent protective film from the viewpoint of preventing deterioration of the polarizer.

In the polarizing plate of the present invention obtained as described above, the thickness of the adhesive layer is usually from 0.01 to 10 μm, preferably from 0.01 to 5 μm, more preferably from 0.01 to 2 μm, still more preferably from 0.01 to 1 μm. If the thickness is too small, the cohesive force of the adhesion force itself cannot be obtained, and the adhesive strength tends to be impossible. If it is too thick, the workability of the polarizing plate tends to be lowered due to cracking during press working or the like.

The adhesive composition of the present invention is an adhesive which is excellent in initial force and adhesion with time, and can be used in various applications, among which, it is particularly suitable for various protective films for polarizing plates and polarizers, especially for protection other than TAC. The film is bonded to the polarizer, and the drying step is not required, the production efficiency of the polarizing plate is also excellent, and the discoloration resistance of the polarizing plate is also excellent. [Examples]

The following examples are more specifically described in the present invention, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. In the examples, "parts" and "%" refer to the weight basis.

Prepare the following ingredients. [Metal or semi-metal compound (A) capable of forming a chelate] (A-1) Tributyl borate (tri-n-butyl borate) manufactured by Kanto Chemical Co., Ltd.) (A-2) Titanium tetraisopropoxide (Matsumoto) "Orgatix TA-l0" manufactured by Fine Chemical Co., Ltd. (A-3) Titanium tetrabutyrate ("Orgatix TA-25" manufactured by Matsumoto Fine Chemical Co., Ltd.) (A-4) Aluminum tridecyl acetonide (Nippon Chemical Industry Co., Ltd.) "NĀCEM Aluminum" (A-5) Boric acid (made by Wako Pure Chemical Industries, Ltd.)

[Photopolymerizable compound (B) containing a functional group capable of forming a chelate with a metal or a semimetal] (B-1) 2-Ethyl ethoxyethyl methacrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) AAEM")

[Photopolymerizable Compound (C)] (C-1) Acryl Group Porphyrin ("ACMO" manufactured by Hiroshi Co., Ltd.) (C-2) Dimethyl acrylamide ("DMAA" manufactured by Hiroshi Co., Ltd.) (C-3) Ethylene glycol diacrylate ("FA-222A" manufactured by Hitachi Chemical Co., Ltd. ")

[Polymerization initiator (D)] (D-1) 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by BASF Corporation) (D-2) 2,4,6-trimethylbenzhydryl-di Phenylphosphine oxide ("Lucirin TPO" manufactured by BASF Corporation)

[Carbamate (meth) acrylate type compound (E)] According to the following Synthesis Example 1, a bifunctional polyether urethane acrylate (E-1) was synthesized. (E-1) Bifunctional polyether urethane acrylate (Synthesis Example 1) 0.3 g of dibutyltin dilaurate and 4-methoxyphenol as a polymerization inhibitor were added to a 500 ml reaction vessel equipped with a stirrer. g, polytetramethylene glycol (molecular weight: 650) 230 g, and the mixture was heated while stirring until the liquid temperature became 40 °C. 185 g of hydrogenated diphenylmethane diisocyanate was slowly added to the reaction solution, and the temperature was raised to 60 ° C over 1 hour. The reaction was continued at 60 ° C, and in this state, the reaction was carried out until the free NCO % became 7.0%, and then 85 g of 2-hydroxyethyl acrylate was added to continue the reaction until the free NCO % became 0.5% or less to obtain a bifunctional polyether urethane acrylate. Ester (E-1). Further, the obtained bifunctional polyether urethane acrylate (E-1) had a weight average molecular weight of 3,200 and a viscosity at 60 ° C of 14,000 mPa ‧ s.

(Polymer (F)) (F-1) Polymethyl methacrylate (manufactured by Aldrich, SP 値 9.1 to 9.5, weight average molecular weight of about 1,000,000, glass transition temperature of 100 ° C) (F-2) Epoxy B Alkenyl propylene oxide ‧ allyl epoxidized ether random copolymer (Alkox CP-A2H, manufactured by Mingcheng Chemical Industry Co., Ltd., SP 値 19.1, weight average molecular weight of about 60,000, glass transition temperature -6 ° C)

[Acid group-containing monomer (G)] (G-1) Acrylic acid (manufactured by Aldrich Co., Ltd.) (G-2) β-carboxyethyl acrylate ("βCEA" manufactured by Daice 1‧Allnex Co., Ltd.)

(Photobase generator (H)) (H-1) (E)-1-[3-(2-Hydroxyphenyl)-2-propenyl) piperidine (Wako Pure Chemical Industries, Ltd. "WPBG-027" (H-2) 9-Mercaptomethyl-N,N-diethylcarbamate ("WBG-018", manufactured by Wako Pure Chemical Industries, Ltd.) [Example 1] <Preparation of an adhesive composition > In the preparation flask, 5 parts of tributyl borate (A-1) (solid content), 2-ethyl acetoxyethyl methacrylate (B-1) 15 parts, dimethyl group 50 parts of acrylamide (C-2), 30 parts of ethylene glycol diacrylate (C-3), 1.5 parts of Irgacure 184 (D-1), 1.5 parts of Lucirin TPO (D-2) and mixed to obtain an adhesive Composition.

[Examples 2 to 8 and Comparative Examples 1 and 2] An adhesive composition was prepared in the same manner as in Example 1 except that the respective blended components prepared above were blended in the proportions shown in Table 1 below.

<Preparation of Polarizing Plate Test Piece> First, a 60 μm PVA film was immersed in a water bath having a water temperature of 30° C., and the state was extended to 1.5 times. Then, it was immersed in a dyeing tank (30 ° C) containing iodine 0.2 g/L and potassium iodide 15 g/L for 240 seconds, and was extended to 1.3 times in this state, and then immersed in boric acid having a composition of 50 g/L of boric acid and 30 g/L of potassium iodide. The tank (50 ° C), at the same time, uniaxially stretched 3.08 times in this state, and took 5 minutes to perform boric acid treatment. After that, it was dried to prepare a polarizer having a total stretching ratio of 6 times. Then, an acrylic film (trade name "ACRYPLEN", manufactured by Mitsubishi Corporation) having a size of 200 mm × 50 mm and a thickness of 75 μm was applied to the adhesive composition obtained by coating the rod (No. 10) to have a film thickness of 5 μm. After two sheets of the acrylic film having the adhesive composition layer were formed, they were placed on both surfaces of the polarizer having a size of 150 mm × 30 mm, and bonded together by a roll press at a tensile force of 2 MPa to obtain a laminated film. Secondly, from both sides of the acrylic film side of the laminate film to ultraviolet irradiation device equipped with a high-pressure mercury lamp at an illuminance peaks: 130mW / cm ^2, accumulated exposure amount: 900mJ / cm ² (365nm) irradiated with ultraviolet rays, so then The composition was cured, and dried in Examples 1 to 7 at 80 ° C for 3 minutes. In Example 8, Comparative Examples 1 and 2 were not dried, and the obtained laminated film was used as a polarizing plate test piece.

Using the polarizing plate test piece obtained above, the performance evaluation was performed in accordance with the following.

[Adhesive property] The polarizing plate test piece was cut into 120 mm × 25 mm, and the degree of adhesion of the acrylic film to the polarizer when a stress of 90 degrees was applied to the two acrylic films was evaluated according to the following criteria. (Evaluation criteria) ◎... Firmly follow ○... Then ╳...not followed

[Decoloration resistance] The polarizing plate test piece was cut into 5 cm × 5 cm, immersed in warm water of 60 ° C, and the color tone of the polarizing plate test piece after 48 hours was observed, and evaluated based on the following criteria. ○... Same as before the test, no color change △... slightly discolored (faded) ╳... completely discolored (faded)

[Water resistance] The polarizing plate test piece was cut into 5 cm × 5 cm, immersed in warm water at 60 ° C, and the adhesion of the polarizing plate test piece after 48 hours was observed, and evaluated according to the following criteria. ○...There is no peeling from the end of the test piece △...There is no peeling in the range of less than 5 mm from the end of the test piece...There is peeling in the range of 5 mm or more from the end of the test piece.

Also, - represents no blending.

Examples 1 to 8 which comprise a chelate-forming metal or semimetal compound (A) and a photopolymerizable compound (B) containing a functional group capable of forming a chelate with the metal or semimetal The composition of the agent can sufficiently adhere the polarizer and the protective film, and has an excellent effect of being excellent in both discoloration resistance and water resistance. On the other hand, Comparative Example 1 containing no metal or semimetal compound (A) capable of forming a chelate compound, and photopolymerizable compound (B) containing a functional group capable of forming a chelate compound with a metal or a semimetal The adhesive composition of Comparative Example 2 is not only excellent in adhesion, but also inferior in discoloration resistance and water resistance, and cannot be practically used as an adhesive composition or the like. From this, it is understood that the adhesive composition of the present invention is very excellent.

(Example 9) <Preparation of the composition of the adhesive: (E) component added> 5 parts of boric acid (A-5) and 2-ethyl acetoxyethyl methacrylate (B) were placed in a flask for preparation. -1) 5 parts, 65 parts of dimethyl decylamine (C-2), and heated to 60 ° C to dissolve boric acid. Then, 5 parts of ethylene glycol diacrylate (C-3) and 20 parts of a bifunctional polyether urethane acrylate (E-1) were added and mixed. After cooling to room temperature, 1.5 parts of Irgacure 184 (D-1) and 1.5 parts of Lucirin TPO (D-2) were added, mixed, and dissolved to obtain an adhesive composition.

(Example 10, Comparative Examples 3 and 4) An adhesive composition was prepared in the same manner as in Example 9 except that the respective blended components prepared above were blended in the proportions shown in Table 2 below.

Then, a polarizing plate test piece was produced in the same manner as in the above-mentioned Example 1, and the performance of the adhesiveness, the discoloration resistance, and the water resistance were evaluated in the same manner as in Example 1 using the polarizing plate test piece. The evaluation results are shown in Table 2 below.

Also, - represents no blending.

a photopolymerizable compound (B) comprising a chelate-forming metal or semimetal compound (A), a functional group capable of forming a chelate with the metal or a semimetal, and a carbamate (meth)acrylic acid The adhesive composition of Examples 9 and 10 in which the ester compound (E) is obtained can sufficiently bond the polarizer and the protective film, and has excellent effects in both decolorization resistance and water resistance. On the other hand, Comparative Example 3 containing no metal or semimetal compound (A) capable of forming a chelate or photopolymerizable compound (B) containing a functional group capable of forming a chelate with a metal or a semimetal The adhesive composition of Comparative Example 4 was not preferable in terms of adhesion, decolorization resistance, and water resistance, and was not actually used as an adhesive composition or the like. From this, it is understood that the adhesive composition of the present invention is very excellent.

(Example 11) <Preparation of an adhesive composition: (F) component addition system> 5 parts of boric acid (A-5) and 2-ethyl acetoxyethyl methacrylate (B) were added to the flask for preparation. -1) 5 parts, 2 parts of polymethyl methacrylate (F-1), and 83 parts of dimethyl decylamine (C-2), and the mixture was heated to 60 ° C to dissolve the solid component. Then, 5 parts of ethylene glycol diacrylate (C-3) was added to make it sufficiently mixed. After cooling to room temperature, 1.5 parts of Irgacure 184 (D-1) and 1.5 parts of Lucirin TPO (D-2) were added, mixed, and dissolved.

(Examples 12 and 13 and Comparative Examples 5 and 6) An adhesive composition was prepared in the same manner as in Example 11 except that the respective blended components prepared above were blended in the same manner as shown in Table 3 below.

Then, a polarizing plate test piece was produced in the same manner as in the above-mentioned Example 1, and the performance of the adhesiveness, the discoloration resistance, and the water resistance were evaluated in the same manner as in Example 1 using the polarizing plate test piece. The evaluation results are shown in the following list 3.

Also, - represents no blending.

An embodiment comprising a metal or semimetal compound (A) capable of forming a chelate compound, a photopolymerizable compound (B) containing a functional group capable of forming a chelate with the metal or a semimetal, and a polymer (F) The adhesive composition of Examples 11 to 13 can sufficiently bond the polarizer and the protective film, and has excellent effects in resistance to discoloration and water resistance. On the other hand, Comparative Example 5 containing no metal or semimetal compound (A) capable of forming a chelate or photopolymerizable compound (B) containing a functional group capable of forming a chelate with a metal or a semimetal The adhesive composition of Comparative Example 6 was not only excellent in adhesion, decolorization resistance, and water resistance, and could not be actually used as an adhesive composition or the like. From this, it is understood that the adhesive composition of the present invention is very excellent.

[Example 14] <Preparation of an adhesive composition: (G) component addition system> 5 parts of boric acid (A-5) and 2-ethyl acetoxyethyl methacrylate were added to the adjustment flask ( B-1) 5 parts, 84 parts of dimethyl decylamine (C-2), and heated to 60 ° C to dissolve boric acid. Then, 5 parts of ethylene glycol diacrylate (C-3) and 1 part of acrylic acid (G-1) were added and thoroughly mixed. After cooling to room temperature, 1.5 parts of Irgacure 184 (D-1) and 1.5 parts of Lucirin TPO (D-2) were added and mixed, and dissolved to obtain an adhesive composition.

(Examples 15 and 16, and Comparative Examples 7 and 8) An adhesive composition was prepared in the same manner as in Example 14 except that the respective blended components prepared above were blended in the proportions shown in Table 4 below.

Then, a polarizing plate test piece was produced in the same manner as in the above-described Example 1, and the performance of adhesion, decoloration resistance, and water resistance was evaluated in the same manner as in Example 1 using the polarizing plate test piece. The evaluation results are shown in Table 4 below.

Also, - represents no blending.

a photopolymerizable compound (B) containing a chelate-forming metal or semimetal compound (A), a functional group capable of forming a chelate compound with the metal or a semimetal, and an acid group-containing monomer (G) The adhesive composition of Examples 14 to 16 can sufficiently bond the polarizer and the protective film, and has excellent effects in both decolorization resistance and water resistance. On the other hand, Comparative Example 7 containing no metal or semimetal compound (A) capable of forming a chelate or photopolymerizable compound (B) containing a functional group capable of forming a chelate with a metal or a semimetal The adhesive composition of Comparative Example 8 was not preferable in terms of adhesion, decolorization resistance, and water resistance, and could not be practically used as an adhesive composition for a polarizing plate. From this, it is understood that the adhesive composition of the present invention is very excellent.

(Example 17) <Preparation of an adhesive composition: (H) component addition system> 5 parts of boric acid (A-5) and 2-ethyl acetoxyethyl methacrylate were added to the flask for preparation ( B-1) 5 parts, 85 parts of dimethyl decylamine (C-2), heated to 60 ° C, and dissolved boric acid. Then, 5 parts of ethylene glycol diacrylate (C-3) was added and thoroughly mixed. After cooling to room temperature, 1.5 parts of Irgacure 184 (D-1), 1.5 parts of Lucirin TP0 (D-2), and (E)-1-[3-(2-hydroxyphenyl)-2-propenyl) were added. Piperidine (H-1) 0.5 parts, and mixed and dissolved to obtain an adhesive composition.

(Examples 18 and 19, Comparative Examples 9 and 10) An adhesive composition was prepared in the same manner as in Example 17 except that the respective blended components prepared above were blended in the proportions shown in Table 5 below.

Then, a polarizing plate test piece was produced in the same manner as in the above-described Example 1, and the performance of adhesion, decoloration resistance, and water resistance was evaluated in the same manner as in Example 1 using the polarizing plate test piece. The evaluation results are shown in Table 5 below.

Also, - represents no blending.

a metal or semimetal compound (A) capable of forming a chelate compound, a photopolymerizable compound (B) containing a functional group capable of forming a chelate compound with the metal or a semimetal, and a photobase generator (H) In the adhesive compositions of Examples 17 to 19, the polarizer and the protective film can be sufficiently bonded, and excellent in decolorization resistance and water resistance. On the other hand, Comparative Example 9 containing no metal or semimetal compound (A) capable of forming a chelate, or photopolymerizable compound (B) containing a functional group capable of forming a chelate with a metal or a semimetal The adhesive composition of Comparative Example 10 was not preferable in terms of adhesion, decolorization resistance, and water resistance, and could not be actually used as an adhesive composition or the like. From this, it is understood that the adhesive composition of the present invention is very excellent. The above embodiments have been disclosed for the specific embodiments of the present invention, but the above embodiments are merely illustrative and not limiting. Various modifications that are obvious to those skilled in the art are intended to be included within the scope of the present invention. (industrial use)

The adhesive composition of the present invention and the adhesive composition for a polarizing plate comprising the adhesive composition are excellent in adhesion between a polarizer and a protective film, and do not require a drying step, and are excellent in productivity, and polarized light. The plate is also excellent in decolorization resistance, and is not particularly limited to a TAC film, and is also useful for bonding a protective film such as an acrylic film or a cyclic polyolefin resin film to a polarizer. Further, in addition to the use of the above-mentioned adhesive for polarizing plate, the adhesive composition of the present invention may be used, for example, for bonding various optical films or sheets, or for electronic components, precision equipment, packaging materials, display materials, and the like. Hehe.

Claims (16)

An adhesive composition comprising: a metal or semimetal compound (A) capable of forming a chelate compound, and a photopolymerizable compound (B) containing a functional group capable of forming a chelate with the metal or semimetal Made. An adhesive composition comprising a metal or semimetal compound (A) capable of forming a chelate compound, and a photopolymerizable compound containing a functional group capable of forming a chelate with the metal or semimetal (B) The chelate compound (AB) formed. The adhesive composition according to claim 1 or 2, wherein the chelate-forming metal or semimetal compound (A) is selected from the group consisting of a boron compound, an aluminum compound, a titanium compound, a zirconium compound, a zinc compound, And at least one of the group consisting of 矽 compounds. An adhesive composition according to claim 1 or 2, wherein the photopolymerizable compound (B) containing a functional group capable of forming a chelate with a metal or a semimetal is an ethylenic group containing an ethyl acetyl group. Saturated compound (b1). An adhesive composition according to claim 4, wherein the ethylenically unsaturated compound (b1) containing an ethylidene group is an aliphatic group containing an alkylene group having 1 to 10 carbon atoms. A (meth)acrylic acid alkyl ester compound. The adhesive composition of claim 1 or 2 further contains a photopolymerizable compound (C) (except that the photopolymerizable compound (B) is excluded). The adhesive composition of the sixth aspect of the invention, wherein the photopolymerizable compound (C) is selected from the group consisting of an ethylenically unsaturated compound having one ethylenically unsaturated group (c1) and having two or more ethylene groups. At least one of the group of unsaturated ethylenically unsaturated compounds (c2). The adhesive composition of the first or second aspect of the patent application is further composed of a polymerization initiator (D). The adhesive composition of the first or second aspect of the patent application is further composed of a urethane (meth)acrylate compound (E). The adhesive composition of claim 1 or 2 is further composed of a polymer (F). The adhesive composition of the first or second aspect of the patent application is further composed of an acid group-containing monomer (G). The adhesive composition according to claim 1 or 2 of the patent application further comprises a photobase generator (H). An adhesive composition for a polarizing plate, which is obtained by using the adhesive composition according to any one of claims 1 to 12. An adhesive for a polarizing plate, characterized in that the polarizing plate of the thirteenth aspect of the patent application is hardened with an adhesive composition. An adhesive for a polarizing plate is obtained by curing an adhesive composition for a polarizing plate according to claim 13 of the patent application by active energy ray irradiation. A polarizing plate characterized by laminating a polarizer and a protective film with an adhesive for interposing a polarizing plate according to claim 14 or 15.