WO2015022825A1

WO2015022825A1 - Adhesive agent composition, adhesive agent composition for polarizing plate, adhesive agent for polarizing plate, and polarizing plate manufactured using said adhesive agent

Info

Publication number: WO2015022825A1
Application number: PCT/JP2014/068108
Authority: WO
Inventors: 照彦小川; 御手洗　宏志
Original assignee: 日本合成化学工業株式会社
Priority date: 2013-08-12
Filing date: 2014-07-08
Publication date: 2015-02-19
Also published as: KR102159761B1; KR20160042813A; CN105229099A; TW201512348A; CN105229099B

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, polarizing plate adhesive composition, polarizing plate adhesive, 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 using the same, and specifically constitutes a polarizing plate used for a liquid crystal display device or the like. The present invention relates to an adhesive composition used for an active energy ray-curable acrylic adhesive suitable for bonding a polarizer and a protective film.

Liquid crystal display devices are widely used as image display devices for liquid crystal televisions, computer displays, mobile phones and digital cameras. Such a liquid crystal display device has a configuration in which polarizing plates are laminated on both sides of a glass substrate in which liquid crystal is encapsulated, and various optical functional films such as a retardation plate are laminated thereon as necessary.

Conventionally, a polarizing plate has been used as a structure in which a protective film is bonded to at least one surface, preferably both surfaces, of a polarizer made of a polyvinyl alcohol film. Here, as a polarizer, a dichroic substance such as iodine is formed in a PVA film formed by using a polyvinyl alcohol resin having a high saponification degree (hereinafter, polyvinyl alcohol is abbreviated as “PVA”). A uniaxially stretched PVA-based film in which the material is dispersed and adsorbed and preferably further crosslinked with a crosslinking agent such as boric acid is widely used. Since such a polarizer is a uniaxially stretched PVA-based film, it easily contracts under high humidity. Therefore, a protective film is bonded to the polarizer for the purpose of supplementing moisture resistance and strength.

As such a protective film, thermoplastic resins such as cellulose resin, polycarbonate resin, cyclic polyolefin resin, (meth) acrylic resin, and polyester resin are transparent, mechanical strength, thermal stability, moisture barrier property, isotropic property, etc. In particular, a protective film made of a triacetyl cellulose (TAC) resin has been widely used.

These protective films are bonded to the polarizer by an adhesive, and as such an adhesive, from the viewpoint of adhesiveness to a polarizer having a hydrophilic surface, it is the same as the PVA resin aqueous solution, particularly the polarizer. A PVA resin aqueous solution mainly composed of a high saponification degree PVA resin is preferably used.

By the way, in recent years, thinning of a polarizing plate has been demanded, and instead of a TAC film that has been most commonly used as a protective film, an acrylic film or a cyclic polyolefin resin film is used. However, these protective films instead of the TAC film cannot be firmly bonded to the polarizer using a conventional PVA adhesive. Therefore, various adhesives suitable for laminating protective films such as acrylic films and cyclic polyolefin resin films have been developed as alternatives to PVA adhesives.

In addition, since the PVA adhesive is used as a solution or dispersion using water, it is necessary to dry the water when the adhesive is cured, and it takes a long time to dry the water. Accordingly, there has been a demand for improvement in that the drying efficiency is poor and the production efficiency of the polarizing plate is lowered.

For example, Patent Document 1 proposes an adhesive composed of a composition containing an epoxy resin that does not contain an aromatic ring as a main component and a photocationic polymerization initiator. Such an adhesive is cationic polymerization by irradiation with active energy rays. Even if a resin film with low moisture permeability is used as the protective film, the protective film is applied to one or both sides of the polarizer with sufficient adhesive strength without causing problems such as poor appearance. It is described that a combined polarizing plate can be provided.

Moreover, in patent document 2, the active energy ray hardening-type adhesive composition containing 3 types of radically polymerizable compounds from which SP value differs as a hardening component is excellent in adhesiveness of a polarizer and a protective film, and durability, It has been proposed as an adhesive with excellent water resistance.

Further, in Patent Document 3, 4-butylhydroxyacrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1 to 70% by weight, other radical polymerizable compound: 0 to 15% by weight, photopolymerization initiator : 0.01-20% by weight, Silane coupling agent: 0-10% by weight, radically polymerizable adhesive for forming a polarizing plate having a glass transition temperature after curing of -80 to 0 ° C A composition has been proposed, and by using the adhesive composition, a PVA polarizer and a hard-to-adhere protective film typified by an acrylic film or a cycloolefin film are used as constituent layers, and the adhesive strength It is said that it is a polarizing plate which can form the small polarizing plate piece which is large and is excellent in durability, and is excellent in the punching workability.

Patent Document 4 discloses an ultraviolet curable composition containing a (meth) acrylamide compound having no hydroxyl group, a (meth) acrylic acid alkyl ester compound having a hydroxyl group, boric acid and a photopolymerization initiator. It has been proposed that by using the adhesive composition, an ultraviolet curable composition having excellent adhesive strength can be obtained not only for various protective films but also for acrylic resin films.

JP 2004-245925 A JP 2012-144690 A JP 2010-282161 A JP2013-194082A

However, the adhesive of Patent Document 1 uses a cationic polymerizable UV curable adhesive instead of a water-based adhesive. However, the cationic polymerizable UV curable adhesive has a dark reaction after UV irradiation. Therefore, when a long cured product is formed into a take-up roll, there is a problem that curling tends to occur during storage. In addition, the cationic polymerizable ultraviolet curable adhesive has a problem that it is easily affected by humidity during curing and the cured state tends to vary.

In the radical polymerizable ultraviolet curable adhesive of Patent Document 2 described above, the adhesive layer is relatively hard, resulting in a decrease in adhesive strength over time, which is not satisfactory in terms of punching resistance and durability. There wasn't.

The radical polymerizable adhesive composition of Patent Document 3 described above was accompanied by curing shrinkage when the (meth) acrylic acid monomer was cured, so that the stability of initial adhesion was low and the adhesive strength was not sufficient.

The ultraviolet curable composition of Patent Document 4 showed an adhesive force to the acrylic resin film, but the adhesive force to the polarizer was not sufficient, and the color loss resistance was weak.

Therefore, although the active energy ray-curable adhesive does not require a drying step and the production efficiency is higher than the PVA adhesive used as an aqueous solution, it can sufficiently bond various protective films for polarizing plates and polarizers. Was difficult and further improvement was required.

In recent years, there has also been a problem that color loss (discoloration) occurs when a polarizing plate is left under high temperature and high humidity for a long time. For example, it is a more severe evaluation, but it is immersed in warm water. Therefore, there is a demand for a polarizing plate that does not lose color or has reduced color loss even in such a state. As a method for obtaining such a polarizing plate having excellent color fading resistance, in the situation where improvement of an adhesive for bonding a polarizer and a protective film is also demanded, the adhesion described in Patent Documents 1 to 4 above. In the case of the agent, such color loss resistance cannot be obtained.

Therefore, in the present invention, under such a background, the adhesive is excellent in adhesive force, and is suitable for bonding various protective films for polarizing plates and polarizers, in particular, protective films other than TAC and polarizers. An object of the present invention is to provide an adhesive composition that is excellent in production efficiency and excellent in resistance to color loss, particularly an adhesive composition for polarizing plates.

However, the present inventors have made extensive studies in view of such circumstances, and as a result, in an adhesive composition for an active energy ray-curable polarizing plate, a metal or semi-metal chelate compound is present when it becomes an adhesive. As a result, it was found that the polarizer and the protective film were excellent in adhesion, and further, the color fading resistance of the polarizing plate was excellent, and the present invention was completed.

That is, the gist of the present invention is an adhesive comprising a chelate-forming metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid. The present invention relates to a composition, and is formed from a chelatable metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid. The present invention relates to an adhesive composition containing a chelate compound (AB).

Furthermore, the present invention provides an adhesive composition for a polarizing plate using the adhesive composition, an adhesive for a polarizing plate obtained by curing the adhesive composition, and a polarizer and a protective film through the adhesive for the polarizing plate. The present invention also provides a polarizing plate in which is attached.

Here, in the present invention, it is important that a metal or metalloid chelate compound is present. This is because the hydroxyl group on the PVA surface forming the polarizer and the chelate-forming functional group in the adhesive are included. It is presumed that the color loss resistance of the polarizing plate is improved in order to form a chemical bond, increase the adhesive strength between the polarizer and the protective film, and prevent the diffusion of iodine in the polarizer.

The adhesive composition of the present invention, especially the adhesive composition for polarizing plates, has high production efficiency of polarizing plates, and various protective films for polarizing plates and polarizers, particularly acrylic films and cyclic polyolefin resin films. Protective films other than TAC and polarizers can be sufficiently bonded, and color loss is suppressed even when the polarizing plate is immersed in high temperature and high humidity or warm water. Excellent polarizing plates can be obtained.

The present invention will be described in detail below, but these show examples of desirable embodiments.
In the present invention, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate.
The acrylic monomer is a monomer having at least one of an acryloyl group and a methacryloyl group, and the acrylic resin is a resin obtained by polymerizing a polymerization component containing at least one acrylic monomer.

(Adhesive composition)
The adhesive composition of the present invention comprises:
[I] A metal or metalloid compound (A) capable of forming a chelate and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid. Yes,
Also,
[II] A chelate compound (AB) formed from a chelate-forming metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid ).

<Metal or metalloid compound (A) capable of chelate formation>
The chelate-forming metal or metalloid compound (A) used in the present invention is not particularly limited as long as it can form a chelate with the photopolymerizable compound (B) described later. For example, a metal or metalloid alcoholate , A hydrolyzate of the alcoholate, a condensate of the alcoholate, a chelate compound of the alcoholate, a partial alcoholate of the chelate compound, and a metal or metalloid acylate. In particular, metal or metalloid alcoholates and chelate compounds of the alcoholates are preferable. Particularly, metal or metalloid alcoholates represented by the following general formula (1), and chelate compounds of the alcoholates Is preferably used.
In addition, as a metal or metalloid compound (A) which can form a chelate, only 1 type may be used from the said compound, and arbitrary 2 or more types may be used together.

Wherein M represents a metal or metalloid atom, R ¹ represents a monovalent organic group having 1 to 10 carbon atoms which may be the same or different, and R ² represents hydrogen or C 1-5 alkyl group or C 1-6 acyl group or phenyl group, m and n each represent an integer of 0 or more, and m + n represents the valence of M.)

In the general formula (1), examples of the metal or metalloid atom represented by M include transition metal, group 2, group 12, group 13, and group 14 metal or metalloid elements. Boron, silicon, aluminum, zirconium, titanium, magnesium, chromium, cobalt, copper, iron, nickel, vanadyl, zinc, indium, calcium, manganese, tin are preferred, and boron, silicon, aluminum, titanium, chromium, copper, Iron, nickel, zinc and indium are preferred. In general, divalent to tetravalent metals or metalloids are used, and boron, silicon, aluminum, titanium and zirconium are particularly preferably used. Further, it is most preferable that the alcoholate or acylate is in a liquid state and boron or silicon is used from the viewpoint of convenience of handling. Moreover, even if it is a solid state, it should just be easily soluble in a photopolymerizable compound (C).

In the general formula (1), the monovalent organic group having 1 to 10 carbon atoms represented by R ¹ includes, for example, methyl when the general formula (1) is a metal or semimetal alcoholate. Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, Alkyl groups such as 2-ethylhexyl group; acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group, (meth) acrylic group In addition to oxy groups, ureido groups, amide groups, fluoroacetamide groups, isocyanate groups, etc., substituted derivatives of these groups can be mentioned. Examples of the substituent in such a substituted derivative include 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, a (meth) acryloxy group, and a ureido group. And ammonium base. However, the carbon number of R ¹ composed of these substituted derivatives is 10 or less including the carbon atom in the substituent.

In the case where the general formula (1) is a metal or metalloid acylate, examples of R ¹ include an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group, a benzoyloxyl group, and a trioyloxyl group. Of the acyloxyl group.
In the above general formula (1), when two or more R ^{1 s} are present, they may be the same or different from each other, but are preferably the same.

In the general formula (1), examples of the alkyl group having 1 to 5 carbon atoms represented by R ² include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec- Examples thereof include a butyl group, a t-butyl group, and an n-pentyl group. Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. Can do. Moreover, what is represented by R ² may be hydrogen.
In the general formula (1), when there are a plurality of R ^{2 s} , they may be the same or different from each other, but the same is preferable.

The hydrolyzate of a metal or metalloid alcoholate in the present invention is a product obtained by hydrolyzing an OR ² group contained in the metal or metalloid alcoholate, but is an OR contained in a metal or metalloid alcoholate. All of ² need not be hydrolyzed. For example, only one of them may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof.

The metal or metalloid alcoholate condensate in the present invention is a product having the MOM structure obtained by condensation of the above metal or metalloid alcoholate hydrolyzate. It is not necessary that all the hydroxyl groups of the hydrolyzate are condensed, and it is a concept that includes a mixture of a small part of the hydroxyl groups, a mixture of those having different degrees of condensation, and the like.

In the present invention, the metal or metalloid alcoholate chelate compound is a compound having a structure in which at least one of metal or metalloid alcoholate ligands is chelate-bonded. Such metal or metalloid alcoholate chelate compounds include metal or metalloid alcoholates and β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylates, hydroxycarboxylic acid esters, ketoalcohols and aminoalcohols. It is preferably obtained by reaction with at least one selected compound.

Among these compounds, β-diketones or β-ketoesters are preferably used. Specific examples thereof include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-. Propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4 -Octane-dione, 2,4-nonane-dione, 5-methyl-hexane-dione and the like. Of these, acetylacetone and ethyl acetoacetate are particularly preferably used.

The hydrolyzate of the chelate compound in the present invention is not necessarily required to hydrolyze all the OR ² groups contained in the chelate compound, like the hydrolyzate of the metal or metalloid alcoholate described above. Only one may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof.

In the present invention, the metal or metalloid acylate is one in which at least one of the ligands of the metal or metalloid alcoholate is an acyloxyl group.

Among these chelate-forming metal or metalloid compounds (A), as specific examples of metal or metalloid alcoholates and metal or metalloid alcoholate chelate compounds,
[1] Boron compounds such as boric acid, trimethyl borate, triethyl borate, tributyl borate (including normal, iso, tertiary, secondary), tripropyl borate, triisopropyl borate, trimethyl carbitol borate;

[2] Aluminum hydroxide, triethoxyaluminum, diethoxy-acetylacetonate aluminum, ethoxy-bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, tripropoxyaluminum, dipropoxy-acetylacetonatoaluminum, propoxy-bis (Acetylacetonato) aluminum, tributoxyaluminum, dibutoxy-acetylacetonatoaluminum, butoxybis (acetylacetonato) aluminum, diethoxyethylacetoacetate aluminum, ethoxybis (ethylacetoacetate) aluminum, tris (ethylacetoacetate) ) Aluminum, dipropoxy ethyl acetoacetate aluminum, propoxy bis Le acetoacetate) aluminum, dibutoxy ethylacetoacetate aluminum, aluminum compounds such as butoxy-bis (ethylacetoacetate) aluminum;

[3] Titanium hydroxide, tetraethoxy titanium, triethoxy acetylacetonato titanium, diethoxy bis (acetylacetonato) titanium, ethoxy tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, tetrapropoxy titanium, Tripropoxy acetylacetonato titanium, dipropoxy bis (acetylacetonato) titanium, propoxy tris (acetylacetonato) titanium, tetrabutoxy titanium, tributoxy acetylacetonato titanium, dibutoxy bis (acetylacetonato) titanium, butoxy・ Tris (acetylacetonate) titanium, triethoxy ethylacetoacetate titanium, diethoxy bis Ethyl acetoacetate) titanium, ethoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, tripropoxy ethyl acetoacetate titanium, dipropoxy bis (ethyl acetoacetate) titanium, propoxy tris (ethyl acetoacetate) Titanium compounds such as titanium, tributoxy ethyl acetoacetate titanium, dibutoxy bis (ethyl acetoacetate) titanium, butoxy tris (ethyl acetoacetate) titanium;

[4] Tetrakis (methoxy) zirconium, tetrakis (ethoxy) zirconium, tetrakis (propoxy) zirconium, tetrakis (isopropoxy) zirconium, tetrakis (butoxy) zirconium, tetrakis (isobutyloxy) zirconium, tetrakis (second butyloxy) zirconium, tetrakis (Tertiary butyloxy) zirconium, tetrakis (amyloxy) zirconium, tetrakis (tertiary amyloxy) zirconium, tetrakis [2- (2-methoxy) ethoxy] zirconium, tetrakis [2- (1-methyl-2-methoxy) propoxy] zirconium Tetrakis [2- (2-methoxy) propoxy] zirconium, tetrakis [2- (dimethylamino) ethoxy] zirconium, tetrakis [2- 2-dimethylamino-1-methyl) propoxy] zirconium, tetrakis [2- (2-dimethylamino) propoxy] zirconium, bis (2-propoxy) bis [2- (2-dimethylamino-1-methyl) propoxy] zirconium Bis (tertiary butoxy) bis [2- (2-dimethylamino-1-methyl) propoxy] zirconium, bis (tertiary butoxy) bis [2- (2-dimethylamino) propoxy] zirconium, (tertiary butoxy) Alkoxyzirconium compounds such as tris [2- (2-dimethylamino-1-methyl) propoxy] zirconium, tris (tert-butoxy) [2- (2-dimethylamino-1-methyl) propoxy] zirconium; tetrakis (dimethylamino) ) Zirconium, tetrakis (diethylamino) zir Ni, tetrakis (ethylmethylamino) zirconium, tetrakis (dipropyl) zirconium, tetrakis (dibutylamino) zirconium, bis (dimethylamino) bis (diethylamino) zirconium, bis (diethylamino) bis (ethylmethylamino) zirconium, (diethylamino) tris (Ethylmethylamino) zirconium, 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 (ethylmethylamino) zirconium, bis (2-propoxy) bis ( Aminozirconium compounds such as diethylamino) zirconium, bis (tertiarybutyl) bis (diethylamino) zirconium, bis (tertiarybutyl) bis (ethylmethylamino) zirconium, (tertiarybutyl) tris (ethylmethyl) zirconium, and tetrakisacetyl Acetonate, tetrakisethyl acetoacetonate, tetrakishexane-2,4-dionate, tetrakis-5-methylhexane-2,4-dionate, tetrakisheptane-2,4-dionate, tetrakis-2-methylheptane-3,5 -Dionate, tetrakis-5-methylheptane-2,4-dionate, tetrakis-6-methylheptane-2,4-dionate, tetrakis-2,2-dimethylheptane-3,5-dionate, tetrakis-2,6- Dimethylhe Tan-3,5-dionate, tetrakis-2,2,6-trimethylheptane-3,5-dionate, tetrakis-2,2,6,6-tetramethylheptane-3,5-dionate, tetrakis-octane-2 , 4-Dionate, Tetrakis-2,2,6-trimethyloctane-3,5-Dionate, Tetrakis-2,6-dimethyloctane-3,5-Dionate, Tetrakis-2-methyl-6-ethyldecane-3,5 -Alkylates β-diketonates such as dionate, tetrakis-2,2-dimethyl-6-ethyldecane-3,5-dionate, tetrakis-1,1,1-trifluoropentane-2,4-dionate, tetrakis-1 , 1,1-trifluoro-5,5-dimethylhexane-2,4-dionate, tetrakis-1,1,1,5 Fluorine-substituted alkyl β-diketonates such as 5,5-hexafluoropentane-2,4-dionate and tetrakis-1,3-diperfluorohexylpropane-1,3-dionate, tetrakis-1,1,5,5 -Tetramethyl-1-methoxyhexane-2,4-dionate, tetrakis-2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dionate, tetrakis-2,2,6,6-tetra Zirconium β-diketone compounds such as ether-substituted β-diketonates such as methyl-1- (2-methoxyethoxy) heptane-3,5-dionate;

[5] Zinc hydroxide, diethoxy zinc, ethoxy acetyl acetonate zinc, bis (acetyl acetonate) zinc, dipropoxy zinc, propoxy acetyl acetonate zinc, dibutoxy zinc, butoxy acetyl acetonate zinc, ethoxy ethyl acetoacetate Zinc compounds such as zinc, bis (ethyl acetoacetate) zinc, propoxy-ethyl acetoacetate zinc, butoxy-ethyl acetoacetate zinc, di (acetylacetonato) zinc, di (ethylacetoacetate) zinc;

[6] Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, etc. Silicon compounds such as tetraalkoxysilane and compounds obtained by hydrolyzing (condensing) them;
Can be mentioned.

Among these metal or metalloid alcoholates and chelate compounds, preferred are boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, aluminum hydroxide, triethoxyaluminum, tripropoxyaluminum, tributoxy. Aluminum, dipropoxy-ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, tris (acetylacetonate) aluminum, titanium hydroxide, dibutoxy bis (acetylacetonato) titanium, dipropoxy bis (acetylacetonato) titanium, diethoxy・ Bis (acetylacetonato) titanium, dibutoxy ・ bis (ethylacetoacetate) titanium, dipropoxy bis ( Examples include tylacetoacetate) titanium, diethoxy bis (ethylacetoacetate) titanium, zinc hydroxide, di (acetylacetonato) zinc, and di (ethylacetoacetate) zinc. Particularly preferred compounds are boric acid and trimethylborate. Triethyl borate, tripropyl borate, tributyl borate, aluminum hydroxide, tripropoxyaluminum, tris (acetylacetonato) aluminum, dibutoxy bis (acetylacetonato) titanium, di (acetylacetonato) zinc and the like. Furthermore, boric acid, trimethyl borate, and triethyl borate from the viewpoint of convenience in handling in a liquid state at room temperature, solubility in the photopolymerizable compound (C), and reactivity with the hydroxyl group of the PVA resin forming the polarizer. Most preferred are trialkyl borates having an alkyl group of 1 to 5 carbon atoms such as tripropyl borate, tributyl borate, etc., particularly tributyl borate.

Specific examples of the metal or metalloid acylate include dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimaloniate. And di-i-propoxy-titanium dibenzoylate, di-n-butoxy-zirconium diacetate, di-i-propylaluminum monomalonate and the like. Particularly preferred compounds are dihydroxy-titanium dibutyrate and di- -Titanium compounds such as i-propoxy titanium diacetate.

<Photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid>
Further, the photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid used in the present invention may be a compound having the functional group and an ethylenically unsaturated group.

Examples of the functional group capable of forming a chelate with the above metal or semimetal include functional groups having a β-diketone structure, such as acetoacetyl groups and malonic esters, which have a β-diketone structure. An acetoacetyl group is preferred from the viewpoint of convenience and reactivity with a hydroxyl group.

In the present invention, when the photopolymerizable compound (B) containing a functional group capable of chelating with a metal or a metalloid is an acetoacetyl group-containing ethylenically unsaturated compound (b1), for example, it is produced by the following method. can do.

(I) A diketene is reacted with the functional group-containing ethylenically unsaturated compound (i). Examples of the functional group include a hydroxyl group, an amide group, a urethane group, an amino group, a carboxyl group, and the like. Preferred examples of the functional group-containing ethylenically unsaturated compound (i) include an alkylene group having 1 to 10 carbon atoms. Aliphatic acetoacetyl group-containing alkyl (meth) acrylate compounds having 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3 -(Meth) acrylate having a C1-C5 hydroxyalkyl group such as chloropropyl (meth) acrylate.

(II) The functional group-containing ethylenically unsaturated compound (i) is transesterified with acetoacetate.

In the case of (I) above, the reaction of diketene is non-catalytic, as well as the presence of tertiary amines, acids (sulfuric acid, etc.), basic salts (sodium acetate, etc.), organometallic compounds (dibutyltin laurate, etc.) Can be done below.
The reaction of (II) acetoacetate is preferably performed in the presence of a transesterification catalyst such as calcium acetate, zinc acetate, lead oxide or the like.
Among the above functional group-containing ethylenically unsaturated compounds (i), a (meth) acrylate having a hydroxyalkyl group is preferable from the viewpoints of versatility and convenience, production stability, and storage stability.

<Photopolymerizable compound (C)>
In the present invention, it is preferable from the viewpoint of coating property, curability, adhesiveness and the like that it further contains a photopolymerizable compound (C) (however, excluding the photopolymerizable compound (B)). .
As the photopolymerizable compound (C) used in the present invention, the photopolymerizable compound (B) is excluded, and an ethylenically unsaturated compound (c1) having one ethylenically unsaturated group and an ethylenically unsaturated compound are used. It is preferably at least one selected from the group of ethylenically unsaturated compounds (c2) having two or more saturated groups.

Examples of the ethylenically unsaturated compound having one ethylenically unsaturated group (hereinafter sometimes abbreviated as “monofunctional monomer”) (c1) include styrene, vinyltoluene, chlorostyrene, α-methylstyrene. , Methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (Meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) ) Acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, Nylphenol propylene oxide modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, etc. ) Acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, dimethylacrylamide, 2-hydroxyethylacrylamide, N-methylol (Meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, polyoxyethylene secondary alkyl ether acrylate and the like.

In addition, a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination. As the Michael adduct of acrylic acid, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid A trimer, an acrylic acid tetramer, a methacrylic acid tetramer, etc. are mentioned. The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxy Examples include ethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, and the like. Furthermore, other oligoester acrylates can also be mentioned.

The ethylenically unsaturated compound having two or more ethylenically unsaturated groups (hereinafter sometimes abbreviated as “polyfunctional monomer”) (c2) includes a bifunctional monomer and a trifunctional or higher functional monomer. It is done.

Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene. Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) ) Acrylate, propylene oxide modified bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, Toxylated cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) Acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (Meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate and the like.

Examples of the tri- or higher functional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth). ) Acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa ( (Meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolact 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 can be mentioned.
The photopolymerizable compound (C) may be used alone or in combination of two or more.

Thus, in the present invention, [I] a chelate-forming metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid, preferably other An adhesive composition comprising a photopolymerizable compound (C) (excluding the photopolymerizable compound (B)), and [II] a chelate-forming metal or metalloid compound (A); A chelate compound (AB) formed from a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid, preferably another photopolymerizable compound (C) ( However, an adhesive composition containing a photopolymerizable compound (B) is used.

With regard to 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 / 90 to 30/70 is preferable. If the value of (A) / (B) is too small, there is a tendency that the adhesive force between the polarizer and the protective film is lowered and the color loss resistance is lowered, and if too large, the durability during the hot water resistance test is lowered. There is a tendency to invite.

In the case of [I] above, (A) to (C) can be appropriately blended to form an adhesive composition. With respect to the content ratios of (A) to (C), (A) is 0.1 to 30% by weight and (B) is 0.9 to 40% by weight with respect to the total of (A) to (C). , (C) is preferably 30 to 99% by weight, in particular, (A) is 0.5 to 20% by weight, (B) is 1.5 to 30% by weight, and (C) is 50 to 98% by weight. %, (A) is preferably 1 to 15% by weight, (B) is preferably 5 to 20% by weight, and (C) is preferably 65 to 94% by weight. If the content of (A) is too small, the adhesive strength between the polarizer and the protective film tends to decrease and the color loss resistance tends to decrease. If the content is too large, the durability decreases during the hot water resistance test, and the polarization There exists a tendency for the adhesive force of a child and a protective film to fall. When there is too little content of this (B), there exists a tendency for the adhesive force of a polarizer and a protective film to fall, and when too large, there exists a tendency for the durability at the time of a hot water resistance test to fall. When there is too little content of this (C), there exists a tendency for the durability at the time of a hot water test to fall, and when too much, there exists a tendency for the adhesive force of a polarizer and a protective film to fall.

In the present invention, an adhesive composition containing (A) and (B), preferably further (C), is applied to a substrate such as a polarizer, and is usually 50 to 200 ° C., particularly preferably 60 to 150. A chelate compound (AB) can be formed by drying at 0 ° C. Further, after preparing an adhesive composition containing (A) and (B), preferably further (C), the reaction between (A) and (B) is usually carried out at 50 to 120 ° C., particularly preferably at 60 to 90 ° C. To form a chelate compound (AB).

In the case of [II], the chelate compound (AB) formed from (A) and (B), and preferably (C), is contained. ), (B), a chelate compound (AB) formed from (A) and (B), and preferably (C).

The content of the chelate compound (AB) is preferably 0.5 to 50% by weight, particularly 1 to 40% by weight, and more preferably 5 to 30% by weight.
If the content is too small, the adhesive force between the polarizer and the protective film tends to decrease and the color loss resistance tends to decrease. If the content is too large, the durability decreases during the hot water resistance test, and the polarizer and the protective film. There is a tendency for the adhesive strength of the steel to decrease.

In forming such a chelate compound (AB), it is usually mixed at 20 to 120 ° C., particularly 30 to 80 ° C.

In the present invention, the presence of the above-mentioned metal or metalloid chelate compound exerts an effect of excellent color fading resistance of the polarizing plate.

In the adhesive composition of the present invention, a polymerization initiator, a silane coupling agent, an antistatic agent, other acrylic adhesives, other adhesives, urethane resins, rosins, as long as the effects of the present invention are not impaired. Rosin ester, hydrogenated rosin ester, phenol resin, aromatic modified terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, styrene resin, xylene resin and other tackifiers, polyol and other plasticizers, coloring Conventionally known additives such as additives, fillers, anti-aging agents, ultraviolet absorbers, functional dyes, and compounds that cause coloration or discoloration upon irradiation with ultraviolet rays or radiation can be incorporated. The blending amount is preferably 30% by weight or less, particularly preferably 20% by weight or less, based on the total composition.

Further, in addition to the above-mentioned additives, a small amount of impurities or the like contained in the raw materials for producing the constituent components of the adhesive composition may be included.

<Polymerization initiator (D)>
In this invention, it is preferable to contain said polymerization initiator (D) and to harden an adhesive composition further.
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. It is preferable to use d1) in that it can be cured by irradiation with active energy rays such as ultraviolet rays for a very short time.

When the photopolymerization initiator (d1) is used, the adhesive composition is cured by irradiation with active energy rays, and when the thermal polymerization initiator (d2) is used, the adhesive composition is cured by heating. However, it is also preferable to use both in combination as necessary.

Examples of the photopolymerization initiator (d1) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether etc. Zoins; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium Benzophenones such as chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy - Thioxanthones such as 2,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Acyl phosphine oxides such as pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, as for these photoinitiators (d1), only 1 type may be used independently and 2 or more types may be used together.

These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.

Examples of the thermal polymerization initiator (d2) include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexyl peroxide). ) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -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-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydro Peroxide, t-butyl hydroperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane , T-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethyl Hexanoyl peroxide, octanoylpa Oxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butyl) Cyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-s-butylperoxydicarbonate, Di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3- Tramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxy Pivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanooate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylper) Oxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t- Hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutylene , T-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy- 2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2, 5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl Peroxide, 3,3 ', 4,4'-teto Organic peroxide initiators such as la (t-butylperoxycarbonyl) benzophenone and 2,3-dimethyl-2,3-diphenylbutane; 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1 -[(1-cyano-1-methylethyl) azo] formamide, 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) dihydrochloride, 2,2'-azobis (2-methyl) -N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine Dihydride chloride, 2,2'-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydro Chloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl Propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3 , 4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] ] Propionamide], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2,2'-azobis [2- Methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'- Azobis (2-methylpropane), dimethyl-2,2-azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl ) Propionitrile] and the like; and the like. In addition, these thermal polymerization initiators (d2) may be used alone or in combination of two or more.

Regarding the content of the polymerization initiator (D), the total of the above (A) and (B) (when (C) is contained, the total of (A) to (C)) is 100 parts by weight, The amount is preferably 0.5 to 20 parts by weight, particularly preferably 0.8 to 15 parts by weight, and further preferably 1 to 10 parts by weight. When the content of the polymerization initiator (D) is too small, the curability tends to be poor and the physical properties tend to become unstable. When the content is too large, the low molecular weight component increases and the crosslinking density decreases, resulting in water resistance and heat resistance. There is a tendency to decrease.

In the present invention, in addition to the above-described components, a urethane (meth) acrylate compound (E), a polymer (F), an acid group-containing monomer (G), and a photobase generator (H) are added as appropriate, respectively. It is preferable to contain as coating properties, curability, adhesiveness, and the like. These may be used alone or in combination of two or more. Among the above compounds, the case where the urethane (meth) acrylate compound (E) is blended is preferable, and the combined system of the urethane (meth) acrylate compound (E) and the polymer (F) is particularly preferable.

<Urethane (meth) acrylate compound (E)>
The urethane (meth) acrylate compound (E) is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (e1), a polyvalent isocyanate compound (e2), and a polyol compound (e3) (E1 ), A hydroxyl group-containing (meth) acrylate compound (e1), and a polyisocyanate compound (e2) (E2) obtained by reaction. Among them, particularly preferred is a urethane (meth) acrylate compound (E1) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (e1), a polyvalent isocyanate compound (e2) and a polyol compound (e3).

The weight average molecular weight of the urethane (meth) acrylate compound (E) used in the present invention is preferably 500 to 50000, more preferably 1000 to 30000. If the weight average molecular weight is too small, curing shrinkage tends to increase and the adhesive force tends to decrease, and if too large, the water resistance tends to decrease.

The above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: Shodex GPC KF-806L (excluded) was subjected to high performance liquid chromatography (manufactured by Showa Denko Co., Ltd., “Shodex GPC system-11 type”). (Limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) Measured by using series.

The viscosity of the urethane (meth) acrylate compound (E) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly preferably 500 to 120,000 mPa · s, and still more preferably 1,000 to 100,000 mPa · s. -S. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.

Examples of the hydroxyl group-containing (meth) acrylate compound (e1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylates, hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) ) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerol di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone modified Pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate Etc.

Among these, a hydroxyl group (meth) acrylate compound having one ethylenically unsaturated group is preferable because it can mitigate cure shrinkage during coating film formation, and more preferably 2-hydroxyethyl (meth). Hydroxyalkyl (meth) acrylates such as acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, It is preferable to use 2-hydroxyethyl (meth) acrylate in terms of excellent reactivity and versatility.
Moreover, these can be used 1 type or in combination of 2 or more types.

Examples of the polyvalent isocyanate compound (e2) include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aliphatic polyisocyanates such as polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanate methyl) Cyclohexane or other alicyclic polyisocyanates, or trimer compounds or multimeric compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates (for example, “manufactured by Nippon Polyurethane Industry Co., Ltd.” Aquanate 100 "," Aquanate 110 "," Aquanate 200 "," Aquanate 210 ", etc.).

Among these, from the point of little yellowing, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1, An alicyclic diisocyanate such as 3-bis (isocyanatomethyl) cyclohexane is preferably used, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate are particularly preferably used in terms of low cure shrinkage. Preferably, isophorone diisocyanate is used in terms of excellent reactivity and versatility.

Examples of the polyol compound (e3) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, polysiloxane polyols, and the like.

Examples of the polyether polyol include, for example, polyether glycols containing an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Coalescence is mentioned.

Examples of the polyester-based polyol include three types of components: a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And the like.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol)

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.

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

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

Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.

The polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.

Examples of the polyolefin-based polyol include those having a saturated hydrocarbon skeleton having a homopolymer or copolymer such as ethylene, propylene and butene, and having a hydroxyl group at the molecular end.

Examples of the polybutadiene-based polyol include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.

Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the molecule of the polymer or copolymer of the (meth) acrylic acid ester. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic And (meth) acrylic acid alkyl esters such as 2-ethylhexyl acid, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate.

Examples of the polysiloxane polyol include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.

Among these, polyester-based polyols and polyether-based polyols are preferable, and polyester-based polyols are particularly preferable because they are excellent in mechanical properties such as flexibility during curing.

The weight-average molecular weight of the polyol compound (e3) is preferably 500 to 8000, particularly preferably 550 to 5000, and more preferably 600 to 3000. If the molecular weight of the polyol compound (e3) is too large, the adhesive force 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 as follows. The following description is about the urethane (meth) acrylate compound (E1) obtained by reacting the hydroxyl group-containing (meth) acrylate compound (e1), the polyvalent isocyanate compound (e2) and the polyol compound (e3). However, the urethane (meth) acrylate compound (E2) obtained by reacting the hydroxyl group-containing (meth) acrylate compound (e1) and the polyvalent isocyanate compound (e2) is also produced by carrying out according to this method. it can.

The production method of the urethane (meth) acrylate compound (E1) is usually the above hydroxyl group-containing (meth) acrylate compound (e1), polyvalent isocyanate compound (e2), polyol compound (e3) in a reactor. The reaction product obtained by reacting the polyol compound (e3) and the polyvalent isocyanate compound (e2) in advance may be added to the reaction product obtained by reacting the polyol compound (e3) and the polyhydric isocyanate compound (e2) in advance. ) Is useful in terms of reaction stability and reduction of by-products.

For the reaction between the polyol compound (e3) and the polyvalent isocyanate compound (e2), known reaction means can be used. At that time, for example, the molar ratio of the isocyanate group in the polyvalent isocyanate compound (e2) to the hydroxyl group in the polyol compound (e3) is usually about 2n: (2n-2) (n is an integer of 2 or more). Thus, after obtaining a terminal isocyanate group-containing urethane (meth) acrylate compound having an isocyanate group remaining, an addition reaction with the hydroxyl group-containing (meth) acrylate compound (e1) is made possible.

The addition reaction of the reaction product obtained by reacting the polyol compound (e3) and the polyvalent isocyanate compound (e2) in advance with the hydroxyl group-containing (meth) acrylate compound (e1) is also a known reaction. Means can be used.

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

In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (e1), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (E) is obtained.

In the reaction between the polyol compound (e3) and the polyvalent isocyanate compound (e2), and the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (e1), a catalyst is used for the purpose of promoting the reaction. It is also preferable to use an organic metal compound such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octoate, tin octoate, cobalt naphthenate, stannous chloride. Metal salts such as stannic chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, Amine catalysts such as N'-tetramethyl-1,3-butanediamine and N-ethylmorpholine, bismuth nitrate, bromide Organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, lauryl Organic acid bismuth such as bismuth acid salt, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate Examples thereof include bismuth-based catalysts such as salts, among which dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferable.

In the reaction between the polyol compound (e3) and the polyvalent isocyanate compound (e2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (e1), it reacts with the isocyanate group. Organic solvents having no functional group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and organic solvents such as aromatics such as toluene and xylene can be used.

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

The number of unsaturated groups of the urethane (meth) acrylate compound (E) used in the present invention is preferably 2 to 6 in view of curing shrinkage, particularly 2 to 4 and more preferably 2.

When the urethane (meth) acrylate compound (E) is used, [I ′] a photopolymerizable polymer containing a chelate-forming metal or metalloid compound (A) and a functional group capable of chelating with the metal or metalloid The compound (B), the urethane (meth) acrylate-based compound (E), and preferably another photopolymerizable compound (C) (however, excluding the photopolymerizable compound (B)) are further contained. The adhesive composition is also formed of [II ′] a chelate-forming metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid. A chelate compound (AB), a urethane (meth) acrylate compound (E), and preferably another photopolymerizable compound (C) (excluding the photopolymerizable compound (B)). The adhesive composition comprising a.

In the case of [I ′] above, (A) to (C) and (E) can be appropriately blended to form an adhesive composition. With respect to each content ratio of (A) to (C) and (E), (A) is 0.1 to 30% by weight with respect to the total of (A) to (C) and (E), (B) Is preferably 0.01 to 30% by weight, (C) is preferably 30 to 99% by weight, and (E) is preferably 0.5 to 50% by weight, in particular (A) is 0.5 to 20% by weight, (B) is 0.05 to 20% by weight, (C) is 50 to 98% by weight, (E) is 1 to 40% by weight, (A) is 1 to 15% by weight, and (B) is 0.8%. 1 to 10% by weight, (C) is preferably 65 to 94% by weight, and (E) is preferably 4 to 30% by weight.

If the content of (A) is too small, the adhesive strength between the polarizer and the protective film tends to decrease and the color loss resistance tends to decrease. If the content is too large, the durability decreases during the hot water resistance test, and the polarization There exists a tendency for the adhesive force of a child and a protective film to fall. When there is too little content of this (B), there exists a tendency for the adhesive force of a polarizer and a protective film to fall, and when too large, there exists a tendency for the durability at the time of a hot water resistance test to fall. When there is too little content of this (C), there exists a tendency for the durability at the time of a hot water test to fall, and when too much, there exists a tendency for the adhesive force of a polarizer and a protective film to fall. If the content of (E) is too small, the water resistance and the adhesive strength tend to decrease, and if too large, the adhesive strength tends to decrease.

In the above, as an adhesive composition containing (A) and (B), preferably further (C), (E), it is applied to a polarizer and usually 50 to 200 ° C., particularly preferably 60 to 150 ° C. The chelate compound (AB) can be formed by performing drying with Also, after preparing an adhesive composition containing (A) and (B), preferably further (C), (E), usually (A) and (A) at 50 to 120 ° C., particularly preferably 60 to 90 ° C. B) can be reacted to form a chelate compound (AB).

In the case of [II ′], a chelate compound (AB) formed from (A) and (B), (E), and preferably (C) is contained. Furthermore, (A), (B), (E), a chelate compound (AB) formed from (A) and (B), and preferably (C) are contained. It will also be a thing.

The content of the chelate compound (AB) is preferably 0.1 to 40% by weight, particularly 0.5 to 30% by weight, and more preferably 1 to 20% by weight. .
If the content is too small, the adhesive force between the polarizer and the protective film tends to decrease and the color loss resistance tends to decrease. If the content is too large, the durability decreases during the hot water resistance test, and the polarizer and the protective film. There is a tendency for the adhesive strength of the steel to decrease.

As described above, by containing the urethane (meth) acrylate compound (E), curing shrinkage can be relaxed, and by being multifunctional, the degree of crosslinking is improved, and the adhesive strength is further increased. It is assumed that the water resistance is improved. It is presumed that the urethane (meth) acrylate compound (E) is polyfunctional but has a polymer portion (having a certain molecular weight due to the repeating structure of the polyol portion), and thus is crosslinked. This is because it is considered that curing shrinkage can be reduced while increasing the degree.

<Polymer (F)>
Next, the polymer (F) as the compounding agent will be described.
Further, the polymer (F) used in the present invention has a polymer solubility parameter (SP value) of 8 to 25, preferably 9 to 20. If the SP value is too low, the compatibility tends to decrease, and if it is too high, the compatibility tends to decrease.

The solubility parameter (SP value) is calculated by the Fedors calculation method ["Polymer Engineering & Science (Polymer Eng. & Sci.)", Vol. 14, No. 2 (1974), pages 148 to 154. ] Is measured by the method.

The weight average molecular weight of the polymer (F) is usually 10,000 to 1,500,000, preferably 30,000 to 1,000,000, particularly preferably 40,000 to 500,000. If the weight average molecular weight is too low, the adhesive force tends to be lowered, and if too high, the compatibility is lowered and the stability as the adhesive composition tends to be lowered.

The above-mentioned weight average molecular weight is based on standard polystyrene molecular weight conversion. Column: Shodex GPC KF is used in high performance liquid chromatography (manufactured by Waters, Japan, “Waters 2695 (main body)” and “Waters 2414 (detector)”). -806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm ) Are used in series.

The glass transition temperature (Tg) of the polymer (F) is usually −20 to 120 ° C., preferably −10 to 110 ° C., particularly 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 adhesive strength tends to decrease.

The Tg in the polymer (F) is measured by using DSC to detect the difference in the amount of heat from the standard sample when the measurement sample undergoes a change with heat balance such as phase transition and melting. Value.

Further, the polymer (F) preferably has an unsaturated group because it contributes to the photoreaction.

Examples of the polymer (F) in the present invention include polyethylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polylactic acid resins, polypropylene resins, polycarbonate resins, polytetrafluoroethylene resins, and polyurethane resins. , Polystyrene resin, ABS resin, acrylic resin, polyacetal resin, polyester resin, polyamide resin, polyalkylene oxide resin, etc., among which acrylic resin (f1) and polyoxyalkylene chain are included At least one of the polymers (f2) to be used is preferably used. These may be used alone or in combination of two or more.

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

The acrylic resin (f1) preferably contains a (meth) acrylic acid ester monomer (f1-1) as a main component as a polymerization component, and if necessary, a functional group-containing monomer (f1-2), Another copolymerizable monomer (f1-3) can also be used as a copolymerization component.
Examples of the (meth) acrylic acid ester monomer (f1-1) include aliphatic (meth) acrylic acid ester monomers such as (meth) acrylic acid alkyl esters and aromatic compounds such as (meth) acrylic acid phenyl esters. And (meth) acrylic acid ester monomers.

In such (meth) acrylic acid alkyl ester, the alkyl group usually has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 4 to 8 carbon atoms, and specifically, methyl (meth) acrylate. , Ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. Can be mentioned. Examples of (meth) acrylic acid phenyl ester include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
Other (meth) acrylic acid ester monomers include tetrahydrofurfuryl (meth) acrylate and the like. These can be used alone or in combination of two or more.

Among these (meth) acrylic acid ester monomers (f1-1), methyl (meth) acrylate and n-butyl (meth) acrylate are preferable in terms of copolymerizability, adhesive properties, ease of handling, and availability of raw materials. 2-ethylhexyl (meth) acrylate is preferably used.

Examples of the functional group-containing monomer (f1-2) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an alkoxy group or phenoxy group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a nitrogen-containing monomer, a glycidyl group-containing monomer, Examples thereof include a phosphoric acid group-containing monomer and a sulfonic acid group-containing monomer, which are used alone or in combination of two or more.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters, caprolactone-modified 2-hydroxyethyl (meth) acrylate and the like Monomers containing primary hydroxyl groups such as caprolactone-modified monomers, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc. -2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy- Secondary hydroxyl group-containing monomers such as 3-phenoxypropyl (meth) acrylate; tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.

In addition, polyethylene glycol derivatives such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, poly (ethylene Oxyalkylene-modified monomers such as glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate may be used.

Examples of the carboxyl group-containing monomer include Michael addition of acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and (meth) acrylic acid. (For example, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2- (meth) acryloyloxyethyl dicarboxylic acid monoester (for example, 2-acryloyloxyethyl) Succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexa Dorofutaru acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid mono ester) and the like. Such a carboxyl group-containing monomer may be used as it is, or may be used in the form of a salt neutralized with an alkali.

Examples of the alkoxy group-containing monomer include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-butoxydiethylene glycol. (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol- Polypropylene glycol- mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, Examples include aliphatic (meth) acrylic acid esters such as loxypolyethylene glycol mono (meth) acrylate. Examples of the phenoxy group-containing monomer include 2-phenoxyethyl (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate. And acrylic acid esters of aromatic (meth) acrylates such as phenoxypolyethylene glycol-polypropylene glycol- (meth) acrylate and nonylphenol ethylene oxide adduct (meth) acrylate.

Examples of the amide group-containing monomer include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N- Examples include diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, and dimethylaminoalkylmethacrylamide.

Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and a quaternized product thereof.
Examples of the nitrogen-containing monomer include acryloylmorpholine.

Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.

Examples of the phosphoric acid group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, and the like.

Examples of the sulfonic acid group-containing monomer include olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, and salts thereof. .
These functional group-containing monomers (f1-2) may be used alone or in combination of two or more.

Examples of other copolymerizable monomers (f1-3) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl. Monomers such as toluene, vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinylketone It is done.

For the purpose of increasing the molecular weight, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate A compound having two or more ethylenically unsaturated groups such as divinylbenzene can also be used in combination.

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

The acrylic resin (f1) in the present invention is preferably a polymer having methyl (meth) acrylate as a polymerization component in terms of water resistance and adhesiveness, and particularly a polymer having methyl methacrylate as a polymerization component. It is preferable to be polymethyl methacrylate.

In the present invention, the acrylic resin (f1) is produced by polymerizing the monomer components (f1-1) to (f1-3). In this polymerization, solution radical polymerization, suspension polymerization are performed. It can be carried out by a conventionally known method such as bulk polymerization or emulsion polymerization. For example, a polymerization monomer such as the (meth) acrylic acid ester monomer (f1-1), functional group-containing monomer (f1-2), other copolymerizable monomer (f1-3) in the organic solvent, polymerization initiation An agent (azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.) is mixed or dropped and polymerized at reflux or at 50 to 90 ° C. for 2 to 20 hours.

The polymer (f2) containing a polyoxyalkylene chain is also preferably an allyl glycidyl ether copolymer containing a polyoxyalkylene chain, and more preferably an ethylene oxide / propylene oxide / all glycidyl ether copolymer. In particular, a random copolymer or a block copolymer is particularly preferable.

When the polymer (F) is used, [I ″] a metal or metalloid compound (A) capable of chelating, and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid; An adhesive composition comprising a polymer (F), and preferably, another photopolymerizable compound (C) (excluding the photopolymerizable compound (B)), and [II '' A chelate compound (AB) formed from a metal or metalloid compound (A) capable of chelating and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid; It is set as the adhesive composition containing a polymer (F) and preferably another photopolymerizable compound (C) (however, except a photopolymerizable compound (B)).

Regarding the blending ratio of (A) and (F), (A) / (F) is preferably 50/50 to 95/5 in weight ratio, particularly 55/45 to 90/10, and more preferably 60 / 40 to 80/20 is preferable. If the value of (A) / (F) is too small, the adhesive strength tends to decrease, and if too large, the adhesive strength tends to decrease.

In the case of the above [I ″], (A) to (C) and (F) can be appropriately blended to form an adhesive composition. With respect to each content ratio of (A) to (C) and (F), (A) is 0.1 to 30% by weight with respect to the total of (A) to (C) and (F), (B) Is preferably 0.5 to 40% by weight, (C) is preferably 30 to 99% by weight, and (F) is preferably 0.01 to 20% by weight, in particular (A) is 0.5 to 20% by weight, (B) is 1 to 30% by weight, (C) is 50 to 98% by weight, (F) is 0.05 to 10% by weight, (A) is 1 to 15% by weight, and (B) is 4 to 4%. It is preferable that 20% by weight, (C) be 65 to 94% by weight, and (F) be 0.1 to 8% by weight. If the content of (A) is too small, the adhesive strength between the polarizer and the protective film tends to decrease and the color loss resistance tends to decrease. If the content is too large, the durability decreases during the hot water resistance test, and the polarization There exists a tendency for the adhesive force of a child and a protective film to fall. When there is too little content of this (B), there exists a tendency for the adhesive force of a polarizer and a protective film to fall, and when too large, there exists a tendency for the durability at the time of a hot water resistance test to fall. When there is too little content of this (C), there exists a tendency for the durability at the time of a hot water test to fall, and when too much, there exists a tendency for the adhesive force of a polarizer and a protective film to fall. If the content of (F) is too small, the adhesive strength tends to decrease, and if too large, the compatibility tends to decrease and the adhesive strength tends to decrease.

In the above, as an adhesive composition containing (A) and (B), preferably further (C), (F), it is applied to a polarizer, usually 50 to 200 ° C., particularly preferably 60 to 150 ° C. The chelate compound (AB) can be formed by performing drying with Also, after preparing an adhesive composition containing (A) and (B), preferably further (C), (F), (A) and (A) are usually at 50 to 120 ° C., particularly preferably at 60 to 90 ° C. B) can be reacted to form a chelate compound (AB).

In the case of [II ″], a chelate compound (AB) formed from (A) and (B), a polymer (F), and preferably (C) is contained. Furthermore, (A), (B), (F), a chelate compound (AB) formed from (A) and (B), and preferably (C) is contained. It will be done.

As described above, by having the polymer (F), the polymer chain enters the polymer network structure at the time of ultraviolet curing, so that the curing shrinkage can be relaxed. It is presumed to improve.

<Acid group-containing monomer (G)>
Next, the acid group-containing monomer (G) as the compounding agent will be described.
Examples of the acid group-containing monomer (G) in the present invention include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, (meth) Michael adducts of acrylic acid (eg, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2- (meth) acryloyloxyethyl dicarboxylic acid monoester (eg, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl ester Sahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, etc.), carboxyethyl acrylate, etc. Among them, carboxyl groups such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. Containing ethylenically unsaturated compounds are preferred, and (meth) acrylic acid, carboxyethyl acrylate and the like are particularly preferably used. These may be used alone or in combination of two or more.

When the acid group-containing monomer (G) is used, [I ′ ″] a photopolymerizable compound containing a chelate-forming metal or metalloid compound (A) and a functional group capable of chelating with the metal or metalloid An adhesive composition comprising (B), an acid group-containing monomer (G), and preferably further containing another photopolymerizable compound (C) (excluding the photopolymerizable compound (B)). And [II ′ ″] a chelate-forming metal or metalloid compound (A) and a chelate formed from a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid An adhesive comprising compound (AB), acid group-containing monomer (G), and preferably further containing another photopolymerizable compound (C) (excluding the photopolymerizable compound (B)). An agent composition is obtained.

Regarding the blending ratio of (A) and (G), (A) / (G) is preferably 50/50 to 95/5 in weight ratio, particularly 55/45 to 90/10, and more preferably 60 / 40 to 80/20 is preferable. If the value of (A) / (G) is too small, the water resistance tends to decrease, and if too large, the adhesive strength tends to decrease.

In the case of the above [I "", (A) to (C) and (G) can be appropriately blended to form an adhesive composition. With respect to each content ratio of (A) to (C) and (G), (A) is 0.1 to 30% by weight with respect to the total of (A) to (C) and (G), and (B) Is preferably 0.5 to 40% by weight, (C) is preferably 30 to 99% by weight, and (G) is preferably 0.01 to 20% by weight, in particular (A) is 0.5 to 20% by weight, (B) is 1 to 30% by weight, (C) is 50 to 98% by weight, (G) is 0.05 to 10% by weight, (A) is 1 to 15% by weight, and (B) is 4 to 4%. It is preferable that 20% by weight, (C) be 65 to 94% by weight, and (G) be 0.1 to 8% by weight. If the content of (A) is too small, the adhesive strength between the polarizer and the protective film tends to decrease and the color loss resistance tends to decrease. If the content is too large, the durability decreases during the hot water resistance test, and the polarization There exists a tendency for the adhesive force of a child and a protective film to fall. When there is too little content of this (B), there exists a tendency for the adhesive force of a polarizer and a protective film to fall, and when too large, there exists a tendency for the durability at the time of a hot water resistance test to fall. When there is too little content of this (C), there exists a tendency for the durability at the time of a hot water test to fall, and when too much, there exists a tendency for the adhesive force of a polarizer and a protective film to fall. If the content of (G) is too small, the adhesive strength tends to decrease, and if it is too large, the water resistance tends to decrease.

In the above, as an adhesive composition containing (A), (B) and (G), preferably further (C), it is applied to a polarizer and usually 50 to 200 ° C., particularly preferably 60 to 150 ° C. The chelate compound (AB) can be formed by performing drying with In addition, after preparing an adhesive composition containing (A), (B) and (G), preferably further (C), usually (A) and (A) at 50 to 120 ° C., particularly preferably 60 to 90 ° C. B) can be reacted to form a chelate compound (AB).

In the case of [II ′ ″], the chelate compound (AB) formed from (A) and (B), the acid group-containing monomer (G), and preferably (C) Furthermore, the chelate compound (AB) formed from (A), (B), (G), (A) and (B), preferably (A), (B), (G), C) will also be contained.

As described above, the enol of tautomerism (keto enol) of the photopolymerizable compound (B) containing a functional group capable of chelating with the metal or semimetal by having the acid group-containing monomer (G) It is estimated that the adhesion is improved and the adhesion is improved. In particular, when the component (B) is an acetoacetyl group-containing ethylenically unsaturated compound (b1), it is considered that by adding an acid group-containing monomer, a large number of hydroxyl groups effective for adhesive force can appear. It is done.

<Photobase generator (H)>
Next, the photobase generator (H) that is the compounding agent will be described.
The photobase generator (H) in the present invention is one or more basic substances that can function as a curing catalyst when the molecular structure is changed or the molecules are cleaved by irradiation with light such as ultraviolet rays or visible light. Is a compound that produces Examples of basic substances include secondary amines and tertiary amines.

Conventionally known photobase generators can be used as the photobase generator, and preferred photobase generators include compounds that can be represented by the following formulas (2) to (7). it can. These may be used alone or in combination of two or more.

Of these, the compounds represented by the above formulas (2) and (3) are particularly preferably used.

The above photobase generator (H) preferably has a maximum molar extinction coefficient of usually 405 nm or less.

When the photobase generator (H) is used, [I ″ ″] a photopolymerizable polymer containing a chelate-forming metal or metalloid compound (A) and a functional group capable of chelating with the metal or metalloid An adhesive composition comprising a compound (B), a photobase generator (H), and preferably further containing another photopolymerizable compound (C) (excluding the photopolymerizable compound (B)). And [II ″ ″] a chelatable metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid. A chelate compound (AB), a photobase generator (H), and preferably further, other photopolymerizable compound (C) (excluding the photopolymerizable compound (B)). It is set as the adhesive composition which becomes.

Regarding the blending ratio of (A) and (H), it is preferable that (A) / (H) is 99.1 / 0.1 to 70/30 in weight ratio, particularly 99/1 to 80/20. Further, it is preferably 95/5 to 85/15. If the value of (A) / (H) is too small, the water resistance tends to decrease, and if too large, the water resistance tends to decrease.

In the case of [I "" "above, (A) to (C) and (H) can be appropriately blended to form an adhesive composition. With respect to each content ratio of (A) to (C) and (H), (A) is 0.1 to 30 wt% with respect to the total of (A) to (C) and (H), (B) Is preferably 0.5 to 40% by weight, (C) is preferably 30 to 99% by weight, and (H) is preferably 0.1 to 20% by weight, in particular (A) is 0.5 to 20% by weight, (B) is 1 to 30% by weight (C) is 50 to 98% by weight, (H) is 0.5 to 15% by weight, (A) is 1 to 15% by weight, and (B) is 4 to 20%. % By weight, (C) is preferably 65 to 94% by weight, and (H) is preferably 1 to 10% by weight. If the content of (A) is too small, the adhesive strength between the polarizer and the protective film tends to decrease and the color loss resistance tends to decrease. If the content is too large, the durability decreases during the hot water resistance test, and the polarization There exists a tendency for the adhesive force of a child and a protective film to fall. When there is too little content of this (B), there exists a tendency for the adhesive force of a polarizer and a protective film to fall, and when too large, there exists a tendency for the durability at the time of a hot water resistance test to fall. When there is too little content of this (C), there exists a tendency for the durability at the time of a hot water test to fall, and when too much, there exists a tendency for the adhesive force of a polarizer and a protective film to fall. If the content of (H) is too small, the water resistance tends to decrease, and if too high, the water resistance tends to decrease.

In the above, an adhesive composition containing (A), (B) and (H), preferably further (C), is applied to a polarizer and usually 50 to 200 ° C., particularly preferably 60 to 150 ° C. The chelate compound (AB) can be formed by performing drying with Further, after preparing an adhesive composition containing (A), (B) and (H), preferably further (C), (A) and (A) at usually 50 to 120 ° C., particularly preferably 60 to 90 ° C. B) can be reacted to form a chelate compound (AB).

In the case of [II ″ ″], a chelate compound (AB) formed from (A) and (B), a photobase generator (H), and preferably (C) In addition, (A), (B), (H), a chelate compound (AB) formed from (A) and (B), preferably (C) will also be contained.

As described above, by having a photobase generator (H), the photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid, particularly an acetoacetyl group-containing ethylenic unsaturation It is presumed that the acidity of the compound (b1) is neutralized, the reactivity of the component (B) is improved, and the water resistance is also improved. In particular, a photobase generator generates a base component upon irradiation with ultraviolet rays or the like and performs anion curing of a double bond. Since the weak acidity of the component (B) adversely affects water resistance, It is considered that neutralization can be achieved by adding a base generator.

Thus, the adhesive composition of the present invention is obtained. The adhesive composition of the present invention preferably functions as an adhesive by being cured by irradiation with active energy rays, and is preferably used as an adhesive for a polarizing plate for bonding a polarizer and a protective film. It is something that can be done.

The adhesive composition of the present invention may contain a solvent or may be used as a solventless composition, but it is better to use it as a solventless composition in terms of excellent adhesive performance. preferable.

(Polarizer)
There is no restriction | limiting in particular as said polarizer, A well-known thing can be used.
For example, (i) A dichroic material such as iodine or a dichroic dye is adsorbed on a vinyl alcohol resin film such as a PVA film, a partially formalized PVA film, or an ethylene-vinyl alcohol resin film. Stretched (for example, see JP-A-2001-296427, JP-A-7-333426), (ii) a birefringent material having liquid crystallinity together with a dichroic material in the above (i) is a vinyl alcohol resin (Iii) a uniaxially stretched thermoplastic norbornene resin film containing a dichroic material (for example, Japanese Patent Application Laid-Open No. 2001-356213) (Iv) PVA resin or ethylene-vinyl alcohol resin is dehydrated or deaceticated. Introducing a polyene structure continue, polyene-based film obtained by stretching them (e.g., see JP Patent 2007-17845.), And the like.
Among these, a uniaxially stretched film in which iodine is adsorbed on a PVA-based film is preferable because of excellent polarization characteristics.

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

(Protective film)
The protective film can make up for deficiency in durability under high humidity, which is a problem of polarizers, by bonding to at least one surface, preferably both surfaces, of the polarizer.
Furthermore, the properties required for the protective film used in the present invention include transparency, mechanical strength, thermal stability, moisture barrier properties, optical isotropy, and the like.

As a material for such a protective film, a cellulose ester resin, a cyclic olefin resin, and a (meth) acrylic resin are preferably used from the viewpoints of optical properties and durability.
Other materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polystyrene resins such as polystyrene and acrylonitrile / styrene copolymers, polyolefin resins such as polyethylene and polypropylene, polyarylate resins, and polycarbonate resins. , Vinyl chloride resins, amide resins such as nylon and aromatic polyamide, (fluorine-containing) polyimide resins, polyether ether ketone resins, polyphenylene sulfide resins, vinylidene chloride resins, polyvinyl acetal resins such as polyvinyl butyral And polyoxymethylene resins and epoxy resins. These may be used alone or in combination of two or more.

Typical examples of the cellulose ester resin used in the cellulose ester resin film include triacetyl cellulose and diacetyl cellulose, but other lower fatty acid esters of cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like. The mixed fatty acid ester can be used.

Examples of the cyclic olefin resin used in the cyclic olefin resin film include norbornene resins. Such norbornene resins include, for example, ring-opening (co) polymers of norbornene monomers, resins obtained by addition polymerization of norbornene monomers, and addition copolymers of norbornene monomers and olefin monomers such as ethylene and α-olefins. Resin etc. are included.

Specific examples of norbornene-based monomers include dimers such as norbornene and norbornadiene; tricyclics such as dicyclopentadiene and dihydroxypentadiene; heptacyclics such as tetracyclopentadiene; these methyl, ethyl, propyl and butyl Substituents such as alkyl, alkenyl such as vinyl, alkylidene such as ethylidene, aryl such as phenyl, tolyl, and naphthyl; and ester groups, ether groups, cyano groups, halogens, alkoxycarbonyl groups, pyridyl groups, hydroxyl groups, carvone Examples include substituents having groups containing elements other than carbon and hydrogen, such as acid groups, amino groups, hydroxyl-free groups, silyl groups, epoxy groups, acryloyl groups, and methacryloyl groups.

Examples of commercially available cyclic olefin-based resin films include “ARTON” manufactured by JSR, “ZEONOR”, “ZEONEX” manufactured by Nippon Zeon, “OPTOREZ” manufactured by Hitachi Chemical, and “APEL” manufactured by Mitsui Chemicals. it can.

Examples of the (meth) acrylic resin used in the (meth) acrylic resin film include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, and methyl methacrylate. -(Meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer, (meth) methyl acrylate-styrene copolymer, polymer having alicyclic hydrocarbon group [For example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.], (meth) having a high glass transition temperature obtained by intramolecular crosslinking or intramolecular cyclization reaction Examples thereof include acrylic resins and rubber-acrylic graft type core-shell polymers.

Examples of such commercially available (meth) acrylic resin films include “Acrypet VRL20A”, “Acrypet IRD-70” manufactured by Mitsubishi Rayon Co., Ltd., and “MUX-60” manufactured by UMGABS.

In addition, the protective film is subjected to surface hydrophilization treatment such as saponification treatment with an alkali solution for a film made of a cellulose ester resin or corona discharge treatment or plasma treatment for a film made of a cyclic olefin resin, as necessary. It may be what you did.

In addition, in order to improve the affinity with the adhesive on the surface of the protective film, it is possible to perform various surface treatments other than hydrophilization, and (meth) acrylic acid ester latex or styrene latex on the surface of the protective film, Examples thereof include an easy-adhesion layer and an anchor coat layer containing polyethyleneimine, polyurethane / polyester copolymer, etc., and a surface treatment method using a coupling agent such as a silane coupling agent and a titanium coupling agent. In addition, it is also possible to use together the above-mentioned various surface treatment methods.
Moreover, what coated the antistatic agent on the surface of the protective film or contained it in the film is also preferably used.

The thickness of such a protective film is not particularly limited, but is usually thicker than that of a polarizer, and has a function of imparting strength as a base material of the polarizer, and is usually 10 to 100 μm, preferably 20 to 80 μm. is there.

In addition, such a protective film can be provided with a hard coat layer on the surface on which the polarizer is not laminated, or can be subjected to various treatments such as anti-sticking, anti-reflection and anti-glare. Furthermore, various optical functional films such as a phase difference plate and a viewing angle widening film can be laminated.

(Polarizer)
The polarizing plate of the present invention is formed by laminating the above polarizer and a protective film via an adhesive for polarizing plates. Specifically, the protective film is bonded to at least one surface, preferably both surfaces, of the polarizer using the polarizing plate adhesive of the present invention, and the liquid adhesive composition is usually polarized. After applying uniformly to a child or a protective film, or both, both are bonded together, pressure-bonded, and irradiated with active energy rays to form a polarizing plate.

When coating such an adhesive composition on a polarizer or a protective film, for example, reverse coater, gravure coater (direct, reverse or offset), bar reverse coater, roll coater, die coater, bar coater, rod coater, etc. Or can be applied by dipping.

For the bonding and pressure bonding, for example, a roll laminator or the like can be used, and the pressure is selected from the range of 0.1 to 10 MPa.

For such active energy ray irradiation, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the standpoint of availability of the device and price. In addition, when performing electron beam irradiation, it can harden | cure even without using the said photoinitiator (d1).

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 light, an LED, or the like is used as a light source for performing such ultraviolet irradiation.
Such ultraviolet irradiation, ² ~ 3000mJ / cm 2, preferably carried out at a 10 ~ 2000mJ / cm ² conditions.

Particularly if the high-pressure mercury lamp, for example, 5 ~ 3000mJ / cm ^2, preferably at a 50 ~ 2000mJ / cm ² conditions.
In the case of the electrodeless lamp, for example, it is performed under the conditions of 2 to 2000 mJ / cm ² , preferably 10 to 1000 mJ / cm ² .

The irradiation time varies depending on the type of light source, the distance between the light source and the coating surface, the coating thickness, and other conditions, but it is usually several seconds to several tens of seconds, and in some cases may be a fraction of a second. On the other hand, in the case of the electron beam irradiation, for example, an electron beam having an energy in the range of 50 to 1000 keV is used, and the irradiation amount is preferably 2 to 50 Mrad.

The irradiation direction of such active energy rays (electron beam, ultraviolet ray, etc.) can be irradiated from any appropriate direction, but it is preferable to irradiate from the transparent protective film side in terms of preventing the polarizer from being deteriorated.

The thickness of the adhesive layer in the polarizing plate of the present invention obtained as described above is usually 0.01 to 10 μm, preferably 0.01 to 5 μm, particularly preferably 0.01 to 2 μm, more preferably 0.01 to 1 μm. It is. If the thickness is too thin, the cohesive force of the adhesive force itself cannot be obtained and the adhesive strength tends not to be obtained. If the thickness is too thick, the workability of the polarizing plate tends to be reduced due to cracks during punching.

The adhesive composition of the present invention is an adhesive having excellent adhesive strength at the initial stage and over time, and can be used for various applications. In particular, various protective films for polarizing plates and polarizers, particularly those other than TAC. The protective film and the polarizer can be suitably used for bonding, and there is no need for a drying step, so that the production efficiency of the polarizing plate is excellent, and the color fading resistance of the polarizing plate is also excellent.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, “parts” and “%” mean weight basis.

The following components were prepared.
[Metal or metalloid compound (A) capable of chelating]
・ (A-1) Tributyl borate (“Tri-n-butyl borate” manufactured by Kanto Chemical Co., Inc.)
・ (A-2) Titanium tetraisopropylate ("Orgatics TA-10" manufactured by Matsumoto Fine Chemical Co., Ltd.)
・ (A-3) Titanium tetra-n-butyrate ("Orgatics TA-25" manufactured by Matsumoto Fine Chemical Co., Ltd.)
・ (A-4) Aluminum triacetylacetonate ("Nasemuarnium" manufactured by Nippon Chemical Industry Co., Ltd.)
・ (A-5) Boric acid (Wako Pure Chemical Industries, Ltd.)

[Photopolymerizable compound (B) containing functional group capable of chelating with metal or metalloid]
(B-1) 2-acetoacetoxyethyl methacrylate (“AAEM” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

[Photopolymerizable compound (C)]
・ (C-1) Acryloylmorpholine (“ACMO” manufactured by Kojin Co., Ltd.)
・ (C-2) Dimethylacrylamide (“DMAA” manufactured by Kojin 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)
(D-2) 2,4,6-trimethylbenzoyl-diphenylphosphine oxide ("Lucirin TPO" manufactured by BASF)

[Urethane (meth) acrylate compound (E)]
A bifunctional polyether urethane acrylate (E-1) was synthesized according to Synthesis Example 1 below.
(E-1) Bifunctional polyether urethane acrylate [Synthesis Example 1]
A 500 ml reaction vessel equipped with a stirrer was charged with 0.3 g of dibutyltin dilaurate, 0.2 g of 4-methoxyphenol as a polymerization inhibitor, and 230 g of polytetramethylene glycol (molecular weight 650). Was heated to 40 ° C.
185 g of hydrogenated diphenylmethane diisocyanate was gradually added to the reaction solution, and the temperature was raised to 60 ° C. over 1 hour. While continuing the reaction at 60 ° C. until the free NCO% becomes 7.0%, 85 g of 2-hydroxyethyl acrylate is added, and the reaction is continued until the free NCO% becomes 0.5% or less. A bifunctional polyether urethane acrylate (E-1) was obtained.
The obtained bifunctional polyether urethane acrylate (E-1) had a weight average molecular weight of 3200 and a viscosity at 60 ° C. of 14000 mPa · s.

[Polymer (F)]
(F-1) polymethyl methacrylate (manufactured by Aldrich, SP value of 9.1 to 9.5, weight average molecular weight of about 1 million, glass transition temperature of 100 ° C.)
(F-2) ethylene oxide / propylene oxide / allyl glycidyl ether random copolymer (“Alcox CP-A2H” manufactured by Meisei Chemical Industry Co., Ltd., SP value 19.1, weight average molecular weight about 60,000, glass transition temperature− 6 ℃)

[Acid group-containing monomer (G)]
・ (G-1) Acrylic acid (Aldrich)
(G-2) β-carboxyethyl acrylate (“βCEA” manufactured by Daicel-Ornex)

[Photobase generator (H)]
(H-1) (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine (“WPBG-027” manufactured by Wako Pure Chemical Industries, Ltd.)
(H-2) 9-anthrylmethyl-N, N-diethylcarbamate (“WPBG-018” manufactured by Wako Pure Chemical Industries, Ltd.)
[Example 1]
<Preparation of adhesive composition>
In a preparation flask, 5 parts (solid content) of tributyl borate (A-1), 15 parts of 2-acetoacetoxyethyl methacrylate (B-1), 50 parts of dimethylacrylamide (C-2), ethylene glycol diacrylate (C— 3) 30 parts, 1.5 parts of Irgacure 184 (D-1) and 1.5 parts of lucillin TPO (D-2) were charged simultaneously and mixed to obtain an adhesive composition.

[Examples 2 to 8, Comparative Examples 1 and 2]
An adhesive composition was prepared in the same manner as in Example 1 except that the blending 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 stretched 1.5 times while immersed in a water bath with a water temperature of 30 ° C. Next, it is stretched 1.3 times while being immersed for 240 seconds in a dyeing tank (30 ° C.) consisting of 0.2 g / L of iodine and 15 g / L of potassium iodide, and further 50 g / L of boric acid and 30 g of potassium iodide. / L was immersed in a boric acid treatment tank (50 ° C.) and boric acid treatment was performed for 5 minutes while simultaneously uniaxially stretching 3.08 times. Thereafter, it was dried to produce a polarizer having a total draw ratio of 6 times.
Next, the adhesive composition obtained above on an acrylic film (trade name “Acryprene” manufactured by Mitsubishi Rayon Co., Ltd.) having a size of 200 mm × 50 mm and a thickness of 75 μm is formed with a bar coater (No. 10) so that the film thickness becomes 5 μm. After two coated acrylic films with an adhesive composition layer were produced, they were superposed on both sides of the above polarizer having a size of 150 mm × 30 mm, and bonded together at a nip pressure of 2 MPa using a roll machine to obtain a laminated film. .
Next, from both sides of the laminated film on the acrylic film side, UV irradiation is performed with an ultraviolet irradiation device equipped with a high-pressure mercury lamp at a peak illuminance of 130 mW / cm ² and an integrated exposure amount of 900 mJ / cm ² (365 nm). The composition was cured, Examples 1 to 7 were dried at 80 ° C. for 3 minutes, and Examples 8 and 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, performance evaluation was performed as follows.

[Adhesiveness]
The polarizing plate test piece was cut into 120 mm × 25 mm, and the degree of adhesion between the acrylic film and the polarizer when the stress in the 90 ° direction was applied to the two acrylic films was evaluated according to the following criteria.
(Evaluation criteria)
◎… Strongly adhered ○… Adhered ×… Not adhered

[Color loss resistance]
The polarizing plate test piece was cut into 5 cm × 5 cm and immersed in warm water at 60 ° C., and the color tone of the polarizing plate test piece after 48 hours was observed and evaluated according to the following criteria.
○: Situation before the test and no change in color tone △… Slight color loss (fading) ×… Color loss completely (fading)

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

Adhesives of Examples 1 to 8 comprising a chelate-forming metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid The composition was able to sufficiently bond the polarizer and the protective film, and had an excellent effect in terms of color loss resistance and water resistance. In contrast, Comparative Example 1 that does not contain a chelate-forming metal or metalloid compound (A) or a comparison that does not contain a photopolymerizable compound (B) containing a functional group capable of chelating with a metal or metalloid The adhesive composition of Example 2 was inferior not only in adhesion but also in color fading resistance and water resistance, and could not be put to practical use as an adhesive composition. This shows that the adhesive composition of the present invention is very excellent.

Example 9
<Preparation of adhesive composition: (E) Component addition system>
A flask for preparation was charged with 5 parts of boric acid (A-5), 5 parts of 2-acetoacetoxyethyl methacrylate (B-1) and 65 parts of dimethylacrylamide (C-2) and heated to 60 ° C. to obtain boric acid. Dissolve. Next, 5 parts of ethylene glycol diacrylate (C-3) and 20 parts of bifunctional polyether urethane acrylate (E-1) are added and mixed thoroughly. After cooling to room temperature, 1.5 parts of Irgacure 184 (D-1) and 1.5 parts of Lucillin TPO (D-2) were charged, 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 blending components prepared above were blended in the proportions shown in Table 2 below.

Next, a polarizing plate test piece was produced in the same manner as in Example 1 above, and the adhesiveness, color loss resistance, and water resistance performance evaluation was performed in the same manner as in Example 1 using the polarizing plate test piece. . The evaluation results are shown in Table 2 below.

A chelate-forming metal or metalloid compound (A), a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid, and a urethane (meth) acrylate compound (E), The adhesive compositions of Examples 9 and 10 contained can sufficiently bond a polarizer and a protective film, and also have an excellent effect on color loss resistance and water resistance. It was. In contrast, Comparative Example 3 that does not contain a chelate-forming metal or metalloid compound (A), or a comparison that does not contain a photopolymerizable compound (B) containing a functional group capable of chelating with a metal or metalloid The adhesive composition of Example 4 was inferior not only in adhesion but also in color fading resistance and water resistance, and could not be practically used as an adhesive composition. This shows that the adhesive composition of the present invention is very excellent.

Example 11
<Preparation of adhesive composition: (F) Component additional system>
In a flask for preparation, 5 parts of boric acid (A-5), 5 parts of 2-acetoacetoxyethyl methacrylate (B-1), 2 parts of polymethyl methacrylate (F-1), 83 parts of dimethylacrylamide (C-2) Charge and heat to 60 ° C. to dissolve the solid components. Next, 5 parts of ethylene glycol diacrylate (C-3) is added and mixed thoroughly. After cooling to room temperature, 1.5 parts of Irgacure 184 (D-1) and 1.5 parts of Lucillin TPO (D-2) were charged, mixed and dissolved to obtain an adhesive composition.

[Examples 12 and 13, Comparative Examples 5 and 6]
An adhesive composition was prepared in the same manner as in Example 11 except that the blending components prepared above were blended in the proportions shown in Table 3 below.

Next, a polarizing plate test piece was produced in the same manner as in Example 1 above, and the adhesiveness, color loss resistance, and water resistance performance evaluation was performed in the same manner as in Example 1 using the polarizing plate test piece. . The evaluation results are shown in Table 3 below.

Example 11 comprising a chelate-forming metal or metalloid compound (A), a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid, and a polymer (F) The adhesive compositions Nos. 13 to 13 were able to sufficiently bond the polarizer and the protective film, and also had excellent effects on color loss resistance and water resistance. In contrast, Comparative Example 5 that does not contain a chelate-forming metal or metalloid compound (A) or a photopolymerizable compound (B) that contains a functional group capable of chelating with a metal or metalloid (B) The adhesive composition of Example 6 was inferior not only in adhesion but also in color fading resistance and water resistance, and could not be put to practical use as an adhesive composition. This shows that the adhesive composition of the present invention is very excellent.

Example 14
<Preparation of adhesive composition: (G) component addition system>
Charge 5 parts of boric acid (A-5), 5 parts of 2-acetoacetoxyethyl methacrylate (B-1), and 84 parts of dimethylacrylamide (C-2) to the flask for adjustment. Dissolve. Next, 5 parts of ethylene glycol diacrylate (C-3) and 1 part of acrylic acid (G-1) are added and mixed thoroughly. After cooling to room temperature, 1.5 parts of Irgacure 184 (D-1) and 1.5 parts of Lucillin TPO (D-2) were charged, mixed and dissolved to obtain an adhesive composition.

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

Next, a polarizing plate test piece was produced in the same manner as in Example 1 above, and the adhesiveness, color loss resistance, and water resistance performance evaluation was performed in the same manner as in Example 1 using the polarizing plate test piece. . The evaluation results are shown in Table 4 below.

A chelate-forming metal or metalloid compound (A), a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid, and an acid group-containing monomer (G) The adhesive compositions of Examples 14 to 16 were able to sufficiently bond the polarizer and the protective film, and had excellent effects in terms of color loss resistance and water resistance. On the other hand, Comparative Example 7 not containing a chelate-forming metal or metalloid compound (A) or a comparison not containing a photopolymerizable compound (B) containing a functional group capable of chelating with a metal or metalloid The adhesive composition of Example 8 was inferior not only in adhesion but also in color fading resistance and water resistance, and could not be put to practical use as an adhesive composition for polarizing plates. This shows that the adhesive composition of the present invention is very excellent.

Example 17
<Production of Adhesive Composition: (H) Component Additional System>
A flask for preparation was charged with 5 parts of boric acid (A-5), 5 parts of 2-acetoacetoxyethyl methacrylate (B-1) and 85 parts of dimethylacrylamide (C-2), and heated to 60 ° C. to prepare boric acid. Dissolve. Next, 5 parts of ethylene glycol diacrylate (C-3) is added and mixed thoroughly. After cooling to room temperature, 1.5 parts of Irgacure 184 (D-1), 1.5 parts of Lucillin TPO (D-2), and (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] An adhesive composition was obtained by adding 0.5 part of piperidine (H-1), mixing, and dissolving.

[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 blending components prepared above were blended in the proportions shown in Table 5 below.

Next, a polarizing plate test piece was produced in the same manner as in Example 1 above, and the adhesiveness, color loss resistance, and water resistance performance evaluation was performed in the same manner as in Example 1 using the polarizing plate test piece. . The evaluation results are shown in Table 5 below.

A chelate-forming metal or metalloid compound (A), a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid, and a photobase generator (H) The adhesive compositions of Examples 17 to 19 were able to sufficiently bond the polarizer and the protective film, and also had excellent effects on color loss resistance and water resistance. In contrast, Comparative Example 9 that does not contain a chelate-forming metal or metalloid compound (A), or a comparison that does not contain a photopolymerizable compound (B) containing a functional group capable of chelating with a metal or metalloid. The adhesive composition of Example 10 was inferior not only in adhesion but also in color loss resistance and water resistance, and could not be practically used as an adhesive composition. This shows that the adhesive composition of the present invention is very excellent.
In the said Example, although the specific form in this invention was shown, the said Example is only a mere illustration and is not interpreted limitedly. Various modifications apparent to those skilled in the art are contemplated to be within the scope of this invention.

The adhesive composition for polarizing plate comprising the adhesive composition of the present invention and such an adhesive composition is excellent in adhesion between the polarizer and the protective film, and also has excellent production efficiency without requiring a drying step. Furthermore, it has excellent anti-color loss properties of the polarizing plate, and is particularly useful not only for the TAC film but also for bonding a protective film such as an acrylic film or a cyclic polyolefin resin film and a polarizer. It is a thing. Moreover, the pressure-sensitive adhesive composition of the present invention can be used for, for example, laminating various optical films or sheets, and laminating electronic parts, precision equipment, packaging materials, display materials, and the like in addition to the polarizing plate adhesive application. It can also be used.

Claims

An adhesive composition comprising a chelate-forming metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid.
Contains a chelate compound (AB) formed from a chelate-forming metal or metalloid compound (A) and a photopolymerizable compound (B) containing a functional group capable of chelating with the metal or metalloid An adhesive composition characterized by comprising:
The chelate-forming metal or metalloid compound (A) is at least one selected from the group consisting of boron compounds, aluminum compounds, titanium compounds, zirconium compounds, zinc compounds, and silicon compounds. The adhesive composition according to 1 or 2.
4. The photopolymerizable compound (B) containing a functional group capable of forming a chelate with a metal or metalloid is an acetoacetyl group-containing ethylenically unsaturated compound (b1). The adhesive composition according to item.
5. The acetoacetyl group-containing ethylenically unsaturated compound (b1) is an aliphatic acetoacetyl group-containing alkyl (meth) acrylate compound having an alkylene group having 1 to 10 carbon atoms. Adhesive composition.
The adhesive composition according to any one of claims 1 to 5, further comprising a photopolymerizable compound (C) (excluding the photopolymerizable compound (B)).
The photopolymerizable compound (C) is selected from the group consisting of an ethylenically unsaturated compound (c1) having one ethylenically unsaturated group and an ethylenically unsaturated compound (c2) having two or more ethylenically unsaturated groups. The adhesive composition according to claim 6, wherein the adhesive composition is at least one.
The adhesive composition according to any one of claims 1 to 7, further comprising a polymerization initiator (D).
The adhesive composition according to any one of claims 1 to 8, further comprising a urethane (meth) acrylate compound (E).
The adhesive composition according to any one of claims 1 to 9, further comprising a polymer (F).
The adhesive composition according to any one of claims 1 to 10, further comprising an acid group-containing monomer (G).
The adhesive composition according to any one of claims 1 to 11, further comprising a photobase generator (H).
An adhesive composition for polarizing plates, characterized by using the adhesive composition according to any one of claims 1 to 12.
A polarizing plate adhesive obtained by curing the polarizing plate adhesive composition according to claim 13.
A polarizing plate adhesive comprising the polarizing plate adhesive composition according to claim 13 cured by irradiation with active energy rays.
A polarizing plate comprising a polarizer and a protective film bonded together through the polarizing plate adhesive according to claim 14 or 15.