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

Adhesive agent composition, adhesive agent composition for polarizing plate, adhesive agent for polarizing plate, and polarizing plate manufactured using said adhesive agent Download PDF

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Publication number
WO2015022825A1
WO2015022825A1 PCT/JP2014/068108 JP2014068108W WO2015022825A1 WO 2015022825 A1 WO2015022825 A1 WO 2015022825A1 JP 2014068108 W JP2014068108 W JP 2014068108W WO 2015022825 A1 WO2015022825 A1 WO 2015022825A1
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Prior art keywords
meth
compound
acrylate
adhesive composition
group
Prior art date
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PCT/JP2014/068108
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French (fr)
Japanese (ja)
Inventor
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 (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2014118699A external-priority patent/JP2015232059A/en
Priority claimed from JP2014118700A external-priority patent/JP2015232060A/en
Priority claimed from JP2014118701A external-priority patent/JP2015232061A/en
Priority claimed from JP2014118702A external-priority patent/JP2015232605A/en
Application filed by 日本合成化学工業株式会社 filed Critical 日本合成化学工業株式会社
Priority to CN201480028065.5A priority Critical patent/CN105229099B/en
Priority to KR1020157032654A priority patent/KR102159761B1/en
Publication of WO2015022825A1 publication Critical patent/WO2015022825A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • 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.
  • 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.
  • 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”).
  • PVA polyvinyl alcohol resin having a high saponification degree
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Patent Document 3 4-butylhydroxyacrylate: 20 to 90% by weight, ⁇ -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.
  • the adhesive of Patent Document 1 uses a cationic polymerizable UV curable adhesive instead of a water-based adhesive.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • (meth) acryl means acryl or methacryl
  • (meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylate means acrylate or methacrylate.
  • the acrylic monomer is a monomer having at least one of an acryloyl group and a methacryloyl group
  • the acrylic resin is a resin obtained by polymerizing a polymerization component containing at least one acrylic monomer.
  • 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 ).
  • 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.
  • 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.
  • metal or metalloid alcoholates and chelate compounds of the alcoholates are preferable.
  • metal or metalloid alcoholates represented by the following general formula (1), and chelate compounds of the alcoholates Is preferably used.
  • 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.
  • 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
  • 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
  • m + n represents the valence of M.
  • 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.
  • divalent to tetravalent metals or metalloids are used, and boron, silicon, aluminum, titanium and zirconium are particularly preferably used.
  • 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).
  • 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.
  • 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.
  • the carbon number of R 1 composed of these substituted derivatives is 10 or less including the carbon atom in the substituent.
  • R 1 examples of R 1 include an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group, a benzoyloxyl group, and a trioyloxyl group.
  • R 1 examples of R 1 include an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group, a benzoyloxyl group, and a trioyloxyl group.
  • acyloxyl group when two or more R 1 s are present, they may be the same or different from each other, but are preferably the same.
  • 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.
  • what is represented by R 2 may be hydrogen.
  • 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.
  • 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.
  • metal or metalloid alcoholate chelate compounds include metal or metalloid alcoholates and ⁇ -diketones, ⁇ -ketoesters, hydroxycarboxylic acids, hydroxycarboxylates, hydroxycarboxylic acid esters, ketoalcohols and aminoalcohols. It is preferably obtained by reaction with at least one selected compound.
  • ⁇ -diketones or ⁇ -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.
  • 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.
  • chelate-forming metal or metalloid compounds 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;
  • 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;
  • Zinc compounds such as zinc, bis (ethyl acetoacetate) zinc, propoxy-ethyl acetoacetate zinc, butoxy-ethyl acetoacetate zinc, di (acetylacetonato) zinc, di (ethylacetoacetate) zinc;
  • metal or metalloid alcoholates and chelate compounds preferred are boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, aluminum hydroxide, triethoxyaluminum, tripropoxyaluminum, tributoxy.
  • Particularly preferred compounds are boric acid and trimethylborate.
  • 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.
  • trialkyl borates having an alkyl group of 1 to 5 carbon atoms such as tripropyl borate, tributyl borate, etc., particularly tributyl borate.
  • metal or metalloid acylate examples 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 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 ⁇ -diketone structure, such as acetoacetyl groups and malonic esters, which have a ⁇ -diketone structure.
  • An acetoacetyl group is preferred from the viewpoint of convenience and reactivity with a hydroxyl group.
  • 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.
  • a diketene is reacted with the functional group-containing ethylenically unsaturated compound (i).
  • 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.
  • 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.
  • a transesterification catalyst such as calcium acetate, zinc acetate, lead oxide or the like.
  • 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)). .
  • 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 include styrene, vinyltoluene, chlorostyrene, ⁇ -methylstyrene.
  • a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination.
  • 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.
  • bifunctional monomer examples 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.
  • tri- or higher functional monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth).
  • 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) is used.
  • (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.
  • (A) to (C) can be appropriately blended to form an adhesive composition.
  • (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.
  • 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).
  • 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.
  • a chelate compound (AB) In forming such a chelate compound (AB), it is usually mixed at 20 to 120 ° C., particularly 30 to 80 ° C.
  • the presence of the above-mentioned metal or metalloid chelate compound exerts an effect of excellent color fading resistance of the polarizing plate.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • the thermal polymerization initiator (d2) is used, the adhesive composition is cured by heating.
  • 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.
  • 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.
  • 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.
  • thermal polymerization initiator (d2) examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexyl peroxide).
  • 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.
  • the content of the polymerization initiator (D) is too small, the curability tends to be poor and the physical properties tend to become unstable.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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”).
  • Shodex GPC KF-806L excludeded
  • high performance liquid chromatography manufactured by Showa Denko Co., Ltd., “Shodex GPC system-11 type”.
  • 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).
  • 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,
  • 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.
  • polyvalent isocyanate compound (e2) examples 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.).
  • 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.
  • isophorone diisocyanate is used in terms of excellent reactivity and versatility.
  • polyol compound (e3) examples include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, polysiloxane polyols, and the like.
  • polyether polyol examples 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.
  • polyester-based polyol examples 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.
  • polyhydric alcohol examples 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)
  • polyvalent carboxylic acid examples 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.
  • 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
  • cyclic ester examples include propiolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
  • polycarbonate polyol examples include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).
  • polyhydric alcohol examples 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.
  • polyolefin-based polyol examples 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.
  • polybutadiene-based polyol examples 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.
  • polysiloxane polyol examples include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.
  • 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.
  • 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.
  • the reaction between the polyol compound (e3) and the polyvalent isocyanate compound (e2) known reaction means can be used.
  • 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).
  • 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.
  • the reaction product: hydroxyl group-containing (meth) acrylate compound (e1) is about 1: 3.
  • 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 a
  • 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.
  • 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.
  • the compound (B), the urethane (meth) acrylate-based compound (E), and preferably another photopolymerizable compound (C) 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.
  • the adhesive composition comprising a.
  • (A) to (C) and (E) can be appropriately blended to form an adhesive composition.
  • (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
  • (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.
  • 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).
  • 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.
  • the urethane (meth) acrylate compound (E) 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.
  • 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.
  • SP value polymer solubility parameter
  • 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 inclusion 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 ⁇ m ) 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.
  • the polymer (F) preferably has an unsaturated group because it contributes to the photoreaction.
  • polymers (F) in the present invention examples include polyethylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polylactic acid resins, polypropylene resins, polycarbonate resins, polytetrafluoroethylene resins, and polyurethane resins.
  • acrylic resin (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.
  • 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.
  • 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.
  • 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.
  • (meth) acrylic acid phenyl ester examples 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.
  • 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.
  • hydroxyl group-containing monomer examples 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.
  • 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.
  • carboxyl group-containing monomer examples 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.
  • 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.
  • alkoxy group-containing monomer examples 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.
  • phenoxy group-containing monomer examples include 2-phenoxyethyl (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate.
  • 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.
  • amino group-containing monomer examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and a quaternized product thereof.
  • nitrogen-containing monomer examples 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.
  • sulfonic acid group-containing monomer examples 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. .
  • olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid
  • 2-acrylamido-2-methylpropane sulfonic acid styrene sulfonic acid
  • Examples of other copolymerizable monomers (f1-3) include acrylonitrile, methacrylonitrile, styrene, ⁇ -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.
  • ethylene glycol di (meth) acrylate 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.
  • 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
  • functional group-containing monomer (f1-2) is preferably 0 to 90% by weight, particularly preferably. 5 to 80% by weight
  • 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.
  • 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.
  • 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.
  • a random copolymer or a block copolymer is particularly preferable.
  • (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.
  • (A) to (C) and (F) can be appropriately blended to form an adhesive composition.
  • (A) is 0.1 to 30% by weight with respect to the total of (A) to (C) and (F)
  • (C) be 65 to 94% by weight
  • (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.
  • 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).
  • 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.
  • 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.
  • 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.
  • the acid group-containing monomer (G) as the compounding agent will be described.
  • 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,
  • 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.
  • [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)).
  • 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.
  • (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.
  • (A) to (C) and (G) can be appropriately blended to form an adhesive composition.
  • (A) is 0.1 to 30% by weight with respect to the total of (A) to (C) and (G)
  • (B) Is preferably 0.5 to 40% by weight
  • (C) is preferably 30 to 99% by weight
  • (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%.
  • (C) be 65 to 94% by weight
  • (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.
  • 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
  • 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).
  • the chelate compound (AB) formed from (A), (B), (G), (A) and (B), preferably (A), (B), (G), C) will also be contained.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the above photobase generator (H) preferably has a maximum molar extinction coefficient of usually 405 nm or less.
  • [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)).
  • [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) / (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.
  • (A) to (C) and (H) can be appropriately blended to form an adhesive composition.
  • (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%.
  • (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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a birefringent material having liquid crystallinity together with a dichroic material in the above is a vinyl alcohol resin
  • a uniaxially stretched thermoplastic norbornene resin film containing a dichroic material for example, Japanese Patent Application Laid-Open No. 2001-356213
  • 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.
  • 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 ⁇ m, preferably 0.5 to 80 ⁇ m, more preferably 1 to 60 ⁇ m.
  • 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.
  • 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.
  • 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 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 ⁇ -olefins. Resin etc. are included.
  • 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.
  • cyclic olefin-based resin films examples 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.
  • acrylic resin films examples include “Acrypet VRL20A”, “Acrypet IRD-70” manufactured by Mitsubishi Rayon Co., Ltd., and “MUX-60” manufactured by UMGABS.
  • 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.
  • 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 ⁇ m, preferably 20 to 80 ⁇ m. is there.
  • 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.
  • various optical functional films such as a phase difference plate and a viewing angle widening film can be laminated.
  • 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.
  • 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.
  • a roll laminator or the like can be used, and the pressure is selected from the range of 0.1 to 10 MPa.
  • rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron beams, proton rays, neutron rays, etc.
  • Curing by ultraviolet irradiation is advantageous from the standpoint of availability of the device and price.
  • electron beam irradiation it can harden
  • 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.
  • the high-pressure mercury lamp for example, 5 ⁇ 3000mJ / cm 2, preferably at a 50 ⁇ 2000mJ / cm 2 conditions.
  • 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.
  • 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 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 ⁇ m, preferably 0.01 to 5 ⁇ m, particularly preferably 0.01 to 2 ⁇ m, more preferably 0.01 to 1 ⁇ m. 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.
  • 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.
  • 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 °C)
  • 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.
  • a 60 ⁇ m 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.
  • 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 ⁇ m is formed with a bar coater (No. 10) so that the film thickness becomes 5 ⁇ m.
  • a bar coater No. 10
  • 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. .
  • 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.
  • 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.
  • 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:
  • A-5 boric acid
  • B-1 2-acetoacetoxyethyl methacrylate
  • C-2 dimethylacrylamide
  • E-1 bifunctional polyether urethane acrylate
  • 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.
  • Example 2 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.
  • 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.
  • 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.
  • A-5 boric acid
  • B-1 2-acetoacetoxyethyl methacrylate
  • F-1 polymethyl methacrylate
  • C-2 dimethylacrylamide
  • Example 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.
  • Example 3 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.
  • 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.
  • A-5 boric acid
  • B-1 2-acetoacetoxyethyl methacrylate
  • C-2 dimethylacrylamide
  • Example 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.
  • Example 4 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.
  • 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 Provide 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.
  • A-5 boric acid
  • B-1 2-acetoacetoxyethyl methacrylate
  • C-2 dimethylacrylamide
  • Example 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.
  • Example 5 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.
  • 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.
  • 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.
  • 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.
  • 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.

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  • Organic Chemistry (AREA)
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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

接着剤組成物、偏光板用接着剤組成物、偏光板用接着剤、およびそれを用いてなる偏光板Adhesive composition, polarizing plate adhesive composition, polarizing plate adhesive, and polarizing plate using the same
　本発明は、接着剤組成物、偏光板用接着剤組成物、偏光板用接着剤、およびそれを用いてなる偏光板に関するものであり、詳しくは液晶表示装置等に用いられる偏光板を構成する偏光子と保護フィルムの貼り合せに好適な活性エネルギー線硬化型のアクリル系接着剤に用いられる接着剤組成物に関するものである。 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.
　液晶表示装置は、液晶テレビ、コンピューターディスプレイ、携帯電話やデジタルカメラなどの画像表示装置として幅広く用いられている。かかる液晶表示装置は、液晶が封入されたガラス基板の両側に偏光板が積層された構成となっており、必要に応じて位相差板などの各種光学機能フィルムがこれに積層されている。 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.
　従来より、偏光板は、ポリビニルアルコール系フィルムよりなる偏光子の少なくとも一方の面、好ましくは両方の面に保護フィルムを貼り合わせた構成として用いられている。ここで、偏光子としては、高ケン化度のポリビニルアルコール系樹脂（以下、ポリビニルアルコールを「ＰＶＡ」と略記する。）を用いて製膜してなるＰＶＡ系フィルム中にヨウ素などの二色性材料が分散、吸着され、好ましくは更にホウ酸などの架橋剤によって架橋された、一軸延伸ＰＶＡ系フィルムが広く用いられている。このような偏光子は、一軸延伸ＰＶＡ系フィルムであるがゆえに、高湿度下においては収縮しやすくなるため、耐湿性や強度を補うことを目的に、偏光子に保護フィルムが貼り合わされる。 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.
　かかる保護フィルムとしては、セルロース樹脂、ポリカーボネート樹脂、環状ポリオレフィン樹脂、（メタ）アクリル樹脂、およびポリエステル樹脂等の熱可塑性樹脂が透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れる点で用いられているが、特にはトリアセチルセルロース（ＴＡＣ）樹脂からなる保護フィルムが広く用いられてきた。 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.
　そして、これらの保護フィルムは、接着剤によって偏光子と貼り合わされるが、かかる接着剤としては、親水性表面をもつ偏光子に対する接着性の点から、ＰＶＡ系樹脂水溶液、特に偏光子と同様の高ケン化度ＰＶＡ系樹脂を主体とするＰＶＡ系樹脂水溶液が好ましく用いられている。 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.
　ところで、近年では、偏光板の薄膜化が求められており、これまで保護フィルムとして最も一般的に使用されてきたＴＡＣフィルムに代えて、アクリル系フィルムや環状ポリオレフィン系樹脂フィルムが使用されるようになってきたが、これらＴＡＣフィルムに代わる保護フィルムにおいては、従来のＰＶＡ系接着剤を用いて偏光子と強固に貼り合せることはできないものである。そのため、ＰＶＡ系接着剤に代わるものとして、アクリル系フィルムや環状ポリオレフィン系樹脂フィルム等の保護フィルムの貼り合せに好適な種々の接着剤の開発が行なわれている。 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.
　また、ＰＶＡ系接着剤は、水を用いて溶液または分散液として使用されるものであるために、接着剤の硬化の際に水を乾燥させる必要があり、かかる水の乾燥に長時間を要してしまい乾燥適正が悪く、偏光板の生産効率が低くなる点の改善も求められていた。 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.
　例えば、特許文献１では、芳香環を含まないエポキシ樹脂を主成分とし、光カチオン重合開始剤を含有する組成物からなる接着剤が提案されており、かかる接着剤は活性エネルギー線照射によるカチオン重合で硬化されるため、透湿度の低い樹脂フィルムを保護膜とする場合であっても、充分な接着強度で、外観不良などの問題を起こすことなく、偏光子の片面又は両面に保護膜が貼合された偏光板を提供できることが記載されている。 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.
　また、特許文献２では、硬化成分としてＳＰ値が異なる３種のラジカル重合性化合物を含有する活性エネルギー線硬化型接着剤組成物が、偏光子と保護フィルムの接着性に優れ、かつ耐久性や耐水性に優れる接着剤として提案されている。 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.
　更に、特許文献３では、４－ブチルヒドロキシアクリレート：２０～９０重量％、ω－カルボキシ－ポリカプロラクトンアクリレート：１～７０重量％、その他のラジカル重合性化合物：０～１５重量％、光重合開始剤：０．０１～２０重量％、シランカップリング剤：０～１０重量％を含有してなり、硬化後のガラス転移温度が－８０～０℃となるような偏光板形成用ラジカル重合性接着剤組成物が提案されており、該接着剤組成物を用いることで、ＰＶＡ系偏光子と、アクリル系フィルムやシクロオレフィン系フィルムに代表される難接着性の保護フィルムとを構成層とし、接着力が大きく耐久性に優れる偏光板小片を形成し得る偏光板であり、打ち抜き加工性にも優れる偏光板が得られるとされている。 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.
　また、特許文献４では、水酸基を有しない（メタ）アクリルアミド化合物、水酸基を有する（メタ）アクリル酸アルキルエステル化合物、ホウ酸及び光重合開始剤を含有することを特徴とする紫外線硬化型組成物が提案されており、該接着剤組成物を用いることで、様々な保護フィルムのみならず、特にアクリル樹脂フィルムに対し、優れた接着強度を有する紫外線硬化型組成物が得られるとされている。 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.
特開２００４－２４５９２５号公報JP 2004-245925 A 特開２０１２－１４４６９０号公報JP 2012-144690 A 特開２０１０－２８２１６１号公報JP 2010-282161 A 特開２０１３－１９４０８２号公報JP2013-194082A
　しかしながら、上記特許文献１の接着剤では、水系接着剤の代わりに、カチオン重合性紫外線硬化型接着剤を使用するものであるが、カチオン重合性紫外線硬化型接着剤は、紫外線照射後に暗反応があるので、長尺の硬化物を巻取りロール状にした場合、保管時に巻き癖がつきやすいという問題があった。しかも、カチオン重合性紫外線硬化型接着剤は、硬化時の湿度の影響を受けやすく、硬化状態がバラつきやすいという問題も有しているものであった。 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.
　上記特許文献２のラジカル重合性紫外線硬化型接着剤では、接着剤層が相対的に硬いために経時での接着力の低下がおこり、耐打ち抜き加工性や耐久性の点で満足のいくものではなかった。 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.
　上記特許文献３のラジカル重合性接着剤組成物では、（メタ）アクリル酸モノマーの硬化時に硬化収縮を伴うために、初期接着の安定性が低くなり接着力が充分でないものであった。 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.
　上記特許文献４の紫外線硬化型組成物では、アクリル樹脂フィルムに対しては接着力を示すが、偏光子への接着力が充分でなく耐色抜け性も惰弱であった。 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.
　従って、上記活性エネルギー線硬化型の接着剤では、乾燥工程が必要なく水溶液として用いられるＰＶＡ系接着剤よりも生産効率は上がるものの、種々の偏光板用保護フィルムと偏光子を充分に接着することは困難であり、更なる改良が求められるものであった。 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.
　また、近年では、偏光板を高温高湿度下に長時間放置している場合に色抜け（退色）してしまうという問題も生じており、例えば、より過酷な評価となるが、温水中に浸漬した状態であっても色抜けしない、或いは色抜けが軽減された偏光板が求められている。このような耐色抜け性に優れた偏光板を得るための方法として、偏光子と保護フィルムとを貼り合わせる接着剤の改良も求められている状況の中で、上記特許文献１～４の接着剤では、かかる耐色抜け性は得られないものであった。 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.
　そこで、本発明ではこのような背景下において、接着力に優れる接着剤であり、種々の偏光板用保護フィルムと偏光子、特にはＴＡＣ以外の保護フィルムと偏光子の貼り合せにも好適であり、生産効率にも優れ、更に耐色抜け性にも優れた接着剤組成物、とりわけ偏光板用接着剤組成物を提供することを目的とするものである。 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.
　しかるに本発明者等は、かかる事情に鑑み鋭意研究を重ねた結果、活性エネルギー線硬化型の偏光板用の接着剤組成物において、接着剤となる際に金属または半金属のキレート化合物を存在させることにより、偏光子と保護フィルムの接着に優れ、更に、偏光板の耐色抜け性にも優れることを見出し、本発明を完成した。 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.
　即ち、本発明の要旨は、キレート形成可能な金属または半金属化合物（Ａ）及び該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有してなる接着剤組成物に関するものであり、また、キレート形成可能な金属または半金属化合物（Ａ）と、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）を含有してなる接着剤組成物に関するものである。 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).
　更に本発明は、前記接着剤組成物を用いてなる偏光板用接着剤組成物、それを硬化してなる偏光板用接着剤、及び、上記偏光板用接着剤を介して偏光子と保護フィルムが貼り合わされてなる偏光板をも提供するものである。 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.
　ここで、本発明においては、金属または半金属のキレート化合物を存在させることが重要であるが、これは偏光子を形成するＰＶＡ表面の水酸基と、接着剤中のキレート形成可能な官能基とが化学的結合を形成し、偏光子と保護フィルムの接着強度を高め、かつ、偏光子中のヨウ素の拡散を防ぐために偏光板の耐色抜け性が向上するものと推察される。 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.
　本発明の接着剤組成物、とりわけ偏光板用接着剤組成物は、偏光板の生産効率が高く、かつ、種々の偏光板用保護フィルムと偏光子、特にはアクリル系フィルムや環状ポリオレフィン系樹脂フィルム等のＴＡＣ以外の保護フィルムと偏光子を充分に接着することができ、更に、偏光板を高温高湿下や温水中に浸漬した状態であっても色抜けが抑制された耐色抜け性にも優れた偏光板を得ることができる。 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.
　以下、本発明を詳細に説明するが、これらは望ましい実施態様の一例を示すものである。
　なお、本発明において、（メタ）アクリルとはアクリルあるいはメタクリルを、（メタ）アクリロイルとはアクリロイルあるいはメタクリロイルを、（メタ）アクリレートとはアクリレートあるいはメタクリレートをそれぞれ意味するものである。
　また、アクリル系モノマーとは、アクリロイル基、メタクリロイル基の少なくとも一方を有するモノマーであり、アクリル系樹脂とは、少なくとも１種のアクリル系モノマーを含む重合成分を重合して得られる樹脂である。 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.
（接着剤組成物）
　本発明の接着剤組成物は、
［Ｉ］キレート形成可能な金属または半金属化合物（Ａ）及び該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有してなることを特徴とするものであり、
また、
［ＩＩ］キレート形成可能な金属または半金属化合物（Ａ）と、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）を含有してなることを特徴とするものである。 (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 ).
〈キレート形成可能な金属または半金属化合物（Ａ）〉
　本発明で用いられるキレート形成可能な金属または半金属化合物（Ａ）としては、後述の光重合性化合物（Ｂ）とキレート形成が可能なものであればよく、例えば、金属または半金属のアルコレート、該アルコレートの加水分解物、該アルコレートの縮合物、アルコレートのキレート化合物、該キレート化合物の部分アルコレート化物、及び、金属または半金属のアシレートの群から選ばれた少なくとも１種であることが好ましく、特には金属または半金属のアルコレート、該アルコレートのキレート化合物が好ましく、殊には下記一般式（１）で表される金属または半金属のアルコレート、該アルコレートのキレート化合物が好ましく用いられる。
　なお、キレート形成可能な金属または半金属化合物（Ａ）としては、上記化合物の中から１種だけを用いてもよいし、任意の２種以上を併用してもよい。 <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.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式中、Ｍは金属または半金属原子を表し、Ｒ１は同一または異なっていてもよい炭素数１～１０の一価の有機基を表し、Ｒ２は同一または異なっていてもよい水素または炭素数１～５のアルキル基または炭素数１～６のアシル基もしくはフェニル基を表し、ｍおよびｎはそれぞれ０以上の整数を表し、ｍ＋ｎはＭの原子価を表す。） 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.)
　上記一般式（１）において、Ｍで表される金属または半金属原子としては、例えば、遷移元素金属、２族、１２族、１３族、１４族の金属または半金属元素が挙げられ、特にはホウ素、ケイ素、アルミニウム、ジルコニウム、チタニウム、マグネシウム、クロム、コバルト、銅、鉄、ニッケル、バナジル、亜鉛、インジウム、カルシウム、マンガン、スズが好ましく、更にはホウ素、ケイ素、アルミニウム、チタニウム、クロム、銅、鉄、ニッケル、亜鉛、インジウムが好ましい。また、通常、２～４価の金属または半金属が用いられ、殊にはホウ素、ケイ素、アルミニウム、チタニウム、ジルコニウムが好ましく用いられる。更には、アルコレートやアシレートの状態が液体で、取り扱いの利便性の点からホウ素、ケイ素であることが最も好ましい。また、固体の状態でも、光重合性化合物（Ｃ）に易溶性であればよい。 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).
　上記一般式（１）において、Ｒ１で表される炭素数１～１０の１価の有機基としては、一般式（１）が金属または半金属のアルコレートである場合には、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基などのアルキル基；アセチル基、プロピオニル基、ブチリル基、バレリル基、ベンゾイル基、トリオイル基などのアシル基；ビニル基、アリル基、シクロヘキシル基、フェニル基、グリシジル基、（メタ）アクリルオキシ基、ウレイド基、アミド基、フルオロアセトアミド基、イソシアネート基などのほか、これらの基の置換誘導体などを挙げることができる。かかる置換誘導体における置換基としては、例えば、ハロゲン原子、置換もしくは非置換のアミノ基、水酸基、メルカプト基、イソシアネート基、グリシドキシ基、３，４－エポキシシクロヘキシル基、（メタ）アクリルオキシ基、ウレイド基、アンモニウム塩基などを挙げることができる。ただし、これらの置換誘導体からなるＲ１　の炭素数は、置換基中の炭素原子を含めて１０以下である。 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.
　また、上記一般式（１）が金属または半金属のアシレートである場合におけるＲ１としては、例えば、アセトキシル基、プロピオニロキシル基、ブチリロキシル基、バレリロキシル基、ベンゾイルオキシル基、トリオイルオキシル基などのアシルオキシル基を挙げることができる。
　なお、上記一般式（１）中に、Ｒ１が２個以上存在するときは、相互に同一でも異なってもよいが、同一である方が好ましい。 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.
　上記一般式（１）において、Ｒ２で表される炭素数１～５のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基などを挙げることができ、炭素数１～６のアシル基としては、例えば、アセチル基、プロピオニル基、ブチリル基、バレリル基、カプロイル基などを挙げることができる。また、Ｒ２で表されるものは水素でもよい。
　なお、上記一般式（１）中に、Ｒ２が複数個存在するときには、相互に同一でも異なってもよいが、同一である方が好ましい。 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.
　本発明における金属または半金属のアルコレートの加水分解物とは、上記金属または半金属アルコレートに含まれるＯＲ２基が加水分解されたものであるが、金属または半金属アルコレートに含まれるＯＲ２がすべて加水分解されている必要はなく、例えば、その１個だけが加水分解されているもの、２個以上が加水分解されているもの、あるいは、これらの混合物であってもよい。 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.
　本発明における金属または半金属のアルコレートの縮合物とは、上記金属または半金属アルコレートの加水分解物が縮合してＭ－Ｏ－Ｍの構造を有するものであるが、本発明では、かかる加水分解物の水酸基がすべて縮合している必要はなく、僅かな一部の水酸基が縮合したもの、縮合の程度が異なっているものの混合物などをも包含した概念である。 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.
　本発明における金属または半金属のアルコレートのキレート化合物とは、金属または半金属アルコレートの配位子のうち少なくとも一つがキレート結合された構造をもつ化合物である。かかる金属または半金属アルコレートのキレート化合物は、金属または半金属アルコレートと、β－ジケトン類、β－ケトエステル類、ヒドロキシカルボン酸、ヒドロキシカルボン酸塩、ヒドロキシカルボン酸エステル、ケトアルコールおよびアミノアルコールから選ばれる少なくとも１種の化合物との反応で得られたものであることが好ましい。 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.
　これらの化合物の中でも、β－ジケトン類またはβ－ケトエステル類を用いることが好ましく、これらの具体例としては、アセチルアセトン、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸－ｎ－プロピル、アセト酢酸－ｉ－プロピル、アセト酢酸－ｎ－ブチル、アセト酢酸－ｓｅｃ－ブチル、アセト酢酸－ｔ－ブチル、２，４－ヘキサン－ジオン、２，４－ヘプタン－ジオン、３，５－ヘプタン－ジオン、２，４－オクタン－ジオン、２，４－ノナン－ジオン、５－メチル－ヘキサン－ジオンなどを挙げることができる。これらの中でも、アセチルアセトン、アセト酢酸エチルを用いることが特に好ましい。 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.
　本発明におけるキレート化合物の加水分解物とは、上記した金属または半金属アルコレートの加水分解物と同様に、キレート化合物に含まれるＯＲ２基がすべて加水分解されている必要はなく、例えば、その１個だけが加水分解されているもの、２個以上が加水分解されているもの、あるいは、これらの混合物であってもよい。 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.
　本発明における金属または半金属のアシレートとは、上記金属または半金属アルコレートの配位子のうち少なくとも一つがアシルオキシル基であるものである。 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.
　これらのキレート形成可能な金属または半金属化合物（Ａ）のうち、金属または半金属アルコレートおよび金属または半金属アルコレートのキレート化合物の具体例としては、
〔１〕ホウ酸、トリメチルボレート、トリエチルボレート、トリブチルボレート（ノルマル、イソ、ターシャリー、セカンダリーを含む）、トリプロピルボレート、トリイソプロピルボレート、トリメチルカルビトールボレートなどのホウ素化合物； 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〕水酸化アルミニウム、トリエトキシアルミニウム、ジエトキシ・アセチルアセトナートアルミニウム、エトキシ・ビス（アセチルアセトナート）アルミニウム、トリス（アセチルアセトナート）アルミニウム、トリプロポキシアルミニウム、ジプロポキシ・アセチルアセトナートアルミニウム、プロポキシ・ビス（アセチルアセトナート）アルミニウム、トリブトキシアルミニウム、ジブトキシ・アセチルアセトナートアルミニウム、ブトキシ・ビス（アセチルアセトナート）アルミニウム、ジエトキシ・エチルアセトアセテートアルミニウム、エトキシ・ビス（エチルアセトアセテート）アルミニウム、トリス（エチルアセトアセテート）アルミニウム、ジプロポキシ・エチルアセトアセテートアルミニウム、プロポキシ・ビス（エチルアセトアセテート）アルミニウム、ジブトキシ・エチルアセトアセテートアルミニウム、ブトキシ・ビス（エチルアセトアセテート）アルミニウムなどのアルミニウム化合物； [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〕水酸化チタン、テトラエトキシチタニウム、トリエトキシ・アセチルアセトナートチタニウム、ジエトキシ・ビス（アセチルアセトナート）チタニウム、エトキシ・トリス（アセチルアセトナート）チタニウム、テトラキス（アセチルアセトナート）チタニウム、テトラプロポキシチタニウム、トリプロポキシ・アセチルアセトナートチタニウム、ジプロポキシ・ビス（アセチルアセトナート）チタニウム、プロポキシ・トリス（アセチルアセトナート）チタニウム、テトラブトキシチタニウム、トリブトキシ・アセチルアセトナートチタニウム、ジブトキシ・ビス（アセチルアセトナート）チタニウム、ブトキシ・トリス（アセチルアセトナート）チタニウム、トリエトキシ・エチルアセトアセテートチタニウム、ジエトキシ・ビス（エチルアセトアセテート）チタニウム、エトキシ・トリス（エチルアセトアセテート）チタニウム、テトラキス（エチルアセトアセテート）チタニウム、トリプロポキシ・エチルアセトアセテートチタニウム、ジプロポキシ・ビス（エチルアセトアセテート）チタニウム、プロポキシ・トリス（エチルアセトアセテート）チタニウム、トリブトキシ・エチルアセトアセテートチタニウム、ジブトキシ・ビス（エチルアセトアセテート）チタニウム、ブトキシ・トリス（エチルアセトアセテート）チタニウムなどのチタニウム化合物； [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〕テトラキス（メトキシ）ジルコニウム、テトラキス（エトキシ）ジルコニウム、テトラキス（プロポキシ）ジルコニウム、テトラキス（イソプロポキシ）ジルコニウム、テトラキス（ブトキシ）ジルコニウム、テトラキス（イソブチルオキシ）ジルコニウム、テトラキス（第２ブチルオキシ）ジルコニウム、テトラキス（第３ブチルオキシ）ジルコニウム、テトラキス（アミロキシ）ジルコニウム、テトラキス（第３アミルオキシ）ジルコニウム、テトラキス［２－（２－メトキシ）エトキシ］ジルコニウム、テトラキス［２－（１－メチル－２－メトキシ）プロポキシ］ジルコニウム、テトラキス［２－（２－メトキシ）プロポキシ］ジルコニウム、テトラキス［２－（ジメチルアミノ）エトキシ］ジルコニウム、テトラキス［２－（２－ジメチルアミノ－１－メチル）プロポキシ］ジルコニウム、テトラキス［２－（２－ジメチルアミノ）プロポキシ］ジルコニウム、ビス（２－プロポキシ）ビス［２－（２－ジメチルアミノ－１－メチル）プロポキシ］ジルコニウム、ビス（第３ブトキシ）ビス［２－（２－ジメチルアミノ－１－メチル）プロポキシ］ジルコニウム、ビス（第３ブトキシ）ビス［２－（２－ジメチルアミノ）プロポキシ］ジルコニウム、（第３ブトキシ）トリス［２－（２－ジメチルアミノ－１－メチル）プロポキシ］ジルコニウム、トリス（第３ブトキシ）［２－（２－ジメチルアミノ－１－メチル）プロポキシ］ジルコニウム等のアルコキシジルコニウム化合物；テトラキス（ジメチルアミノ）ジルコニウム、テトラキス（ジエチルアミノ）ジルコニウム、テトラキス（エチルメチルアミノ）ジルコニウム、テトラキス（ジプロピル）ジルコニウム、テトラキス（ジブチルアミノ）ジルコニウム、ビス（ジメチルアミノ）ビス（ジエチルアミノ）ジルコニウム、ビス（ジエチルアミノ）ビス（エチルメチルアミノ）ジルコニウム、（ジエチルアミノ）トリス（エチルメチルアミノ）ジルコニウム等や、ビス（メトキシ）ビス（ジメチルアミノ）ジルコニウム、ビス（メトキシ）ビス（ジエチルアミノ）ジルコニウム、ビス（メトキシ）ビス（エチルメチルアミノ）ジルコニウム、ビス（エトキシ）ビス（ジメチルアミノ）ジルコニウム、ビス（エトキシ）ビス（ジエチルアミノ）ジルコニウム、ビス（エトキシ）ビス（エチルメチルアミノ）ジルコニウム、ビス（２－プロポキシ）ビス（ジエチルアミノ）ジルコニウム、ビス（第３ブチル）ビス（ジエチルアミノ）ジルコニウム、ビス（第３ブチル）ビス（エチルメチルアミノ）ジルコニウム、（第３ブチル）トリス（エチルメチル）ジルコニウム等のアミノジルコニウム化合物や、テトラキスアセチルアセトネート、テトラキスエチルアセトアセトネート、テトラキスヘキサン－２，４－ジオネート、テトラキス－５－メチルヘキサン－２，４－ジオネート、テトラキスヘプタン－２，４－ジオネート、テトラキス－２－メチルヘプタン－３，５－ジオネート、テトラキス－５－メチルヘプタン－２，４－ジオネート、テトラキス－６－メチルヘプタン－２，４－ジオネート、テトラキス－２，２－ジメチルヘプタン－３，５－ジオネート、テトラキス－２，６－ジメチルヘプタン－３，５－ジオネート、テトラキス－２，２，６－トリメチルヘプタン－３，５－ジオネート、テトラキス－２，２，６，６－テトラメチルヘプタン－３，５－ジオネート、テトラキス－オクタン－２，４－ジオネート、テトラキス－２，２，６－トリメチルオクタン－３，５－ジオネート、テトラキス－２，６－ジメチルオクタン－３，５－ジオネート、テトラキス－２－メチル－６－エチルデカン－３，５－ジオネート、テトラキス－２，２－ジメチル－６－エチルデカン－３，５－ジオネート等のアルキル置換β－ジケトネート類、テトラキス－１，１，１－トリフルオロペンタン－２，４－ジオネート、テトラキス－１，１，１－トリフルオロ－５，５－ジメチルヘキサン－２，４－ジオネート、テトラキス－１，１，１，５，５，５－ヘキサフルオロペンタン－２，４－ジオネート、テトラキス－１，３－ジパーフルオロヘキシルプロパン－１，３－ジオネート等のフッ素置換アルキルβ－ジケトネート類、テトラキス－１，１，５，５－テトラメチル－１－メトキシヘキサン－２，４－ジオネート、テトラキス－２，２，６，６－テトラメチル－１－メトキシヘプタン－３，５－ジオネート、テトラキス－２，２，６，６－テトラメチル－１－（２－メトキシエトキシ）ヘプタン－３，５－ジオネート等のエーテル置換β－ジケトネート類等のジルコニウムβ－ジケトン化合物； [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〕水酸化亜鉛、ジエトキシ亜鉛、エトキシ・アセチルアセトナート亜鉛、ビス（アセチルアセトナート）亜鉛、ジプロポキシ亜鉛、プロポキシ・アセチルアセトナート亜鉛、ジブトキシ亜鉛、ブトキシ・アセチルアセトナート亜鉛、エトキシ・エチルアセトアセテート亜鉛、ビス（エチルアセトアセテート）亜鉛、プロポキシ・エチルアセトアセテート亜鉛、ブトキシ・エチルアセトアセテート亜鉛、ジ（アセチルアセトナート）亜鉛、ジ（エチルアセトアセテート）亜鉛などの亜鉛化合物； [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〕テトラメトキシシラン、テトラエトキシシラン、テトラ－ｎ－プロポキシシラン、テトライソプロポキシシラン、テトラ－ｎ－ブトキシシラン、テトライソブトキシシラン、テトラ－sec－ブトキシシラン、テトラ－tert－ブトキシシラン等のテトラアルコキシシラン、およびこれらを加水分解（縮合）することにより得られる化合物などのケイ素化合物；
を挙げることができる。 [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.
　これらの金属または半金属のアルコレートおよび該キレート化合物のうち好ましいものとしては、ホウ酸、トリメチルボレート、トリエチルボレート、トリプロピルボレート、トリブチルボレート、水酸化アルミニウム、トリエトキシアルミニウム、トリプロポキシアルミニウム、トリブトキシアルミニウム、ジプロポキシ・エチルアセトアセテートアルミニウム、トリス（エチルアセトアセテート）アルミニウム、トリス（アセチルアセトナート）アルミニウム、水酸化チタン、ジブトキシ・ビス（アセチルアセトナート）チタニウム、ジプロポキシ・ビス（アセチルアセトナート）チタニウム、ジエトキシ・ビス（アセチルアセトナート）チタニウム、ジブトキシ・ビス（エチルアセトアセテート）チタニウム、ジプロポキシ・ビス（エチルアセトアセテート）チタニウム、ジエトキシ・ビス（エチルアセトアセテート）チタニウム、水酸化亜鉛、ジ（アセチルアセトナート）亜鉛、ジ（エチルアセトアセテート）亜鉛を挙げることができ、特に好ましい化合物はホウ酸、トリメチルボレート、トリエチルボレート、トリプロピルボレート、トリブチルボレート、水酸化アルミニウム、トリプロポキシアルミニウム、トリス（アセチルアセトナート）アルミニウム、ジブトキシ・ビス（アセチルアセトナート）チタニウム、ジ（アセチルアセトナート）亜鉛などである。更には、常温液状での取り扱いの利便性、光重合性化合物（Ｃ）への溶解性や、偏光子を形成するＰＶＡ系樹脂の水酸基との反応性の点からホウ酸、トリメチルボレート、トリエチルボレート、トリプロピルボレート、トリブチルボレート等の炭素数１～５のアルキル基を有するトリアルキルボレート、特にはトリブチルボレートであることが最も好ましい。 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.
　また、金属または半金属のアシレートの具体例としては、ジヒドロキシ・チタンジブチレート、ジ－ｉ－プロポキシ・チタンジアセテート、ジ－ｉ－プロポキシ・チタンジプロピオネート、ジ－ｉ－プロポキシ・チタンジマロニエート、ジ－ｉ－プロポキシ・チタンジベンゾイレート、ジ－ｎ－ブトキシ・ジルコニウムジアセテート、ジ－ｉ－プロピルアルミニウムモノマロニエートなどを挙げることができ、特に好ましい化合物はジヒドロキシ・チタンジブチレート、ジ－ｉ－プロポキシ・チタンジアセテートなどのチタン化合物である。 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.
〈該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）〉
　また、本発明で用いられる上記の金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）としては、該官能基とエチレン性不飽和基を有する化合物であればよい。 <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.
　上記の金属または半金属とキレート形成可能な官能基としては、例えば、β－ジケトン構造を有する、アセトアセチル基、マロン酸エステル類等のβ－ジケトン構造を有する官能基が挙げられるが、汎用性や利便性、水酸基との反応性の点からアセトアセチル基が好ましい。 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.
　本発明において、金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）が、アセトアセチル基含有エチレン性不飽和化合物（ｂ１）である場合、例えば、次の方法によって製造することができる。 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）官能基含有エチレン性不飽和化合物（ｉ）にジケテンを反応させる。該官能基としてはヒドロキシル基、アミド基、ウレタン基、アミノ基、カルボキシル基等が挙げられ、官能基含有エチレン性不飽和化合物（ｉ）として好適なものは、炭素数１～１０のアルキレン基を有する脂肪族系アセトアセチル基含有アルキル（メタ）アクリレート系化合物であり、特に好ましくは、２－ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－クロロプロピル（メタ）アクリレート等の炭素数１～５のヒドロキシアルキル基を有する（メタ）アクリレート等である。 (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）上記官能基含有エチレン性不飽和化合物（ｉ）とアセト酢酸エステルとをエステル交換反応する。 (II) The functional group-containing ethylenically unsaturated compound (i) is transesterified with acetoacetate.
　上記の（Ｉ）の場合のジケテンの反応は、無触媒の他、第３級アミン、酸（硫酸等）、塩基性塩（酢酸ナトリウム等）、有機金属化合物（ジブチルスズラウレート等）の触媒存在下に行うことができる。
　上記の（ＩＩ）アセト酢酸エステルの反応は、酢酸カルシウム、酢酸亜鉛、酸化鉛等のエステル交換触媒の存在下に行うことが好ましい。
　上記の官能基含有エチレン性不飽和化合物（ｉ）の中でも、汎用性や利便性、製造上もしくは保存時の安定性等の点からヒドロキシアルキル基を有する（メタ）アクリレートであることが好ましい。 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.
〈光重合性化合物（Ｃ）〉
　本発明においては、更に、光重合性化合物（Ｃ）（但し、上記光重合性化合物（Ｂ）を除く。）を含有してなることが塗工性、硬化性、接着性等の点から好ましい。
　本発明で用いられる光重合性化合物（Ｃ）としては、上記光重合性化合物（Ｂ）を除くものであり、エチレン性不飽和基を１つ有するエチレン性不飽和化合物（ｃ１）及びエチレン性不飽和基を２つ以上有するエチレン性不飽和化合物（ｃ２）の群から選ばれる少なくとも１種であることが好ましい。 <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.
　エチレン性不飽和基を１つ有するエチレン性不飽和化合物（以下、「単官能モノマー」と略記することがある。）（ｃ１）としては、例えば、スチレン、ビニルトルエン、クロロスチレン、α－メチルスチレン、メチル（メタ）アクリレート、エチル（メタ）アクリレート、アクリロニトリル、酢酸ビニル、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、２－フェノキシ－２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、グリシジル（メタ）アクリレート、ラウリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリルレート、ジシクロペンタニル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ｎ－ステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノールエチレンオキサイド変性（ｎ＝２）（メタ）アクリレート、ノニルフェノールプロピレンオキサイド変性（ｎ＝２．５）（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルアシッドホスフェート、２－（メタ）アクリロイルオキシ－２－ヒドロキシプロピルフタレート等のフタル酸誘導体のハーフ（メタ）アクリレート、フルフリル（メタ）アクリレート、カルビトール（メタ）アクリレート、ベンジル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、アリル（メタ）アクリレート、アクリロイルモルホリン、ジメチルアクリルアミド、２－ヒドロキシエチルアクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ビニルピロリドン、２－ビニルピリジン、ポリオキシエチレン第２級アルキルエーテルアクリレート等が挙げられる。 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.
　更に、その他に、アクリル酸のミカエル付加物あるいは２－アクリロイルオキシエチルジカルボン酸モノエステルも併用可能であり、アクリル酸のミカエル付加物としては、アクリル酸ダイマー、メタクリル酸ダイマー、アクリル酸トリマー、メタクリル酸トリマー、アクリル酸テトラマー、メタクリル酸テトラマー等が挙げられる。また、２－アクリロイルオキシエチルジカルボン酸モノエステルとしては、特定の置換基をもつカルボン酸であり、例えば２－アクリロイルオキシエチルコハク酸モノエステル、２－メタクリロイルオキシエチルコハク酸モノエステル、２－アクリロイルオキシエチルフタル酸モノエステル、２－メタクリロイルオキシエチルフタル酸モノエステル、２－アクリロイルオキシエチルヘキサヒドロフタル酸モノエステル、２－メタクリロイルオキシエチルヘキサヒドロフタル酸モノエステル等が挙げられる。更に、その他オリゴエステルアクリレートも挙げられる。 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.
　また、エチレン性不飽和基を２つ以上有するエチレン性不飽和化合物（以下、「多官能モノマー」と略記することがある。）（ｃ２）としては、２官能モノマー、３官能以上のモノマーが挙げられる。 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.
　２官能モノマーとしては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、エトキシ化シクロヘキサンジメタノールジ（メタ）アクリレート、ジメチロールジシクロペンタンジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、エチレングリコールジグリシジルエーテルジ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、フタル酸ジグリシジルエステルジ（メタ）アクリレート、ヒドロキシピバリン酸変性ネオペンチルグリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジアクリレート等が挙げられる。 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.
　３官能以上のモノマーとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリ（メタ）アクリロイルオキシエトキシトリメチロールプロパン、グリセリンポリグリシジルエーテルポリ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性トリアクリレート、カプロラクトン変性ジペンタエリスリトールペンタ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールトリ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールテトラ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールペンタ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールテトラ（メタ）アクリレート、エトキシ化グリセリントリアクリレート等が挙げられる。
　光重合性化合物（Ｃ）は上記の中から１種を用いてもよいし２種以上併用してもよい。 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.
　かくして本発明においては、［Ｉ］キレート形成可能な金属または半金属化合物（Ａ）及び該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物、また、［ＩＩ］キレート形成可能な金属または半金属化合物（Ａ）と、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物とするわけである。 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.
　（Ａ）と（Ｂ）の配合割合については、（Ａ）／（Ｂ）が重量比で１／９９～５０／５０であることが好ましく、特には５／９５～４０／６０、更には１０／９０～３０／７０であることが好ましい。かかる（Ａ）／（Ｂ）の値は小さすぎると偏光子と保護フィルムの接着力の低下や耐色抜け性の低下となる傾向があり、大きすぎると耐温水試験時の耐久性の低下を招く傾向がある。 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.
　上記の［Ｉ］の場合には、（Ａ）～（Ｃ）を適宜配合して接着剤組成物とすることができる。（Ａ）～（Ｃ）の各含有割合については、（Ａ）～（Ｃ）の合計に対して、（Ａ）が０．１～３０重量％、（Ｂ）が０．９～４０重量％、（Ｃ）が３０～９９重量％であることが好ましく、特には（Ａ）が０．５～２０重量％、（Ｂ）が１．５～３０重量％、（Ｃ）が５０～９８重量％、更には（Ａ）が１～１５重量％、（Ｂ）が５～２０重量％、（Ｃ）が６５～９４重量％であることが好ましい。かかる（Ａ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｂ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下となる傾向がある。かかる（Ｃ）の含有量が少なすぎると耐温水試験時の耐久性の低下となる傾向があり、多すぎると偏光子と保護フィルムの接着力の低下となる傾向がある。 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.
　本発明においては、（Ａ）及び（Ｂ）、好ましくは更に（Ｃ）を含有する接着剤組成物として、偏光子等の基材に塗布し、通常５０～２００℃、特に好ましくは６０～１５０℃で乾燥を行うことにより、キレート化合物（Ａ－Ｂ）を形成することができる。また、（Ａ）及び（Ｂ）、好ましくは更に（Ｃ）を含有する接着剤組成物とした後、通常５０～１２０℃、特に好ましくは６０～９０℃で（Ａ）と（Ｂ）を反応させてキレート化合物（Ａ－Ｂ）を形成することができる。 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).
　また、［ＩＩ］の場合には、（Ａ）と（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、好ましくは（Ｃ）が含有されることになるが、更には、（Ａ）と、（Ｂ）と、（Ａ）と（Ｂ）から形成されてなるキレート化合物（Ａ－Ｂ）と、好ましくは（Ｃ）が含有されることにもなる。 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).
　かかるキレート化合物（Ａ－Ｂ）の含有量は、０．５～５０重量％であることが好ましく、特には、１～４０重量％、更には、５～３０重量％であることが好ましい。
　かかる含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。 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.
　かかるキレート化合物（Ａ－Ｂ）を形成させるに当たっては、通常２０～１２０℃、特には３０～８０℃で混合すればよい。 In forming such a chelate compound (AB), it is usually mixed at 20 to 120 ° C., particularly 30 to 80 ° C.
　本発明においては、上記の金属または半金属のキレート化合物を存在させることにより、偏光板の耐色抜け性に優れる効果を発揮することとなる。 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.
　本発明の接着剤組成物には、本発明の効果を損なわない範囲において、重合開始剤、シランカップリング剤、帯電防止剤、その他のアクリル系接着剤、その他の接着剤、ウレタン樹脂、ロジン、ロジンエステル、水添ロジンエステル、フェノール樹脂、芳香族変性テルペン樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、スチレン系樹脂、キシレン系樹脂等の粘着付与剤、ポリオールなどの可塑剤、着色剤、充填剤、老化防止剤、紫外線吸収剤、機能性色素等の従来公知の添加剤や、紫外線あるいは放射線照射により呈色あるいは変色を起こすような化合物を配合することができるが、これら添加剤の配合量は、組成物全体の３０重量％以下であることが好ましく、特に好ましくは２０重量％以下である。 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.
　また、上記添加剤の他にも、接着剤組成物の構成成分の製造原料等に含まれる不純物等が少量含有されたものであってもよい。 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.
〈重合開始剤（Ｄ）〉
　本発明においては、さらに上記の重合開始剤（Ｄ）を含有させ、接着剤組成物を硬化させることが好ましい。
　上記重合開始剤（Ｄ）としては、例えば、光重合開始剤（ｄ１）、熱重合開始剤（ｄ２）等の種々の重合開始剤を用いることが可能であるが、特には光重合開始剤（ｄ１）を使用することが、ごく短時間の紫外線等の活性エネルギー線照射により硬化させることが可能となる点で好ましい。 <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.
　また、上記光重合開始剤（ｄ１）を用いるときは、活性エネルギー線照射により接着剤組成物を硬化させ、熱重合開始剤（ｄ２）を用いるときは、加熱により接着剤組成物を硬化させるのであるが、必要に応じて、両方を併用することも好ましい。 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.
　上記光重合開始剤（ｄ１）としては、例えば、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、ベンジルジメチルケタール、４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－２－モルホリノ（４－チオメチルフェニル）プロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタノン、２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノンオリゴマー等のアセトフェノン類；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類；ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４－ベンゾイル－４′－メチル－ジフェニルサルファイド、３，３′，４，４′－テトラ（ｔ－ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４－ベンゾイル－Ｎ，Ｎ－ジメチル－Ｎ－［２－（１－オキソ－２－プロペニルオキシ）エチル］ベンゼンメタナミニウムブロミド、（４－ベンゾイルベンジル）トリメチルアンモニウムクロリド等のベンゾフェノン類；２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、１－クロロ－４－プロポキシチオキサントン、２－（３－ジメチルアミノ－２－ヒドロキシ）－３，４－ジメチル－９Ｈ－チオキサントン－９－オンメソクロリド等のチオキサントン類；２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等のアシルフォスフォンオキサイド類；等が挙げられる。なお、これら光重合開始剤（ｄ１）は、１種のみが単独で用いられてもよいし、２種以上が併用されてもよい。 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.
　また、これらの助剤として、トリエタノールアミン、トリイソプロパノールアミン、４，４′－ジメチルアミノベンゾフェノン（ミヒラーケトン）、４，４′－ジエチルアミノベンゾフェノン、２－ジメチルアミノエチル安息香酸、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸（ｎ－ブトキシ）エチル、４－ジメチルアミノ安息香酸イソアミル、４－ジメチルアミノ安息香酸２－エチルヘキシル、２，４－ジエチルチオキサンソン、２，４－ジイソプロピルチオキサンソン等を併用することも可能である。 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.
　これらの中でも、ベンジルジメチルケタール、１－ヒドロキシシクロヘキシルフェニルケトン、ベンゾイルイソプロピルエーテル、４－（２－ヒドロキシエトキシ）－フェニル（２－ヒドロキシ－２－プロピル）ケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オンを用いることが好ましい。 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.
　また、上記熱重合開始剤（ｄ２）としては、例えば、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、メチルアセトアセテートパーオキサイド、アセチルアセテートパーオキサイド、１，１－ビス（ｔ－ヘキシルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ヘキシルパーオキシ）－シクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）－２－メチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）－シクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）シクロドデカン、１，１－ビス（ｔ－ブチルパーオキシ）ブタン、２，２－ビス（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）プロパン、ｐ－メンタンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ｔ－ヘキシルハイドロパーオキサイド、ｔ－ブチルハイドロパーオキサイド、α，α′－ビス（ｔ－ブチルパーオキシ）ジイソプロピルベンゼン、ジクミルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキシン－３、イソブチリルパーオキサイド、３，５，５－トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ラウロイルパーオキサイド、ステアロイルパーオキサイド、スクシン酸パーオキサイド、ｍ－トルオイルベンゾイルパーオキサイド、ベンゾイルパーオキサイド、ジ－ｎ－プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ビス（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ－２－エトキシエチルパーオキシジカーボネート、ジ－２－エトキシヘキシルパーオキシジカーボネート、ジ－３－メトキシブチルパーオキシジカーボネート、ジ－ｓ－ブチルパーオキシジカーボネート、ジ（３－メチル－３－メトキシブチル）パーオキシジカーボネート、α，α′－ビス（ネオデカノイルパーオキシ）ジイソプロピルベンゼン、クミルパーオキシネオデカノエート、１，１，３，３－テトラメチルブチルパーオキシネオデカノエート、１－シクロヘキシル－１－メチルエチルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシネオデカノエート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノオエート、２，５－ジメチル－２，５－ビス（２－エチルヘキサノイルパーオキシ）ヘキサノエート、１－シクロヘキシル－１－メチルエチルパーオキシ－２－エチルヘキサノエート、ｔ－ヘキシルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ヘキシルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシイソブチレート、ｔ－ブチルパーオキシマレート、ｔ－ブチルパーオキシ－３，５，５－トリメトルヘキサノエート、ｔ－ブチルパーオキシラウレート、ｔ－ブチルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキシルモノカーボネート、ｔ－ブチルパーオキシアセテート、ｔ－ブチルパーオキシ－ｍ－トルイルベンゾエート、ｔ－ブチルパーオキシベンゾエート、ビス（ｔ－ブチルパーオキシ）イソフタレート、２，５－ジメチル－２，５－ビス（ｍ－トルイルパーオキシ）ヘキサン、ｔ－ヘキシルパーオキシベンゾエート、２，５－ジメチル－２，５－ビス（ベンゾイルパーオキシ）ヘキサン、ｔ－ブチルパーオキシアリルモノカーボネート、ｔ－ブチルトリメチルシリルパーオキサイド、３，３′，４，４′－テトラ（ｔ－ブチルパーオキシカルボニル）ベンゾフェノン、２，３－ジメチル－２，３－ジフェニルブタン等の有機過酸化物系開始剤；２－フェニルアゾ－４－メトキシ－２，４－ジメチルバレロニトリル、１－［（１－シアノ－１－メチルエチル）アゾ］ホルムアミド、１，１′－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２′－アゾビス（２－メチルブチロニトリル）、２，２′－アゾビスイソブチロニトリル、２，２′－アゾビス（２，４－ジメチルバレロニトリル）、２，２′－アゾビス（２－メチルプロピオンアミジン）ジヒドロクロリド、２，２′－アゾビス（２－メチル－Ｎ－フェニルプロピオンアミジン）ジヒドロクロリド、２，２′－アゾビス［Ｎ－（４－クロロフェニル）－２－メチルプロピオンアミジン］ジヒドリドクロリド、２，２′－アゾビス［Ｎ－（４－ヒドロフェニル）－２－メチルプロピオンアミジン］ジヒドロクロリド、２，２′－アゾビス［２－メチル－Ｎ－（フェニルメチル）プロピオンアミジン］ジヒドロクロリド、２，２′－アゾビス［２－メチル－Ｎ－（２－プロペニル）プロピオンアミジン］ジヒドロクロリド、２，２′－アゾビス［Ｎ－（２－ヒドロキシエチル）－２－メチルプロピオンアミジン］ジヒドロクロリド、２，２′－アゾビス［２－（５－メチル－２－イミダゾリン－２－イル）プロパン］ジヒドロクロリド、２，２′－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］ジヒドロクロリド、２，２′－アゾビス［２－（４，５，６，７－テトラヒドロ－１Ｈ－１，３－ジアゼピン－２－イル）プロパン］ジヒドロクロリド、２，２′－アゾビス［２－（３，４，５，６－テトラヒドロピリミジン－２－イル）プロパン］ジヒドロクロリド、２，２′－アゾビス［２－（５－ヒドロキシ－３，４，５，６－テトラヒドロピリミジン－２－イル）プロパン］ジヒドロクロリド、２，２′－アゾビス［２－［１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル］プロパン］ジヒドロクロリド、２，２′－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］、２，２′－アゾビス［２－メチル－Ｎ－［１，１－ビス（ヒドロキシメチル）－２－ヒドロキシエチル］プロピオンアミド］、２，２′－アゾビス［２－メチル－Ｎ－［１，１－ビス（ヒドロキシメチル）エチル］プロピオンアミド］、２，２′－アゾビス［２－メチル－Ｎ－（２－ヒドロキシエチル）プロピオンアミド］、２，２′－アゾビス（２－メチルプロピオンアミド）、２，２′－アゾビス（２，４，４－トリメチルペンタン）、２，２′－アゾビス（２－メチルプロパン）、ジメチル－２，２－アゾビス（２－メチルプロピオネート）、４，４′－アゾビス（４－シアノペンタン酸）、２，２′－アゾビス［２－（ヒドロキシメチル）プロピオニトリル］等のアゾ系開始剤；等が挙げられる。なお、これらの熱重合開始剤（ｄ２）は、１種のみが単独で用いられてもよいし、２種以上が併用されてもよい。 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.
　上記重合開始剤（Ｄ）の含有量については、上記（Ａ）及び（Ｂ）の合計（（Ｃ）が含有される場合は（Ａ）～（Ｃ）の合計）１００重量部に対して、０．５～２０重量部であることが好ましく、特に好ましくは０．８～１５重量部、さらに好ましくは１～１０重量部である。上記重合開始剤（Ｄ）の含有量が少なすぎると、硬化性に乏しく物性が安定しなくなる傾向がみられ、多すぎると低分子量成分が多くなり架橋密度が低下し耐水性や耐熱性などが低下する傾向がある。 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.
　本発明においては、上記成分に加え、さらに、ウレタン（メタ）アクリレート系化合物（Ｅ）、ポリマー（Ｆ）、酸基含有モノマー（Ｇ）、光塩基発生剤（Ｈ）を、各々適宜、配合剤として含有することが、塗工性、硬化性、接着性等の点から好ましい。これらは単独でもしくは２種以上併せて用いられる。上記化合物の中でも、ウレタン（メタ）アクリレート系化合物（Ｅ）を配合する場合が好ましく、特にはウレタン（メタ）アクリレート系化合物（Ｅ）とポリマー（Ｆ）の併用系が更に好ましい。 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.

〈ウレタン（メタ）アクリレート系化合物（Ｅ）〉
　上記のウレタン（メタ）アクリレート系化合物（Ｅ）としては、水酸基含有（メタ）アクリレート系化合物（ｅ１）、多価イソシアネート系化合物（ｅ２）及びポリオール系化合物（ｅ３）を反応させてなるもの（Ｅ１）や、水酸基含有（メタ）アクリレート系化合物（ｅ１）、多価イソシアネート系化合物（ｅ２）を反応させてなるもの（Ｅ２）が挙げられる。中でも特に好ましくは、水酸基含有（メタ）アクリレート系化合物（ｅ１）、多価イソシアネート系化合物（ｅ２）及びポリオール系化合物（ｅ３）を反応させてなるウレタン（メタ）アクリレート系化合物（Ｅ１）である。
<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).
　本発明で用いられるウレタン（メタ）アクリレート系化合物（Ｅ）の重量平均分子量は、５００～５００００であることが好ましく、更に好ましくは１０００～３００００である。かかる重量平均分子量が小さすぎると硬化収縮が大きくなって接着力が低下する傾向があり、大きすぎると耐水性が低下する傾向がある。 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.
　なお、上記の重量平均分子量は、標準ポリスチレン分子量換算による重量平均分子量であり、高速液体クロマトグラフィー（昭和電工社製、「Ｓｈｏｄｅｘ　ＧＰＣ　ｓｙｓｔｅｍ－１１型」）に、カラム：Ｓｈｏｄｅｘ　ＧＰＣ　ＫＦ－８０６Ｌ（排除限界分子量：２×１０7、分離範囲：１００～２×１０7、理論段数：１０，０００段／本、充填剤材質：スチレン－ジビニルベンゼン共重合体、充填剤粒径：１０μｍ）の３本直列を用いることにより測定される。 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.
　上記ウレタン（メタ）アクリレート系化合物（Ｅ）の６０℃における粘度は、５００～１５万ｍＰａ・ｓであることが好ましく、特に好ましくは５００～１２万ｍＰａ・ｓ、更に好ましくは１０００～１０万ｍＰａ・ｓである。かかる粘度が上記範囲外では塗工性が低下する傾向がある。
　なお、粘度の測定法はＥ型粘度計による。 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.
　水酸基含有（メタ）アクリレート系化合物（ｅ１）としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート、２－ヒドロキシエチルアクリロイルホスフェート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシプロピルフタレート、カプロラクトン変性２－ヒドロキシエチル（メタ）アクリレート、ジプロピレングリコール（メタ）アクリレート、脂肪酸変性－グリシジル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、グリセリンジ（メタ）アクリレート、２－ヒドロキシ－３－アクリロイル－オキシプロピルメタクリレート、ペンタエリスリトールトリ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールトリ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールペンタ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールペンタ（メタ）アクリレート等が挙げられる。 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.
　これらの中でも、エチレン性不飽和基を１個有する水酸基（メタ）アクリレート系化合物が塗膜形成の際の硬化収縮を緩和することができる理由から好ましく、更に好ましくは、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートであり、特には２－ヒドロキシエチル（メタ）アクリレートを用いることが、反応性および汎用性に優れる点で好ましい。
　また、これらは１種または２種以上組み合わせて使用することができる。 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.
　多価イソシアネート系化合物（ｅ２）としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ポリフェニルメタンポリイソシアネート、変性ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、フェニレンジイソシアネート、ナフタレンジイソシアネート等の芳香族系ポリイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等の脂肪族系ポリイソシアネート、水添化ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン等の脂環式系ポリイソシアネート、或いはこれらポリイソシアネートの３量体化合物又は多量体化合物、アロファネート型ポリイソシアネート、ビュレット型ポリイソシアネート、水分散型ポリイソシアネート（例えば、日本ポリウレタン工業社製の「アクアネート１００」、「アクアネート１１０」、「アクアネート２００」、「アクアネート２１０」等）、等が挙げられる。 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.).
　これらの中でも、黄変が少ない点から、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族系ジイソシアネート、水添化ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン等の脂環式系ジイソシアネートが、好ましく用いられ、特に好ましくは硬化収縮が小さい点でイソホロンジイソシアネート、水添化ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネートが用いられ、更に好ましくは、反応性および汎用性に優れる点でイソホロンジイソシアネートが用いられる。 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.
　ポリオール系化合物（ｅ３）としては、例えば、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリカーボネート系ポリオール、ポリオレフィン系ポリオール、ポリブタジエン系ポリオール、（メタ）アクリル系ポリオール、ポリシロキサン系ポリオール等が挙げられる。 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.
　上記ポリエーテル系ポリオールとしては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリブチレングリコール、ポリヘキサメチレングリコール等のアルキレン構造含有ポリエーテル系ポリオールや、これらポリアルキレングリコールのランダム或いはブロック共重合体が挙げられる。 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.
　上記ポリエステル系ポリオールとしては、例えば、多価アルコールと多価カルボン酸との縮合重合物；環状エステル（ラクトン）の開環重合物；多価アルコール、多価カルボン酸及び環状エステルの３種類の成分による反応物などが挙げられる。 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.
　前記多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリメチレングリコール、１，４－テトラメチレンジオール、１，３－テトラメチレンジオール、２－メチル－１，３－トリメチレンジオール、１，５－ペンタメチレンジオール、ネオペンチルグリコール、１，６－ヘキサメチレンジオール、３－メチル－１，５－ペンタメチレンジオール、２，４－ジエチル－１，５－ペンタメチレンジオール、グリセリン、トリメチロールプロパン、トリメチロールエタン、シクロヘキサンジオール類（１，４－シクロヘキサンジオールなど）、ビスフェノール類（ビスフェノールＡなど）、糖アルコール類（キシリトールやソルビトールなど）などが挙げられる。 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)
　前記多価カルボン酸としては、例えば、マロン酸、マレイン酸、フマル酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカンジオン酸等の脂肪族ジカルボン酸；１，４－シクロヘキサンジカルボン酸等の脂環式ジカルボン酸；テレフタル酸、イソフタル酸、オルトフタル酸、２，６－ナフタレンジカルボン酸、パラフェニレンジカルボン酸、トリメリット酸等の芳香族ジカルボン酸などが挙げられる。 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.
　前記環状エステルとしては、例えば、プロピオラクトン、β－メチル－δ－バレロラクトン、ε－カプロラクトンなどが挙げられる。 Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.
　上記ポリカーボネート系ポリオールとしては、例えば、多価アルコールとホスゲンとの反応物；環状炭酸エステル（アルキレンカーボネートなど）の開環重合物などが挙げられる。 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).
　前記多価アルコールとしては、前記ポリエステル系ポリオールの説明中で例示の多価アルコール等が挙げられ、上記アルキレンカーボネートとしては、例えば、エチレンカーボネート、トリメチレンカーボネート、テトラメチレンカーボネート、ヘキサメチレンカーボネートなどが挙げられる。 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.
　なお、ポリカーボネート系ポリオールは、分子内にカーボネート結合を有し、末端がヒドロキシル基である化合物であればよく、カーボネート結合とともにエステル結合を有していてもよい。 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.
　上記ポリオレフィン系ポリオールとしては、飽和炭化水素骨格としてエチレン、プロピレン、ブテン等のホモポリマーまたはコポリマーを有し、その分子末端に水酸基を有するものが挙げられる。 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.
　上記ポリブタジエン系ポリオールとしては、炭化水素骨格としてブタジエンの共重合体を有し、その分子末端に水酸基を有するものが挙げられる。
　ポリブタジエン系ポリオールは、その構造中に含まれるエチレン性不飽和基の全部または一部が水素化された水添化ポリブタジエンポリオールであってもよい。 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.
　上記（メタ）アクリル系ポリオールとしては、（メタ）アクリル酸エステルを重合体又は共重合体の分子内にヒドロキシル基を少なくとも２つ有しているものが挙げられ、かかる（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸オクタデシル等の（メタ）アクリル酸アルキルエステル等が挙げられる。 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.
　上記ポリシロキサン系ポリオールとしては、例えば、ジメチルポリシロキサンポリオールやメチルフェニルポリシロキサンポリオール等が挙げられる。 Examples of the polysiloxane polyol include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.
　これらの中でも、ポリエステル系ポリオール、ポリエーテル系ポリオールが好ましく、特に好ましくは硬化時に柔軟性等の機械的物性に優れる点でポリエステル系ポリオールである。 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.
　上記ポリオール系化合物（ｅ３）の重量平均分子量としては、５００～８０００が好ましく、特に好ましくは５５０～５０００、更に好ましくは６００～３０００である。ポリオール系化合物（ｅ３）の分子量が大きすぎると、接着力が低下する傾向があり、小さすぎると耐水性が低下する傾向がある。 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.
　本発明において、ウレタン（メタ）アクリレート系化合物（Ｅ）は、次のようにして製造することができる。下記の説明は、水酸基含有（メタ）アクリレート系化合物（ｅ１）、多価イソシアネート系化合物（ｅ２）及びポリオール系化合物（ｅ３）を反応させてなるウレタン（メタ）アクリレート系化合物（Ｅ１）についての説明であるが、かかる方法に準じて行うことにより、水酸基含有（メタ）アクリレート系化合物（ｅ１）、多価イソシアネート系化合物（ｅ２）を反応させてなるウレタン（メタ）アクリレート系化合物（Ｅ２）も製造できる。 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.
　ウレタン（メタ）アクリレート系化合物（Ｅ１）の製造法は、通常、上記水酸基含有（メタ）アクリレート系化合物（ｅ１）、多価イソシアネート系化合物（ｅ２）、ポリオール系化合物（ｅ３）を、反応器に一括又は別々に仕込み反応させればよいが、ポリオール系化合物（ｅ３）と多価イソシアネート系化合物（ｅ２）とを予め反応させて得られる反応生成物に、水酸基含有（メタ）アクリレート系化合物（ｅ１）を反応させるのが、反応の安定性や副生成物の低減等の点で有用である。 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.
　ポリオール系化合物（ｅ３）と多価イソシアネート系化合物（ｅ２）との反応には、公知の反応手段を用いることができる。その際、例えば、多価イソシアネート系化合物（ｅ２）中のイソシアネート基：ポリオール系化合物（ｅ３）中の水酸基とのモル比を、通常２ｎ：（２ｎ－２）（ｎは２以上の整数）程度にすることにより、イソシアネート基を残存させた末端イソシアネート基含有ウレタン（メタ）アクリレート系化合物を得た後、水酸基含有（メタ）アクリレート系化合物（ｅ１）との付加反応を可能にする。 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.
　上記ポリオール系化合物（ｅ３）と多価イソシアネート系化合物（ｅ２）とを予め反応させて得られる反応生成物と、水酸基含有（メタ）アクリレート系化合物（ｅ１）との付加反応にも、公知の反応手段を用いることができる。 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.
　反応生成物と水酸基含有（メタ）アクリレート系化合物（ｅ１）との反応モル比は、例えば、多価イソシアネート系化合物（ｅ２）のイソシアネート基が２個で、水酸基含有（メタ）アクリレート系化合物（ｅ１）の水酸基が１個である場合は、反応生成物：水酸基含有（メタ）アクリレート系化合物（ｅ１）が１：２程度であり、多価イソシアネート系化合物（ｅ２）のイソシアネート基が３個で、水酸基含有（メタ）アクリレート系化合物（ｅ１）の水酸基が１個である場合は、反応生成物：水酸基含有（メタ）アクリレート系化合物（ｅ１）が１：３程度である。 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.
　この反応生成物と水酸基含有（メタ）アクリレート系化合物（ｅ１）との付加反応においては、反応系の残存イソシアネート基含有率が０．５重量％以下になる時点で反応を終了させることにより、ウレタン（メタ）アクリレート系化合物（Ｅ）が得られる。 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.
　かかるポリオール系化合物（ｅ３）と多価イソシアネート系化合物（ｅ２）との反応、更にその反応生成物と水酸基含有（メタ）アクリレート系化合物（ｅ１）との反応においては、反応を促進する目的で触媒を用いることも好ましく、かかる触媒としては、例えば、ジブチル錫ジラウレート、トリメチル錫ヒドロキシド、テトラ－ｎ－ブチル錫等の有機金属化合物、オクトエ酸亜鉛、オクトエ酸錫、ナフテン酸コバルト、塩化第１錫、塩化第２錫等の金属塩、トリエチルアミン、ベンジルジエチルアミン、１，４－ジアザビシクロ［２，２，２］オクタン、１，８－ジアザビシクロ［５，４，０］ウンデセン、Ｎ，Ｎ，Ｎ′，Ｎ′－テトラメチル－１，３－ブタンジアミン、Ｎ－エチルモルホリン等のアミン系触媒、硝酸ビスマス、臭化ビスマス、ヨウ化ビスマス、硫化ビスマス等の他、ジブチルビスマスジラウレート、ジオクチルビスマスジラウレート等の有機ビスマス化合物や、２－エチルヘキサン酸ビスマス塩、ナフテン酸ビスマス塩、イソデカン酸ビスマス塩、ネオデカン酸ビスマス塩、ラウリル酸ビスマス塩、マレイン酸ビスマス塩、ステアリン酸ビスマス塩、オレイン酸ビスマス塩、リノール酸ビスマス塩、酢酸ビスマス塩、ビスマスリビスネオデカノエート、ジサリチル酸ビスマス塩、ジ没食子酸ビスマス塩等の有機酸ビスマス塩等のビスマス系触媒等が挙げられ、中でも、ジブチル錫ジラウレート、１，８－ジアザビシクロ［５，４，０］ウンデセンが好適である。 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.
　またポリオール系化合物（ｅ３）と多価イソシアネート系化合物（ｅ２）との反応、更にその反応生成物と水酸基含有（メタ）アクリレート系化合物（ｅ１）との反応においては、イソシアネート基に対して反応する官能基を有しない有機溶剤、例えば、酢酸エチル、酢酸ブチル等のエステル類、メチルエチルケトン、メチルイソブチルケトン等のケトン類、トルエン、キシレン等の芳香族類等の有機溶剤を用いることができる。 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.
　また、反応温度は、通常３０～９０℃、好ましくは４０～８０℃であり、反応時間は、通常２～１０時間、好ましくは３～８時間である。 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.
　本発明で用いられるウレタン（メタ）アクリレート系化合物（Ｅ）の不飽和基の数は、硬化収縮の点で、２～６個が好ましく、特には２～４個、更には２個が好ましい。 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.
　ウレタン（メタ）アクリレート系化合物（Ｅ）を用いる場合、［Ｉ’］キレート形成可能な金属または半金属化合物（Ａ）と、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）と、ウレタン（メタ）アクリレート系化合物（Ｅ）と、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物、また、［ＩＩ’］キレート形成可能な金属または半金属化合物（Ａ）及び該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、ウレタン（メタ）アクリレート系化合物（Ｅ）と、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物とする。 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.
　上記の［Ｉ’］の場合には、（Ａ）～（Ｃ）および（Ｅ）を適宜配合して接着剤組成物とすることができる。（Ａ）～（Ｃ）および（Ｅ）の各含有割合については、（Ａ）～（Ｃ）および（Ｅ）の合計に対して、（Ａ）が０．１～３０重量％、（Ｂ）が０．０１～３０重量％、（Ｃ）が３０～９９重量％、（Ｅ）が０．５～５０重量％であることが好ましく、特には（Ａ）が０．５～２０重量％、（Ｂ）が０．０５～２０重量％、（Ｃ）が５０～９８重量％、（Ｅ）が１～４０重量％、更には（Ａ）が１～１５重量％、（Ｂ）が０．１～１０重量％、（Ｃ）が６５～９４重量％、（Ｅ）が４～３０重量％であることが好ましい。 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.
　かかる（Ａ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｂ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下となる傾向がある。かかる（Ｃ）の含有量が少なすぎると耐温水試験時の耐久性の低下となる傾向があり、多すぎると偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｅ）の含有量が少なすぎると耐水性や接着力が低下する傾向があり、多すぎても接着力が低下する傾向がある。 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.
　上記においては、（Ａ）及び（Ｂ）、好ましくは更に（Ｃ）、（Ｅ）を含有する接着剤組成物として、偏光子に塗布し、通常５０～２００℃、特に好ましくは６０～１５０℃で乾燥を行うことにより、キレート化合物（Ａ－Ｂ）を形成することができる。また、（Ａ）及び（Ｂ）、好ましくは更に（Ｃ）、（Ｅ）を含有する接着剤組成物とした後、通常５０～１２０℃、特に好ましくは６０～９０℃で（Ａ）と（Ｂ）を反応させてキレート化合物（Ａ－Ｂ）を形成することができる。 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).
　また、［ＩＩ’］の場合には、（Ａ）及び（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、（Ｅ）と、好ましくは（Ｃ）とが含有されることになるが、更には、（Ａ）と、（Ｂ）と、（Ｅ）と、（Ａ）と（Ｂ）から形成されてなるキレート化合物（Ａ－Ｂ）と、好ましくは（Ｃ）が含有されることにもなる。 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.
　かかるキレート化合物（Ａ－Ｂ）の含有量は、０．１～４０重量％であることが好ましく、特には、０．５～３０重量％、更には、１～２０重量％であることが好ましい。
　かかる含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。 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.
　上記のように、ウレタン（メタ）アクリレート系化合物（Ｅ）を含有することにより、硬化収縮を緩和させることができ、また、多官能であることにより架橋度を向上させ、さらに接着強度を高め、耐水性の向上を図るものと推察される。このように推察されるのは、上記ウレタン（メタ）アクリレート系化合物（Ｅ）は、多官能でありながら、ポリマー部位（ポリオール部分の繰り返し構造により、ある程度の分子量を持たせる）を有するため、架橋度をアップさせながら、硬化収縮を小さくすることができるものと考えられるからである。 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.
〈ポリマー（Ｆ）〉
　つぎに前記配合剤であるポリマー（Ｆ）について説明する。
　さらに、本発明で用いられる上記のポリマー（Ｆ）は、ポリマーの溶解性パラメータ（ＳＰ値）が、８～２５であり、好ましくは９～２０である。ＳＰ値が低すぎると相溶性が低下する傾向となり、高すぎても相溶性が低下する傾向となる。 <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.
　上記溶解性パラメータ（ＳＰ値）は、Ｆｅｄｏｒｓの算出法［「ポリマー・エンジニアリング・アンド・サイエンス（Ｐｏｌｙｍｅｒ　Ｅｎｇ．＆　Ｓｃｉ．）」，第１４巻，第２号（１９７４），第１４８～１５４ページ参照］の方法によって測定される。 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.
　ポリマー（Ｆ）の重量平均分子量については、通常、１万～１５０万、好ましくは３万～１００万、特に好ましくは４万～５０万である。かかる重量平均分子量が低すぎると接着力が低下する傾向があり、高すぎると相溶性が低下し接着剤組成物としての安定性が低下する傾向がある。 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.
　上記の重量平均分子量は、標準ポリスチレン分子量換算によるものであり、高速液体クロマトグラフィー（日本Ｗａｔｅｒｓ社製、「Ｗａｔｅｒｓ ２６９５（本体）」と「Ｗａｔｅｒｓ ２４１４（検出器）」）に、カラム：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ－８０６Ｌ（排除限界分子量：２×１０7、分離範囲：１００～２×１０7、理論段数：１０，０００段／本、充填剤材質：スチレン－ジビニルベンゼン共重合体、充填剤粒径：１０μｍ）の３本直列を用いることにより測定されるものである。 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.
　ポリマー（Ｆ）のガラス転移温度（Ｔｇ）は、通常、－２０～１２０℃、好ましくは－１０～１１０℃、特に好ましくは－５～１００℃である。かかるガラス転移温度が低すぎると耐水性が低下する傾向があり、高すぎると接着力が低下する傾向がある。 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.
　なお、上記ポリマー（Ｆ）におけるＴｇは、ＤＳＣを用いて、測定試料が相転移・融解など熱の収支を伴う変化が起こった時の標準試料との熱量の差を検出することにより測定される値である。 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.
　また、ポリマー（Ｆ）は不飽和基を有することが、光反応に寄与することから好ましい。 Further, the polymer (F) preferably has an unsaturated group because it contributes to the photoreaction.
　本発明におけるポリマー（Ｆ）は、例えば、ポリエチレン系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリ乳酸系樹脂、ポリプロピレン系樹脂、ポリカーボネート系樹脂、ポリテトラフルオロエチレン系樹脂、ポリウレタン系樹脂、ポリスチレン系樹脂、ＡＢＳ系樹脂、アクリル系樹脂、ポリアセタール系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリアルキレンオキサイド系樹脂等が挙げられ、中でもアクリル系樹脂（ｆ１）、およびポリオキシアルキレン鎖を含有するポリマー（ｆ２）の少なくとも一方が好ましく用いられる。これらは単独でもしくは２種以上併せて用いられる。 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.
　本発明におけるアクリル系樹脂（ｆ１）とは、（メタ）アクリル系モノマーを含有するモノマー成分を重合してなるものである。アクリル系樹脂（ｆ１）は、１種のみを単独で用いてもよいし、２種以上を併用してもよい。 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.
　アクリル系樹脂（ｆ１）は、好ましくは、重合成分として、（メタ）アクリル酸エステル系モノマー（ｆ１－１）を主成分として含有し、必要に応じて、官能基含有モノマー（ｆ１－２）、その他の共重合性モノマー（ｆ１－３）を共重合成分とすることもできる。
　かかる（メタ）アクリル酸エステル系モノマー（ｆ１－１）としては、例えば（メタ）アクリル酸アルキルエステル等の脂肪族系（メタ）アクリル酸エステル系モノマー、（メタ）アクリル酸フェニルエステル等の芳香族系（メタ）アクリル酸エステル系モノマーが挙げられる。 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.
　かかる（メタ）アクリル酸アルキルエステルについては、アルキル基の炭素数が、通常１～１２、特には１～８、更には４～８であることが好ましく、具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等が挙げられる。また、（メタ）アクリル酸フェニルエステルとしては、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等が挙げられる。
　その他（メタ）アクリル酸エステル系モノマーとしては、テトラヒドロフルフリル（メタ）アクリレート等が挙げられる。これらは１種を単独で又は２種以上を併せて用いることができる。 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.
　かかる（メタ）アクリル酸エステル系モノマー（ｆ１－１）の中でも、共重合性、粘着物性、取り扱いやすさ及び原料入手しやすさの点で、メチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレートが好ましく用いられる。 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.
　官能基含有モノマー（ｆ１－２）としては、例えば、水酸基含有モノマー、カルボキシル基含有モノマー、アルコキシ基又はフェノキシ基含有モノマー、アミド基含有モノマー、アミノ基含有モノマー、窒素含有モノマー、グリシジル基含有モノマー、リン酸基含有モノマー、スルホン酸基含有モノマー等が挙げられ、単独又は２種以上併用して用いられる。 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.
　上記水酸基含有モノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等の（メタ）アクリル酸ヒドロキシアルキルエステル、カプロラクトン変性２－ヒドロキシエチル（メタ）アクリレート等のカプロラクトン変性モノマー、２－アクリロイロキシエチル－２－ヒドロキシエチルフタル酸、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド等の１級水酸基含有モノマー；２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等の２級水酸基含有モノマー；２，２－ジメチル－２－ヒドロキシエチル（メタ）アクリレート等の３級水酸基含有モノマーが挙げられる。 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.
　また、ジエチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等のポリエチレングリコール誘導体、ポリプロピレングリコールモノ（メタ）アクリレート等のポリプロピレングリコール誘導体、ポリエチレングリコール－ポリプロピレングリコール－モノ（メタ）アクリレート、ポリ（エチレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート、ポリ（プロピレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート等のオキシアルキレン変性モノマーを用いてもよい。 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.
　上記カルボキシル基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、アクリルアミドＮ－グリコール酸、ケイ皮酸、（メタ）アクリル酸のミカエル付加物（例えば、アクリル酸ダイマー、メタクリル酸ダイマー、アクリル酸トリマー、メタクリル酸トリマー、アクリル酸テトラマー、メタクリル酸テトラマー等）、２－（メタ）アクリロイルオキシエチルジカルボン酸モノエステル（例えば、２－アクリロイルオキシエチルコハク酸モノエステル、２－メタクリロイルオキシエチルコハク酸モノエステル、２－アクリロイルオキシエチルフタル酸モノエステル、２－メタクリロイルオキシエチルフタル酸モノエステル、２－アクリロイルオキシエチルヘキサヒドロフタル酸モノエステル、２－メタクリロイルオキシエチルヘキサヒドロフタル酸モノエステル等）等が挙げられる。なお、かかるカルボキシル基含有モノマーは、酸のまま用いてもよいし、アルカリで中和された塩の形で用いてもよい。 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.
　上記アルコキシ基含有モノマーとしては、例えば、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、３－メトキシブチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－ブトキシジエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、オクトキシポリエチレングリコール- ポリプロピレングリコール- モノ（メタ）アクリレート、ラウロキシポリエチレングリコールモノ（メタ）アクリレート、ステアロキシポリエチレングリコールモノ（メタ）アクリレート等の脂肪族系の（メタ）アクリル酸エステル等が挙げられ、フェノキシ基含有モノマーとしては、例えば、２－フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール－ポリプロピレングリコール－（メタ）アクリレート、ノニルフェノールエチレンオキサイド付加物（メタ）アクリレート等の芳香族（メタ）アクリレートのアクリル酸エステル等があげられる。 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.
　上記アミド基含有モノマーとしては、例えば、アクリルアミド、メタクリルアミド、Ｎ－（ｎ－ブトキシアルキル）アクリルアミド、Ｎ－（ｎ－ブトキシアルキル）メタクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、アクリルアミド－３－メチルブチルメチルアミン、ジメチルアミノアルキルアクリルアミド、ジメチルアミノアルキルメタクリルアミド等が挙げられる。 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.
　上記アミノ基含有モノマーとしては、例えば、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレートやその４級化物等が挙げられる。
　上記窒素含有モノマーとしては、例えば、アクリロイルモルホリン等が挙げられる。 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.
　上記グリシジル基含有モノマーとしては、例えば、グリシジル（メタ）アクリレート、アリルグリシジルエーテル等が挙げられる。 Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
　上記リン酸基含有モノマーとしては、例えば、２－（メタ）アクリロイロキシエチルアシッドホスフェート、ビス（２－（メタ）アクリロイロキシエチル）アシッドホスフェート等が挙げられる。 Examples of the phosphoric acid group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, and the like.
　上記スルホン酸基含有モノマーとしては、例えば、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸、２－アクリルアミド－２－メチルプロパンスルホン酸、スチレンスルホン酸あるいはその塩等が挙げられる。
　これら官能基含有モノマー（ｆ１－２）は、１種又は２種以上併用して用いてもよい。 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.
　その他の共重合性モノマー（ｆ１－３）としては、例えば、アクリロニトリル、メタクリロニトリル、スチレン、α－メチルスチレン、酢酸ビニル、プロピオン酸ビニル、ステアリン酸ビニル、塩化ビニル、塩化ビニリデン、アルキルビニルエーテル、ビニルトルエン、ビニルピリジン、ビニルピロリドン、イタコン酸ジアルキルエステル、フマル酸ジアルキルエステル、アリルアルコール、アクリルクロライド、メチルビニルケトン、Ｎ－アクリルアミドメチルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン等のモノマーが挙げられる。 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.
　また、高分子量化を目的とする場合、エチレングリコールジ（メタ) アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジビニルベンゼン等のエチレン性不飽和基を二つ以上有する化合物等を併用することもできる。 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.
　アクリル系樹脂（ｆ１）において、（メタ）アクリル酸エステル系モノマー（ｆ１－１）、官能基含有モノマー（ｆ１－２）、及びその他共重合性モノマー（ｆ１－３）の含有割合は、（メタ）アクリル酸エステル系モノマー（ｆ１－１）が好ましくは１０～１００重量％、特に好ましくは２０～９５重量％、官能基含有モノマー（ｆ１－２）が好ましくは０～９０重量％、特に好ましくは５～８０重量％、その他共重合性モノマー（ｆ１－３）が好ましくは０～５０重量％、特に好ましくは５～４０重量％であればよい。 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.
　本発明におけるアクリル系樹脂（ｆ１）としては、耐水性や接着性の点でメチル（メタ）アクリレートを重合成分とする重合体であることが好ましく、特にはメチルメタクリレートを重合成分とする重合体であることが好ましく、更にはポリメチルメタクリレートであることが好ましい。 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.
　本発明においては、上記（ｆ１－１）～（ｆ１－３）のモノマー成分を重合することによりアクリル系樹脂（ｆ１）を製造するのであるが、かかる重合に当たっては、溶液ラジカル重合、懸濁重合、塊状重合、乳化重合などの従来公知の方法により行うことができる。例えば、有機溶媒中に、上記（メタ）アクリル酸エステル系モノマー（ｆ１－１）、官能基含有モノマー（ｆ１－２）、その他の共重合性モノマー（ｆ１－３）等の重合モノマー、重合開始剤（アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、過酸化ベンゾイル等）を混合あるいは滴下し、還流状態あるいは５０～９０℃で２～２０時間重合する。 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.
　また、ポリオキシアルキレン鎖を含有するポリマー（ｆ２）としては、ポリオキシアルキレン鎖を含有するアリルグリシジルエーテル共重合体も好ましく、さらに好適には、エチレンオキサイド・プロピレンオキサイド・アルルグリシジルエーテル共重合体であり、ランダム共重合体やブロック共重合体であることが特に好ましい。 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.
　ポリマー（Ｆ）を用いる場合、［Ｉ’’］キレート形成可能な金属または半金属化合物（Ａ）と、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）と、ポリマー（Ｆ）と、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物、また、［ＩＩ’’］キレート形成可能な金属または半金属化合物（Ａ）及び該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、ポリマー（Ｆ）と、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物とする。 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)).
　（Ａ）と（Ｆ）の配合割合については、（Ａ）／（Ｆ）が重量比で５０／５０～９５／５であることが好ましく、特には５５／４５～９０／１０、更には６０／４０～８０／２０であることが好ましい。かかる（Ａ）／（Ｆ）の値は小さすぎると接着力が低下する傾向があり、大きすぎても接着力が低下する傾向がある。 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.
　上記の［Ｉ’’］の場合には、（Ａ）～（Ｃ）及び（Ｆ）を適宜配合して接着剤組成物とすることができる。（Ａ）～（Ｃ）及び（Ｆ）の各含有割合については、（Ａ）～（Ｃ）及び（Ｆ）の合計に対して、（Ａ）が０．１～３０重量％、（Ｂ）が０．５～４０重量％、（Ｃ）が３０～９９重量％、（Ｆ）が０．０１～２０重量％であることが好ましく、特には（Ａ）が０．５～２０重量％、（Ｂ）が１～３０重量％、（Ｃ）が５０～９８重量％、（Ｆ）が０．０５～１０重量％、更には（Ａ）が１～１５重量％、（Ｂ）が４～２０重量％、（Ｃ）が６５～９４重量％、（Ｆ）が０．１～８重量％であることが好ましい。かかる（Ａ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｂ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下となる傾向がある。かかる（Ｃ）の含有量が少なすぎると耐温水試験時の耐久性の低下となる傾向があり、多すぎると偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｆ）の含有量が少なすぎると接着力が低下する傾向があり、多すぎても相溶性が低下し接着力が低下する傾向がある。 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.
　上記においては、（Ａ）及び（Ｂ）、好ましくは更に（Ｃ）、（Ｆ）を含有する接着剤組成物として、偏光子に塗布し、通常５０～２００℃、特に好ましくは６０～１５０℃で乾燥を行うことにより、キレート化合物（Ａ－Ｂ）を形成することができる。また、（Ａ）及び（Ｂ）、好ましくは更に（Ｃ）、（Ｆ）を含有する接着剤組成物とした後、通常５０～１２０℃、特に好ましくは６０～９０℃で（Ａ）と（Ｂ）を反応させてキレート化合物（Ａ－Ｂ）を形成することができる。 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).
　また、［ＩＩ’’］の場合には、（Ａ）及び（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、ポリマー（Ｆ）と、好ましくは（Ｃ）とが含有されることになるが、更には、（Ａ）と、（Ｂ）と、（Ｆ）と、（Ａ）と（Ｂ）から形成されてなるキレート化合物（Ａ－Ｂ）と、好ましくは（Ｃ）が含有されることにもなる。 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.
　かかるキレート化合物（Ａ－Ｂ）の含有量は、０．１～４０重量％であることが好ましく、特には、０．５～３０重量％、更には、１～２０重量％であることが好ましい。
　かかる含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。 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.
　上記のように、ポリマー（Ｆ）を有することにより、高分子鎖が紫外線硬化時に高分子網目構造内に入り込むことで、硬化収縮を緩和させることができることから、さらに接着強度を高め、耐水性の向上を図るものと推察される。 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.
〈酸基含有モノマー（Ｇ）〉
　つぎに前記配合剤である酸基含有モノマー（Ｇ）について説明する。
　本発明における酸基含有モノマー（Ｇ）としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、アクリルアミドＮ－グリコール酸、ケイ皮酸、（メタ）アクリル酸のミカエル付加物（例えば、アクリル酸ダイマー、メタクリル酸ダイマー、アクリル酸トリマー、メタクリル酸トリマー、アクリル酸テトラマー、メタクリル酸テトラマー等）、２－（メタ）アクリロイルオキシエチルジカルボン酸モノエステル（例えば、２－アクリロイルオキシエチルコハク酸モノエステル、２－メタクリロイルオキシエチルコハク酸モノエステル、２－アクリロイルオキシエチルフタル酸モノエステル、２－メタクリロイルオキシエチルフタル酸モノエステル、２－アクリロイルオキシエチルヘキサヒドロフタル酸モノエステル、２－メタクリロイルオキシエチルヘキサヒドロフタル酸モノエステル等）、カルボキシエチルアクリレート等が挙げられ、中でも、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸等のカルボキシル基含有エチレン性不飽和化合物が好ましく、特に、（メタ）アクリル酸、カルボキシエチルアクリレート等が好ましく用いられる。これらは単独でもしくは２種以上併せて用いられる。 <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.
　酸基含有モノマー（Ｇ）を用いる場合、［Ｉ’’’］キレート形成可能な金属または半金属化合物（Ａ）と、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）と、酸基含有モノマー（Ｇ）と、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物、また、［ＩＩ’’’］キレート形成可能な金属または半金属化合物（Ａ）及び該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、酸基含有モノマー（Ｇ）と、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物とする。 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.
　（Ａ）と（Ｇ）の配合割合については、（Ａ）／（Ｇ）が重量比で５０／５０～９５／５であることが好ましく、特には５５／４５～９０／１０、更には６０／４０～８０／２０であることが好ましい。かかる（Ａ）／（Ｇ）の値は小さすぎると耐水性が低下する傾向があり、大きすぎると接着力が低下する傾向がある。 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.
　上記の［Ｉ’’’］の場合には、（Ａ）～（Ｃ）と（Ｇ）を適宜配合して接着剤組成物とすることができる。（Ａ）～（Ｃ）と（Ｇ）の各含有割合については、（Ａ）～（Ｃ）と（Ｇ）の合計に対して、（Ａ）が０．１～３０重量％、（Ｂ）が０．５～４０重量％、（Ｃ）が３０～９９重量％、（Ｇ）が０．０１～２０重量％であることが好ましく、特には（Ａ）が０．５～２０重量％、（Ｂ）が１～３０重量％、（Ｃ）が５０～９８重量％、（Ｇ）が０．０５～１０重量％、更には（Ａ）が１～１５重量％、（Ｂ）が４～２０重量％、（Ｃ）が６５～９４重量％、（Ｇ）が０．１～８重量％であることが好ましい。かかる（Ａ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｂ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下となる傾向がある。かかる（Ｃ）の含有量が少なすぎると耐温水試験時の耐久性の低下となる傾向があり、多すぎると偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｇ）の含有量が少なすぎると接着力が低下する傾向があり、多すぎると耐水性が低下する傾向がある。 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.
　上記においては、（Ａ）、（Ｂ）及び（Ｇ）、好ましくは更に（Ｃ）を含有する接着剤組成物として、偏光子に塗布し、通常５０～２００℃、特に好ましくは６０～１５０℃で乾燥を行うことにより、キレート化合物（Ａ－Ｂ）を形成することができる。また、（Ａ）、（Ｂ）及び（Ｇ）、好ましくは更に（Ｃ）を含有する接着剤組成物とした後、通常５０～１２０℃、特に好ましくは６０～９０℃で（Ａ）と（Ｂ）を反応させてキレート化合物（Ａ－Ｂ）を形成することができる。 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).
　また、［ＩＩ’’’］の場合には、（Ａ）及び（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、酸基含有モノマー（Ｇ）と、好ましくは（Ｃ）とが含有されることになるが、更には、（Ａ）と、（Ｂ）と、（Ｇ）と、（Ａ）と（Ｂ）から形成されてなるキレート化合物（Ａ－Ｂ）と、好ましくは（Ｃ）が含有されることにもなる。 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.
　かかるキレート化合物（Ａ－Ｂ）の含有量は、０．１～４０重量％であることが好ましく、特には、０．５～３０重量％、更には、１～２０重量％であることが好ましい。
　かかる含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。 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.
　上記のように、酸基含有モノマー（Ｇ）を有することにより、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）の互変異性（ケト⇔エノール）のエノール化が促進され、接着力が向上するものと推測される。特に、上記（Ｂ）成分がアセトアセチル基含有エチレン性不飽和化合物（ｂ１）である場合、酸基含有モノマーを配合することで、接着力に有効な水酸基を多く出現させることができるものと考えられる。 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.
〈光塩基発生剤（Ｈ）〉
　つぎに前記配合剤である光塩基発生剤（Ｈ）について説明する。
　本発明における光塩基発生剤（Ｈ）は、紫外線や可視光等の光照射により、分子構造が変化する、または、分子が開裂することにより、硬化触媒として機能しうる１種以上の塩基性物質を生成する化合物である。塩基性物質として、例えば、２級アミン、３級アミンが挙げられる。 <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.
　光塩基発生剤として、従来から知られている光塩基発生剤を用いることができるが、好ましい光塩基発生剤としては、下記一式（２）～（７）で表すことができる化合物を挙げることができる。これらは単独でもしくは２種以上併せて用いられる。 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.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　上記の中でも、特に上記式（２）および（３）に示される化合物が好ましく用いられる。 Of these, the compounds represented by the above formulas (2) and (3) are particularly preferably used.
　上記の光塩基発生剤（Ｈ）は、通常４０５ｎｍ以下に最大モル吸光係数を有するものであることが好ましい。 The above photobase generator (H) preferably has a maximum molar extinction coefficient of usually 405 nm or less.
　光塩基発生剤（Ｈ）を用いる場合、［Ｉ’’’’］キレート形成可能な金属または半金属化合物（Ａ）と、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）と、光塩基発生剤（Ｈ）と、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物、また、［ＩＩ’’’’］キレート形成可能な金属または半金属化合物（Ａ）及び該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、光塩基発生剤（Ｈ）と、好ましくは更に、その他の光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなる接着剤組成物とする。 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.
　（Ａ）と（Ｈ）の配合割合については、（Ａ）／（Ｈ）が重量比で９９．１／０．１～７０／３０であることが好ましく、特には９９／１～８０／２０、更には９５／５～８５／１５であることが好ましい。かかる（Ａ）／（Ｈ）の値は小さすぎると耐水性が低下する傾向があり、大きすぎても耐水性が低下する傾向がある。 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.
　上記の［Ｉ’’’’］の場合には、（Ａ）～（Ｃ）及び（Ｈ）を適宜配合して接着剤組成物とすることができる。（Ａ）～（Ｃ）及び（Ｈ）の各含有割合については、（Ａ）～（Ｃ）及び（Ｈ）の合計に対して、（Ａ）が０．１～３０重量％、（Ｂ）が０．５～４０重量％、（Ｃ）が３０～９９重量％、（Ｈ）が０．１～２０重量％であることが好ましく、特には（Ａ）が０．５～２０重量％、（Ｂ）が１～３０重量％（Ｃ）が５０～９８重量％、（Ｈ）が０．５～１５重量％、更には（Ａ）が１～１５重量％、（Ｂ）が４～２０重量％、（Ｃ）が６５～９４重量％、（Ｈ）が１～１０重量％であることが好ましい。かかる（Ａ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｂ）の含有量が少なすぎると偏光子と保護フィルムの接着力の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下となる傾向がある。かかる（Ｃ）の含有量が少なすぎると耐温水試験時の耐久性の低下となる傾向があり、多すぎると偏光子と保護フィルムの接着力の低下となる傾向がある。かかる（Ｈ）の含有量が少なすぎると耐水性が低下する傾向があり、多すぎても耐水性が低下する傾向がある。 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.
　上記においては、（Ａ）、（Ｂ）及び（Ｈ）、好ましくは更に（Ｃ）を含有する接着剤組成物として、偏光子に塗布し、通常５０～２００℃、特に好ましくは６０～１５０℃で乾燥を行うことにより、キレート化合物（Ａ－Ｂ）を形成することができる。また、（Ａ）、（Ｂ）及び（Ｈ）、好ましくは更に（Ｃ）を含有する接着剤組成物とした後、通常５０～１２０℃、特に好ましくは６０～９０℃で（Ａ）と（Ｂ）を反応させてキレート化合物（Ａ－Ｂ）を形成することができる。 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).
　また、［ＩＩ’’’’］の場合には、（Ａ）及び（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）と、光塩基発生剤（Ｈ）と、好ましくは（Ｃ）とが含有されることになるが、更には、（Ａ）と、（Ｂ）と、（Ｈ）と、（Ａ）と（Ｂ）から形成されてなるキレート化合物（Ａ－Ｂ）と、好ましくは（Ｃ）が含有されることにもなる。 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.
　かかるキレート化合物（Ａ－Ｂ）の含有量は、０．５～５０重量％であることが好ましく、特には、１～４０重量％、更には、５～３０重量％であることが好ましい。
　かかる含有量が少なすぎると偏光子と保護フィルムの接着力の低下や、耐色抜け性の低下となる傾向があり、多すぎると耐温水試験時の耐久性の低下や、偏光子と保護フィルムの接着力の低下となる傾向がある。　 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.
　上記のように、光塩基発生剤（Ｈ）を有することにより、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）の、特にアセトアセチル基含有エチレン性不飽和化合物（ｂ１）の酸性度の中和が行われ、上記（Ｂ）成分の反応性が向上し、耐水性も向上するものと推測される。特に、光塩基発生剤は、紫外線等の照射により塩基成分が発生し、二重結合のアニオン硬化を行うものであり、上記（Ｂ）成分の弱酸性は耐水性に悪影響を及ぼすことから、光塩基発生剤を配合することで、中和の意味合いも有することができるものと考えられる。 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.
　かくして本発明の接着剤組成物が得られる。本発明の接着剤組成物は、好ましくは活性エネルギー線照射により硬化することにより、接着剤として機能するものであり、偏光子と保護フィルムを接着するための偏光板用接着剤として好適に用いることができるものである。 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.
　また、本発明の接着剤組成物は溶剤を含んでいてもよいし、無溶剤型の組成物として用いてもよいが、接着性能に優れる点で、無溶剤型の組成物として用いた方が好ましい。 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.
（偏光子）
　上記偏光子としては、特に制限はなく、公知のものを使用することができる。
　例えば、（ｉ）ＰＶＡ系フィルム、部分ホルマール化ＰＶＡ系フィルム、エチレン－ビニルアルコール系樹脂フィルム、等のビニルアルコール系樹脂フィルムに、ヨウ素や二色性色素などの二色性材料を吸着させて一軸延伸したもの（例えば、特開２００１－２９６４２７号公報、特開平７－３３３４２６号公報参照。）、（ｉｉ）上記（ｉ）において二色性材料とともに液晶性を有する複屈折材料をビニルアルコール系樹脂フィルム中に有するもの（例えば、特開２００７－７２２０３号公報参照。）、（ｉｉｉ）二色性材料を含有する熱可塑性ノルボルネン系樹脂フィルムを一軸延伸したもの（例えば、特開２００１－３５６２１３号公報参照。）、（ｉｖ）ＰＶＡ系樹脂やエチレン－ビニルアルコール系樹脂を脱水あるいは脱酢酸して連続するポリエン構造を導入し、これを延伸して得られるポリエン系フィルム（例えば、特開２００７－１７８４５号公報参照。）、などを挙げることができる。
　中でも、偏光特性が優れる点から、ＰＶＡ系フィルムにヨウ素が吸着された一軸延伸フィルムが好適である。 (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.
　かかる偏光子の厚さは、通常０．１～１００μｍであり、特に０．５～８０μｍ、更に１～６０μｍのものが好適に用いられる。 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.
（保護フィルム）
　上記保護フィルムは、偏光子の少なくとも一方の面、好ましくは両面に貼り合わせることで、偏光子の問題点である高湿度下での耐久性不足を補うことができるものである。
　さらに、本発明で用いられる保護フィルムに求められる特性としては、透明性、機械強度、熱安定性、水分遮断性、光学的等方性などを挙げることができる。 (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.
　かかる保護フィルムの材料としては、光学特性や耐久性などの点から、セルロースエステル系樹脂、環状オレフィン系樹脂、（メタ）アクリル系樹脂が好適に用いられる。
　また、その他の材料として、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系樹脂、ポリスチレンやアクリロニトリル・スチレン共重合体等のポリスチレン系樹脂、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリアリレート系樹脂、ポリカーボネート系樹脂、塩化ビニル系樹脂、ナイロンや芳香族ポリアミド等のアミド系樹脂、（含フッ素）ポリイミド系樹脂、ポリエーテルエーテルケトン系樹脂、ポリフェニレンスルフィド系樹脂、塩化ビニリデン系樹脂、ポリビニルブチラールなどのポリビニルアセタール系樹脂、ポリオキシメチレン系樹脂、エポキシ樹脂などを挙げることができる。これらは単独でもしくは２種以上併せて用いられる。 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.
　上記セルロースエステル系樹脂フィルムに用いられるセルロースエステル系樹脂としては、トリアセチルセルロースやジアセチルセルロースが代表的であるが、その他にもセルロースの低級脂肪酸エステルや、セルロースアセテートプロピオネートやセルロースアセテートブチレートなどの混合脂肪酸エステルを用いることができる。 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.
　上記環状オレフィン系樹脂フィルムに用いられる環状オレフィン系樹脂としてはノルボルネン系樹脂を挙げることができる。かかるノルボルネン系樹脂には、例えば、ノルボルネン系モノマーの開環（共）重合体、ノルボルネンモノマーを付加重合させた樹脂、ノルボルネン系モノマーとエチレンやα－オレフィンなどのオレフィン系モノマーと付加共重合させた樹脂などを包含するものである。 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.
　ノルボルネン系モノマーの具体例としては、ノルボルネン、ノルボルナジエンなどの二量体；ジシクロペンタジエン、ジヒドロキシペンタジエンなどの三環体；テトラシクロペンタジエンなどの七環体；これらのメチル、エチル、プロピル、ブチルなどのアルキル、ビニルなどのアルケニル、エチリデンなどのアルキリデン、フェニル、トリル、ナフチルなどのアリールなどの置換体；さらにこれらのエステル基、エーテル基、シアノ基、ハロゲン、アルコキシカルボニル基、ピリジル基、ヒドロキシル基、カルボン酸基、アミノ基、無水酸基、シリル基、エポキシ基、アクリロイル基、メタクリロイル基などの炭素、水素以外の元素を含有する基を有する置換体などが挙げられる。 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.
　環状オレフィン系樹脂フィルムの市販品としては、ＪＳＲ社製「ＡＲＴＯＮ」、日本ゼオン社製「ＺＥＯＮＯＲ」、「ＺＥＯＮＥＸ」、日立化成社製「ＯＰＴＯＲＥＺ」、三井化学社製「ＡＰＥＬ」などを挙げることができる。 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.
　上記（メタ）アクリル系樹脂フィルムに用いられる（メタ）アクリル系樹脂としては、ポリメタクリル酸メチルなどのポリ（メタ）アクリル酸エステル、メタクリル酸メチル－（メタ）アクリル酸共重合体、メタクリル酸メチル－（メタ）アクリル酸エステル共重合体、メタクリル酸メチル－アクリル酸エステル－（メタ）アクリル酸共重合体、（メタ）アクリル酸メチル－スチレン共重合体、脂環族炭化水素基を有する重合体〔例えば、メタクリル酸メチル－メタクリル酸シクロヘキシル共重合体、メタクリル酸メチル－（メタ）アクリル酸ノルボルニル共重合体など〕、分子内架橋や分子内環化反応により得られる高ガラス転移温度の（メタ）アクリル系樹脂、ゴム－アクリル系グラフト型コアシェルポリマーなどが挙げられる。 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.
　かかる（メタ）アクリル系樹脂フィルムの市販品としては、三菱レイヨン社製「アクリペットＶＲＬ２０Ａ」、「アクリペットＩＲＤ－７０」、ＵＭＧＡＢＳ社製「ＭＵＸ－６０」などが挙げられる。 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.
　なお、上記保護フィルムは、必要に応じて、セルロースエステル系樹脂からなるフィルムに対するアルカリ液によるケン化処理や、環状オレフィン系樹脂からなるフィルムに対するコロナ放電処理やプラズマ処理などの表面親水化処理を施したものであってもよい。 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.
　また、保護フィルム表面の接着剤との親和性を高めるために、親水化以外の各種表面処理を行うことも可能であり、保護フィルムの表面に（メタ）アクリル酸エステル系ラテックスやスチレン系ラテックス、ポリエチレンイミン、ポリウレタン／ポリエステル共重合体などを含有する易接着層やアンカーコート層を設けたり、シランカップリング剤やチタンカップリング剤などのカップリング剤による表面処理方法などを挙げることができる。なお、上述の各種表面処理法を併用することも可能である。
　また、帯電防止剤を保護フィルム表面に塗布あるいはフィルム中に含有させたものも好ましく用いられる。 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.
　かかる保護フィルムの厚みは特に限定されないが、通常は偏光子よりも厚いものが用いられ、偏光子の基材として強度付与の機能をもつものであり、通常１０～１００μｍ、好ましくは２０～８０μｍである。 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.
　また、かかる保護フィルムは、偏光子の積層されない面にハードコート層を設けたり、スティッキング防止、反射防止、アンチグレアなどの各種処理を施すことも可能である。さらに、位相差板や視野角拡大フィルムなどの、各種光学機能フィルムを、積層することも可能である。 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.
（偏光板）
　本発明の偏光板は、偏光板用接着剤を介して上記の偏光子と保護フィルムが貼り合わされてなるものである。詳しくは、偏光子の少なくとも一方の面、好ましくは両面に、本発明の偏光板用接着剤を用いて保護フィルムを貼り合わせてなるものであり、通常は、液状とした接着剤組成物を偏光子あるいは保護フィルム、あるいはその両方に均一に塗布した後、両者を貼り合わせ、圧着し、活性エネルギー線照射を行なうことで偏光板が形成される。 (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.
　かかる接着剤組成物を偏光子あるいは保護フィルム上に塗工するにあたっては、例えば、リバースコーター、グラビアコーター（ダイレクト，リバースやオフセット）、バーリバースコーター、ロールコーター、ダイコーター、バーコーター、ロッドコーター等を用いたり、ディッピング方式による塗工を行なうことができる。 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.
　かかる貼り合わせ、および圧着には、例えばロールラミネーターなどを用いることができ、その圧力は０．１～１０ＭＰａの範囲から選択される。 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.
　かかる活性エネルギー線照射には、遠紫外線、紫外線、近紫外線、赤外線等の光線、Ｘ線、γ線等の電磁波の他、電子線、プロトン線、中性子線等が利用できるが、硬化速度、照射装置の入手のし易さ、価格等から紫外線照射による硬化が有利である。なお、電子線照射を行なう場合は、上記光重合開始剤（ｄ１）を用いなくても硬化可能である。 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).
　かかる紫外線照射を行なう時の光源としては、高圧水銀灯、無電極ランプ、超高圧水銀灯、カーボンアーク灯、キセノン灯、メタルハライドランプ、ケミカルランプ、ブラックライト、ＬＥＤ等が用いられる。
　かかる紫外線照射は、２～３０００ｍＪ／ｃｍ２、好ましくは１０～２０００ｍＪ／ｃｍ２の条件で行われる。 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.
　特に上記高圧水銀灯の場合は、例えば、５～３０００ｍＪ／ｃｍ２、好ましくは５０～２０００ｍＪ／ｃｍ２の条件で行われる。
　また、上記無電極ランプの場合は、例えば、２～２０００ｍＪ／ｃｍ２、好ましくは１０～１０００ｍＪ／ｃｍ２の条件で行われる。 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 .
　そして、照射時間は、光源の種類、光源と塗布面との距離、塗工厚、その他の条件によっても異なるが、通常は、数秒～数十秒、場合によっては数分の１秒でもよい。一方、上記電子線照射の場合には、例えば、５０～１０００ｋｅＶの範囲のエネルギーを持つ電子線を用い、２～５０Ｍｒａｄの照射量とするのがよい。 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.
　かかる活性エネルギー線（電子線、紫外線等）の照射方向は、任意の適切な方向から照射することができるが、偏光子の劣化を防げる点で、透明保護フィルム側から照射することが好ましい。 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.
　上記により得られる本発明の偏光板における接着剤層の厚さは、通常０．０１～１０μｍ、好ましくは０．０１～５μｍ、特に好ましくは０．０１～２μｍ、更に好ましくは０．０１～１μｍである。かかる厚さが薄すぎると接着力自体の凝集力が得られず、接着強度が得られない傾向があり、厚すぎると打ち抜き加工時の割れ等により偏光板の加工性が低下する傾向がある。 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.
　本発明の接着剤組成物は、初期および経時での接着力に優れる接着剤となり、種々の用途に利用可能であるが、中でも特に、種々の偏光板用保護フィルムと偏光子、特にはＴＡＣ以外の保護フィルムと偏光子の貼り合せに好適に用いることができ、更に乾燥工程が必要なく偏光板の生産効率にも優れ、また、偏光板の耐色抜け性にも優れたものである。 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.
　以下、実施例をあげて本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、例中、「部」、「％」とあるのは、重量基準を意味する。 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.
　以下の各成分を用意した。
〔キレート形成可能な金属または半金属化合物（Ａ）〕
・（Ａ－１）トリブチルボレート（関東化学社製「ほう酸トリ－ｎ－ブチル」）
・（Ａ－２）チタンテトライソプロピレート（マツモトファインケミカル社製「オルガチックスＴＡ－１０」）
・（Ａ－３）チタンテトラ－ｎ－ブチレート（マツモトファインケミカル社製「オルガチックスＴＡ－２５」）
・（Ａ－４）アルミニウムトリアセチルアセトネート（日本化学産業社製「ナーセムアルニウム」）
・（Ａ－５）ホウ酸（和光純薬工業社製） 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.)
〔金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）〕
・（Ｂ－１）２－アセトアセトキシエチルメタクリレート（日本合成化学工業社製「ＡＡＥＭ」） [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.)
〔光重合性化合物（Ｃ）〕
・（Ｃ－１）アクリロイルモルホリン（興人社製「ＡＣＭＯ」）
・（Ｃ－２）ジメチルアクリルアミド（興人社製「ＤＭＡＡ」）
・（Ｃ－３）エチレングリコールジアクリレート（日立化成社製「ＦＡ－２２２Ａ」） [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.)
〔重合開始剤（Ｄ）〕
・（Ｄ－１）１－ヒドロキシシクロヘキシルフェニルケトン（ＢＡＳＦ社製「イルガキュア１８４」）
・（Ｄ－２）２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド（ＢＡＳＦ社製「ルシリンＴＰＯ」） [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)
〔ウレタン（メタ）アクリレート系化合物（Ｅ）〕
　下記合成例１に従って、２官能ポリエーテル系ウレタンアクリレート（Ｅ－１）を合成した。
・（Ｅ－１）２官能ポリエーテル系ウレタンアクリレート
〔合成例１〕
　撹拌機を備えた５００ｍｌ反応容器に、ジブチル錫ジラウレートを０．３ｇ、重合禁止剤として４－メトキシフェノールを０．２ｇ、ポリテトラメチレングリコール（分子量６５０）２３０ｇを仕込み、これらを撹拌しながら液温が４０℃になるまで加温した。
　反応溶液に水添ジフェニルメタンジイソシアネート１８５ｇを徐々に添加し、１時間かけて６０℃まで昇温した。６０℃で反応を続けながら遊離ＮＣＯ％が７．０％になるまで反応を継続した後に、２－ヒドロキシエチルアクリレート８５ｇを添加し、遊離ＮＣＯ％が０．５％以下になるまで反応を継続し、２官能ポリエーテル系ウレタンアクリレート（Ｅ－１）を得た。
　なお、得られた２官能ポリエーテル系ウレタンアクリレート（Ｅ－１）の重量平均分子量は、３２００であり、６０℃における粘度は１４０００ｍＰａ・ｓであった。 [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.
〔ポリマー（Ｆ）〕
・（Ｆ－１）ポリメタクリル酸メチル（アルドリッチ社製、ＳＰ値９．１～９．５、重量平均分子量約１００万、ガラス転移温度１００℃）
・（Ｆ－２）エチレンオキサイド・プロピレンオキサイド・アリルグリシジルエーテルランダム共重合体（明成化学工業社製「アルコックスＣＰ－Ａ２Ｈ」、ＳＰ値１９．１、重量平均分子量約６万、ガラス転移温度－６℃） [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 ℃)
〔酸基含有モノマー（Ｇ）〕
・（Ｇ－１）アクリル酸（アルドリッチ社製）
・（Ｇ－２）β－カルボキシエチルアクリレート（ダイセル・オルネクス社製「βＣＥＡ」） [Acid group-containing monomer (G)]
・ (G-1) Acrylic acid (Aldrich)
(G-2) β-carboxyethyl acrylate (“βCEA” manufactured by Daicel-Ornex)
〔光塩基発生剤（Ｈ）〕
・（Ｈ－１）（Ｅ）－１－［３－（２－ヒドロキシフェニル）－２－プロペノイル］ピペリジン（和光純薬工業社製「ＷＰＢＧ－０２７」）
・（Ｈ－２）９－アントリルメチル－Ｎ，Ｎ－ジエチルカルバメート（和光純薬工業社製「ＷＰＢＧ－０１８」）　
〔実施例１〕
＜接着剤組成物の作製＞
　調製用フラスコにトリブチルボレート（Ａ－１）を５部（固形分）、２－アセトアセトキシエチルメタクリレート（Ｂ－１）１５部、ジメチルアクリルアミド（Ｃ－２）５０部、エチレングリコールジアクリレート（Ｃ－３）３０部、イルガキュア１８４（Ｄ－１）１．５部、ルシリンＴＰＯ（Ｄ－２）１．５部を同時に仕込み、混合することで接着剤組成物を得た。 [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.
〔実施例２～８、比較例１～２〕
　上記で用意した各配合成分を、後記の表１に示す割合で配合すること以外は実施例１と同様にして接着剤組成物を調製した。 [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.
＜偏光板試験片の作製＞
　まず、６０μｍのＰＶＡフィルムを、水温３０℃の水槽に浸漬しつつ、１．５倍に延伸した。次に、ヨウ素０．２ｇ／Ｌ、ヨウ化カリウム１５ｇ／Ｌよりなる染色槽（３０℃）にて２４０秒浸漬しつつ１．３倍に延伸し、さらにホウ酸５０ｇ／Ｌ、ヨウ化カリウム３０ｇ／Ｌの組成のホウ酸処理槽（５０℃）に浸漬するとともに、同時に３．０８倍に一軸延伸しつつ５分間にわたってホウ酸処理を行った。その後、乾燥して総延伸倍率６倍の偏光子を製造した。
　次いで、大きさ２００ｍｍ×５０ｍｍ、厚み７５μｍアクリルフィルム（三菱レイヨン社製、商品名「アクリプレン」）に上記で得られた接着剤組成物をバーコーター（Ｎｏ．１０）で膜厚５μｍとなるように塗工した接着剤組成物層付きアクリルフィルムを２枚作製した後、大きさ１５０ｍｍ×３０ｍｍの上記偏光子の両面に重ね合わせ、ロール機を用いてニップ圧２ＭＰａで貼り合わせ、積層フィルムを得た。
　次いで、積層フィルムのアクリルフィルム側の両側から、高圧水銀灯の取り付けられた紫外線照射装置にてピーク照度：１３０ｍＷ／ｃｍ２、積算露光量：９００ｍＪ／ｃｍ２（３６５ｎｍ）で紫外線照射を行ない、接着剤組成物を硬化させ、実施例１～７は８０℃で３分乾燥させ、実施例８，比較例１，２は乾燥せずに、得られた積層フィルムを偏光板試験片とした。 <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.
　上記で得られた偏光板試験片を用いて、下記の通り性能評価を行った。 Using the polarizing plate test piece obtained above, performance evaluation was performed as follows.
［接着性］
　偏光板試験片を１２０ｍｍ×２５ｍｍにカットし、２枚のアクリルフィルムに９０°方向の応力をかけた際のアクリルフィルムと偏光子の接着具合を下記基準で評価した。
（評価基準）
◎…強固に接着している
○…接着している
×…接着していない [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
［耐色抜け性］
　偏光板試験片を５ｃｍ×５ｃｍにカットし、６０℃の温水に浸漬させ、４８時間後の偏光板試験片の色調を観察し、下記基準で評価した。
○…試験前の状況と色調変化なし
△…僅かに色抜け（退色）した
×…完全に色抜け（退色）した [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)
［耐水性］
　偏光板試験片を５ｃｍ×５ｃｍにカットし、６０℃の温水に浸漬させ、４８時間後の偏光板試験片の密着性を観察し、下記基準で評価した。
○…試験片端部からの剥がれなし
△…試験片端部から５ｍｍ未満の範囲において剥がれあり
×…試験片端部から５ｍｍ以上の範囲に剥がれあり [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
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　キレート形成可能な金属または半金属化合物（Ａ）、及び、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有してなる実施例１～８の接着剤組成物は、偏光子と保護フィルムを充分に貼り合せることができるうえに、耐色抜け性にも耐水性にも優れた効果を有するものであった。これに対して、キレート形成可能な金属または半金属化合物（Ａ）を含有しない比較例１や、金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有しない比較例２の接着剤組成物では、接着性はおろか、耐色抜け性や耐水性の点においても劣るものであり、接着剤組成物として実用に供することなどできないものであった。このことから、本発明の接着剤組成物が非常に優れていることがわかる。 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.
〔実施例９〕
＜接着剤組成物の作製：（Ｅ）成分追加系＞
　調製用フラスコに、ホウ酸（Ａ－５）５部、２－アセトアセトキシエチルメタクリレート（Ｂ－１）５部、ジメチルアクリルアミド（Ｃ－２）６５部を仕込み、６０℃に加温してホウ酸を溶解する。次に、エチレングリコールジアクリレート（Ｃ－３）５部、２官能ポリエーテル系ウレタンアクリレート（Ｅ－１）２０部を加え充分に混合する。室温まで冷却後、イルガキュア１８４（Ｄ－１）１．５部、ルシリンＴＰＯ（Ｄ－２）１．５部を仕込み、混合、溶解することで接着剤組成物を得た。 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.
〔実施例１０、比較例３及び４〕
　上記で用意した各配合成分を、後記の表２示す割合で配合すること以外は実施例９と同様にして接着剤組成物を調製した。 [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.
　つぎに、上記実施例１と同様に、偏光板試験片を作製し、その偏光板試験片を用いて実施例１と同様、接着性、耐色色抜け性、及び耐水性の性能評価を行った。その評価結果を下記表２に示す。 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.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　キレート形成可能な金属または半金属化合物（Ａ）、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）、及び、ウレタン（メタ）アクリレート系化合物（Ｅ）、を含有してなる実施例９及び１０の接着剤組成物は、偏光子と保護フィルムを充分に貼り合せることができるうえに、耐色抜け性にも耐水性にも優れた効果を有するものであった。これに対して、キレート形成可能な金属または半金属化合物（Ａ）を含有しない比較例３や、金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有しない比較例４の接着剤組成物では、接着性はおろか、耐色抜け性や耐水性の点においても劣るものであり、接着剤組成物として実用に供することなどできないものであった。このことから、本発明の接着剤組成物が非常に優れていることがわかる。 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.
〔実施例１１〕
＜接着剤組成物の作製：（Ｆ）成分追加系＞
　調製用フラスコにホウ酸（Ａ－５）５部、２－アセトアセトキシエチルメタクリレート（Ｂ－１）５部、ポリメタクリル酸メチル（Ｆ－１）２部、ジメチルアクリルアミド（Ｃ－２）８３部を仕込み、６０℃に加温して固形成分を溶解する。次に、エチレングリコールジアクリレート（Ｃ－３）５部を加え充分に混合する。室温まで冷却後、イルガキュア１８４（Ｄ－１）１．５部、ルシリンＴＰＯ（Ｄ－２）１．５部を仕込み、混合、溶解することで接着剤組成物を得た。 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.
〔実施例１２及び１３、比較例５及び６〕
　上記で用意した各配合成分を、下記の表３示す割合で配合すること以外は実施例１１と同様にして接着剤組成物を調製した。 [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.
　つぎに、上記実施例１と同様に、偏光板試験片を作製し、その偏光板試験片を用いて実施例１と同様、接着性、耐色色抜け性、及び耐水性の性能評価を行った。その評価結果を下記表３に示す。 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.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　キレート形成可能な金属または半金属化合物（Ａ）、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）、及び、ポリマー（Ｆ）を含有してなる実施例１１～１３の接着剤組成物は、偏光子と保護フィルムを充分に貼り合せることができるうえに、耐色抜け性にも耐水性にも優れた効果を有するものであった。これに対して、キレート形成可能な金属または半金属化合物（Ａ）を含有しない比較例５や、金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有しない比較例６の接着剤組成物では、接着性はおろか、耐色抜け性や耐水性の点においても劣るものであり、接着剤組成物として実用に供することなどできないものであった。このことから、本発明の接着剤組成物が非常に優れていることがわかる。
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.
〔実施例１４〕
＜接着剤組成物の作製：（Ｇ）成分追加系＞
　調整用フラスコにホウ酸（Ａ－５）５部、２－アセトアセトキシエチルメタクリレート（Ｂ－１）５部、ジメチルアクリルアミド（Ｃ－２）８４部を仕込み、６０℃に加温してホウ酸を溶解する。次に、エチレングリコールジアクリレート（Ｃ－３）５部、アクリル酸（Ｇ－１）１部を加え充分に混合する。室温まで冷却後、イルガキュア１８４（Ｄ－１）１．５部、ルシリンＴＰＯ（Ｄ－２）１．５部を仕込み、混合、溶解することで接着剤組成物を得た。 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.
〔実施例１５及び１６、比較例７及び８〕
　上記で用意した各配合成分を、後記の表４示す割合で配合すること以外は実施例１４と同様にして接着剤組成物を調製した。 [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.
　つぎに、上記実施例１と同様に、偏光板試験片を作製し、その偏光板試験片を用いて実施例１と同様、接着性、耐色色抜け性、及び耐水性の性能評価を行った。その評価結果を下記表４に示す。 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.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　キレート形成可能な金属または半金属化合物（Ａ）、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）、及び、酸基含有モノマー（Ｇ）を含有してなる実施例１４～１６の接着剤組成物は、偏光子と保護フィルムを充分に貼り合せることができるうえに、耐色抜け性にも耐水性にも優れた効果を有するものであった。これに対して、キレート形成可能な金属または半金属化合物（Ａ）を含有しない比較例７や、金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有しない比較例８の接着剤組成物では、接着性はおろか、耐色抜け性や耐水性の点においても劣るものであり、偏光板用接着剤組成物として実用に供することなどできないものであった。このことから、本発明の接着剤組成物が非常に優れていることがわかる。 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.
〔実施例１７〕
＜接着剤組成物の作製：（Ｈ）成分追加系＞
　調製用フラスコにホウ酸（Ａ－５）５部、２－アセトアセトキシエチルメタクリレート（Ｂ－１）５部、ジメチルアクリルアミド（Ｃ－２）８５部を仕込み、６０℃に加温してホウ酸を溶解する。次に、エチレングリコールジアクリレート（Ｃ－３）５部を加え充分に混合する。室温まで冷却後、イルガキュア１８４（Ｄ－１）１．５部、ルシリンＴＰＯ（Ｄ－２）１．５部、及び（Ｅ）－１－［３－（２－ヒドロキシフェニル）－２－プロペノイル］ピペリジン（Ｈ－１）０．５部を仕込み、混合、溶解することで接着剤組成物を得た。 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.
〔実施例１８及び１９、比較例９及び１０〕
　上記で用意した各配合成分を、後記の表５示す割合で配合すること以外は実施例１７と同様にして接着剤組成物を調製した。 [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.
　つぎに、上記実施例１と同様に、偏光板試験片を作製し、その偏光板試験片を用いて実施例１と同様、接着性、耐色色抜け性、及び耐水性の性能評価を行った。その評価結果を下記表５に示す。 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.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　キレート形成可能な金属または半金属化合物（Ａ）、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）、及び、光塩基発生剤（Ｈ）を含有してなる実施例１７～１９の接着剤組成物は、偏光子と保護フィルムを充分に貼り合せることができるうえに、耐色抜け性にも耐水性にも優れた効果を有するものであった。これに対して、キレート形成可能な金属または半金属化合物（Ａ）を含有しない比較例９や、金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有しない比較例１０の接着剤組成物では、接着性はおろか、耐色抜け性や耐水性の点においても劣るものであり、接着剤組成物として実用に供することなどできないものであった。このことから、本発明の接着剤組成物が非常に優れていることがわかる。　
　上記実施例においては、本発明における具体的な形態について示したが、上記実施例は単なる例示にすぎず、限定的に解釈されるものではない。当業者に明らかな様々な変形は、本発明の範囲内であることが企図されている。 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.
　本発明の接着剤組成物、更にかかる接着剤組成物からなる偏光板用接着剤組成物は、偏光子と保護フィルムとの接着性に優れるうえ、乾燥工程が必要なく生産効率にも優れたものであり、更に、偏光板の耐色抜け性にも優れたものであり、とりわけ、ＴＡＣフィルムに限らず、アクリル系フィルムや環状ポリオレフィン系樹脂フィルム等の保護フィルムと偏光子の貼り合せにも有用なものである。また、本発明の粘着剤組成物は、上記偏光板用接着剤用途の他にも、例えば、各種光学フィルム又はシートの貼り合わせや、電子部品、精密機器、包装材料、表示材料などの貼り合わせに用いることもできる。 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 (16)

  1. 　キレート形成可能な金属または半金属化合物（Ａ）及び該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）を含有してなることを特徴とする接着剤組成物。 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.
  2. 　キレート形成可能な金属または半金属化合物（Ａ）と、該金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）より形成されてなるキレート化合物（Ａ－Ｂ）を含有してなることを特徴とする接着剤組成物。 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:
  3. 　キレート形成可能な金属または半金属化合物（Ａ）が、ホウ素化合物、アルミニウム化合物、チタニウム化合物、ジルコニウム化合物、亜鉛化合物、及びケイ素化合物からなる群から選ばれる少なくとも１種であることを特徴とする請求項１または２記載の接着剤組成物。 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. 　金属または半金属とキレート形成可能な官能基を含有する光重合性化合物（Ｂ）が、アセトアセチル基含有エチレン性不飽和化合物（ｂ１）であることを特徴とする請求項１～３いずれか一項に記載の接着剤組成物。 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. 　アセトアセチル基含有エチレン性不飽和化合物（ｂ１）が、炭素数１～１０のアルキレン基を有する脂肪族系アセトアセチル基含有アルキル（メタ）アクリレート系化合物であることを特徴とする請求項４記載の接着剤組成物。 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.
  6. 　さらに光重合性化合物（Ｃ）（但し、光重合性化合物（Ｂ）を除く。）を含有してなることを特徴とする請求項１～５いずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 5, further comprising a photopolymerizable compound (C) (excluding the photopolymerizable compound (B)).
  7. 　光重合性化合物（Ｃ）が、エチレン性不飽和基を１つ有するエチレン性不飽和化合物（ｃ１）及びエチレン性不飽和基を２つ以上有するエチレン性不飽和化合物（ｃ２）の群から選ばれる少なくとも１種であることを特徴とする請求項６記載の接着剤組成物。 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.
  8. 　さらに重合開始剤（Ｄ）を含有してなることを特徴とする請求項１～７いずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 7, further comprising a polymerization initiator (D).
  9. 　さらにウレタン（メタ）アクリレート系化合物（Ｅ）を含有してなることを特徴とする請求項１～８いずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 8, further comprising a urethane (meth) acrylate compound (E).
  10. 　さらにポリマー（Ｆ）を含有してなることを特徴とする請求項１～９いずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 9, further comprising a polymer (F).
  11. 　さらに酸基含有モノマー（Ｇ）を含有してなることを特徴とする請求項１～１０いずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 10, further comprising an acid group-containing monomer (G).
  12. 　さらに光塩基発生剤（Ｈ）を含有してなることを特徴とする請求項１～１１いずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 11, further comprising a photobase generator (H).
  13. 　請求項１～１２いずれか一項に記載の接着剤組成物を用いてなることを特徴とする偏光板用接着剤組成物。 An adhesive composition for polarizing plates, characterized by using the adhesive composition according to any one of claims 1 to 12.
  14. 　請求項１３に記載の偏光板用接着剤組成物を硬化してなることを特徴とする偏光板用接着剤。 A polarizing plate adhesive obtained by curing the polarizing plate adhesive composition according to claim 13.
  15. 　請求項１３に記載の偏光板用接着剤組成物を活性エネルギー線照射により硬化してなることを特徴とする偏光板用接着剤。 A polarizing plate adhesive comprising the polarizing plate adhesive composition according to claim 13 cured by irradiation with active energy rays.
  16. 　請求項１４または１５記載の偏光板用接着剤を介して偏光子と保護フィルムが貼り合わされてなることを特徴とする偏光板。 A polarizing plate comprising a polarizer and a protective film bonded together through the polarizing plate adhesive according to claim 14 or 15.
PCT/JP2014/068108 2013-08-12 2014-07-08 Adhesive agent composition, adhesive agent composition for polarizing plate, adhesive agent for polarizing plate, and polarizing plate manufactured using said adhesive agent WO2015022825A1 (en)

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