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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• 2014
  • 2014-07-08 WO PCT/JP2014/068108 patent/WO2015022825A1/ja active Application Filing
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