Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

• the present invention relates to a pressure-sensitive adhesive composition for a polarizing plate, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet, and a polarizing plate with a pressure-sensitive adhesive layer.
• the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates (eg, a glass plate).
• a polarizing plate is attached to the surface of the substrate constituting the liquid crystal cell via an adhesive layer.
• a polarizing plate generally has a structure in which a polarizer protective film such as a triacetyl cellulose film is laminated on both sides of a polarizer having a polarizing function. Has been.
• Patent Document 1 is obtained by polymerizing a monomer component containing 19 to 99.5% by mass of an alkyl (meth) acrylate having a branched alkyl group having 10 to 24 carbon atoms at the terminal of the ester group (meth).
• a pressure-sensitive adhesive containing an acrylic polymer is described.
• problems such as cracks and shrinkage when the polarizer protective film is omitted and the pressure-sensitive adhesive layer is directly laminated on the polarizer.
• Patent Document 2 is an adhesive polarizing plate having a polarizing plate and an adhesive layer provided on the polarizing plate, the polarizing plate having a transparent protective film only on one side of the polarizer, The structure provided in the polarizer of the side which does not have the said transparent protective film is described for the adhesive layer.
• problems such as cracks, shrinkage and optical performance associated with the omission of the transparent protective film.
• An object of the present invention is applicable to a configuration in which at least one of the polarizer protective films usually formed on both surfaces of the polarizer is omitted, and is excellent in durability even in a high-humidity environment and suppresses the contraction of the polarizer. It is in providing the adhesive composition for polarizing plates which can form the adhesive layer excellent in this.
• the present inventors diligently studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a polarizing plate pressure-sensitive adhesive composition having the following specific configuration, and the present invention has been completed.
• the present invention includes, for example, the following [1] to [5].
• a pressure-sensitive adhesive composition for a polarizing plate which is used for forming a pressure-sensitive adhesive layer in direct contact with a polarizer.
• a pressure-sensitive adhesive layer for a polarizing plate formed from the pressure-sensitive adhesive composition according to [1].
• the present invention it is applicable to a configuration in which at least one of the polarizer protective films normally formed on both sides of the polarizer is omitted, and is excellent in durability even in a high-humidity environment and suppresses the contraction of the polarizer. It is possible to provide a pressure-sensitive adhesive composition for polarizing plates excellent in the above. Moreover, the adhesive layer for polarizing plates formed from the said composition, the adhesive sheet for polarizing plates which has the said adhesive layer, and the polarizing plate with an adhesive layer which has the said adhesive layer can be provided.
• the pressure-sensitive adhesive composition for polarizing plate, the pressure-sensitive adhesive layer for polarizing plate, the pressure-sensitive adhesive sheet for polarizing plate and the polarizing plate with the pressure-sensitive adhesive layer will be described.
• the pressure-sensitive adhesive composition for polarizing plate, the pressure-sensitive adhesive layer for polarizing plate and the pressure-sensitive adhesive sheet for polarizing plate of the present invention are also referred to as “pressure-sensitive adhesive composition”, “pressure-sensitive adhesive layer” and “pressure-sensitive adhesive sheet”, respectively.
• the pressure-sensitive adhesive composition for polarizing plates of the present invention contains a (meth) acrylic copolymer (A) and a crosslinking agent (B) described below.
• the composition may contain at least one selected from a silane coupling agent (C) and an antistatic agent (D) as necessary, and may contain an organic solvent (E).
• the (meth) acrylic copolymer (A) contains 50% by mass or more of a methacrylic acid alkyl ester (a1) having a glass transition temperature (Tg) of a homopolymer of less than ⁇ 10 ° C. and an alkyl group having 8 or more carbon atoms. 99.5% by mass or less, a copolymer of monomer components containing the crosslinkable functional group-containing monomer (a2) in an amount of 0.5% by mass or more and less than 10% by mass, that is, obtained by copolymerizing the monomer components. Copolymer.
• a1 methacrylic acid alkyl ester
• Tg glass transition temperature
• acrylic and methacryl are collectively referred to as “(meth) acryl”.
• the structural unit derived from a certain monomer A contained in the polymer is also referred to as “monomer A unit”.
• the (a1) and (a2) are also referred to as “monomer (a1)” and “monomer (a2)”, respectively.
• Tg glass transition temperature of the homopolymer of (meth) acrylic acid alkyl ester
• a value described in Polymer Handbook Fourth Edition (Wiley-Interscience 2003) is adopted.
• combined on the following conditions is measured on the following conditions, for example.
• a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube is charged with 100 parts by mass of monomer and 100 parts by mass of ethyl acetate, and heated to 80 ° C. while introducing nitrogen gas.
• the monomer (a1) is a methacrylic acid alkyl ester having a homopolymer Tg of less than ⁇ 10 ° C. and an alkyl group having 8 or more carbon atoms.
• the above-mentioned monomer in which the Tg of the homopolymer is -80 ° C. or higher and lower than ⁇ 10 ° C. and the alkyl group has 8 or more carbon atoms is preferred, the Tg is ⁇ 70 to ⁇ 30 ° C. and the alkyl group has 8 or more carbon atoms.
• the monomer having a Tg of ⁇ 70 to ⁇ 30 ° C. and an alkyl having 10 or more carbon atoms is more preferable.
• the upper limit of the carbon number of the alkyl group is 18, for example.
• Hydrophobic that can prevent the entry of moisture into the polarizer by using the copolymer (A) obtained by copolymerizing the monomer (a1), and thus the copolymer (A) having the monomer (a1) unit. And a pressure-sensitive adhesive having an appropriate water vapor permeability can be obtained.
• Examples of the monomer (a1) include octyl methacrylate ( ⁇ 20 ° C.), isooctyl methacrylate ( ⁇ 45 ° C.), isodecyl methacrylate ( ⁇ 41 ° C.), lauryl methacrylate ( ⁇ 65 ° C.), tetradecyl methacrylate ( ⁇ 72 ° C.). ) And isostearyl methacrylate (-18 ° C.). The numerical value in parenthesis shows Tg of the homopolymer of each monomer.
• a (meth) acrylic copolymer containing a structural unit derived from a methacrylic acid alkyl ester having a low homopolymer Tg When a (meth) acrylic copolymer containing a structural unit derived from a methacrylic acid alkyl ester having a low homopolymer Tg is used, appropriate stress relaxation characteristics can be imparted to the pressure-sensitive adhesive layer.
• a long chain alkyl group of methacrylic acid alkyl ester is used, hydrophobicity can be imparted in addition to stress relaxation characteristics.
• a monomer (a1) may be used individually by 1 type, and may use 2 or more types.
• the amount of the monomer (a1) used is 50% by mass or more and 99.5% by mass or less, preferably 70 to 99% by mass, more preferably 80 to 98.5% by mass.
• the usage-amount of a monomer (a1) exists in the said range, it is preferable at the point which the adhesive layer obtained can express sufficient hydrophobic function.
• the monomer component which is a raw material monomer of the copolymer (A) includes a monomer having a crosslinkable functional group capable of reacting with the crosslinker (B), that is, a crosslinkable functional group-containing monomer (a2).
• the polymer (A) has a monomer (a2) unit. Examples of the monomer (a2) include a hydroxyl group-containing monomer and a carboxyl group-containing monomer.
• hydroxyl group-containing monomer examples include a hydroxyl group-containing (meth) acrylate, and specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
• hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate.
• the number of carbon atoms of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate is usually 2 to 8, preferably 2 to 6.
• carboxyl group-containing monomer examples include ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ⁇ -carboxypolycaprolactone mono (meth) acrylate.
• Carboxyl group-containing (meth) acrylates such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid.
• the monomer (a2) preferably has a methacrylic structure in order to improve the hydrophobicity of the pressure-sensitive adhesive layer, and the monomer (a2) may be used alone or in combination of two or more. Good.
• the amount of the monomer (a2) used is 0.5% by mass or more and less than 10% by mass, preferably 1 to 8% by mass, more preferably 2 to 6% by mass.
• the amount of the monomer (a2) used is less than or less than the above upper limit, the crosslinking density formed by the copolymer (A) and the crosslinking agent (B) does not become too high, and the pressure-sensitive adhesive has excellent stress relaxation characteristics. A layer is obtained.
• the usage-amount of a monomer (a2) is more than the said lower limit, a crosslinked structure is formed effectively and the adhesive layer which has appropriate intensity
• the type and amount of the monomer (a2) are preferably set so that the acid value (mgKOH / g) of the copolymer (A) is 15 or less, more preferably 13 or less, still more preferably 12 or less. is there.
• the acid value is less than or equal to the above upper limit, the polarity of the copolymer (A) is lowered, so that the hydrophobicity is further increased and a pressure-sensitive adhesive layer having a high effect of suppressing moisture intrusion into the polarizer is obtained.
• the acid value of a copolymer (A) is computed by the following formula
• 56.1 is the molecular weight of KOH.
• ⁇ Other monomers As a monomer component which is a raw material monomer of the copolymer (A), as long as the physical properties of the copolymer (A) are not impaired, for example, (meth) acrylic acid alkyl esters other than the monomer (a1), alkoxyalkyl ( (Meth) acrylate, alkoxy polyalkylene glycol mono (meth) acrylate, alicyclic group or aromatic ring-containing (meth) acrylate, acid group-containing monomer other than carboxyl group-containing monomer, amino group-containing monomer, amide group-containing monomer, nitrogen-based Other monomers such as a heterocyclic ring-containing monomer and a cyano group-containing monomer can also be used.
• (meth) acrylic acid alkyl esters other than the monomer (a1) alkoxyalkyl ( (Meth) acrylate, alkoxy polyalkylene glycol mono (meth) acrylate, alicyclic group or aromatic ring
• the (meth) acrylic acid alkyl ester other than the monomer (a1) is represented, for example, by the formula: CH 2 ⁇ CR 1 —COOR 2 .
• R 1 is hydrogen or a methyl group
• R 2 is an alkyl group having 1 to 18 carbon atoms.
• Examples include (meth) acrylate, lauryl acrylate, stearyl (meth) acrylate, and isostearyl acrylate.
• alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
• alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
• Examples of the alicyclic group or aromatic ring-containing (meth) acrylate include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate.
• Examples of the acid group-containing monomer include maleic anhydride, itaconic anhydride, a (meth) acrylic monomer having a phosphate group in the side chain, and a (meth) acrylic monomer having a sulfate group in the side chain.
• Examples of the amino group-containing monomer include amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
• Examples of the amide group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-hexyl (meth) acrylamide.
• Examples of the nitrogen heterocycle-containing monomer include vinyl pyrrolidone, acryloyl morpholine, and vinyl caprolactam.
• Examples of the cyano group-containing monomer include cyano (meth) acrylate and (meth) acrylonitrile.
• copolymerizable monomers such as styrene monomers and vinyl acetate can be used as long as the physical properties of the copolymer (A) are not impaired.
• styrenic monomer examples include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, and other alkyl styrenes; fluorostyrene, chlorostyrene, bromostyrene, Halogenated styrene such as dibromostyrene and iodinated styrene; nitrostyrene, acetylstyrene, and methoxystyrene.
• Other monomers may be used alone or in combination of two or more.
• the total amount of the above other monomers Is preferably 0 to 45% by mass, more preferably 0 to 25% by mass.
• (meth) acrylic copolymer (A) is not specifically limited, For example, it can manufacture by a solution polymerization method. Specifically, a polymerization solvent and a monomer component are charged into a reaction vessel, a polymerization initiator is added in an inert gas atmosphere such as nitrogen gas, and the reaction start temperature is usually 40 to 100 ° C., preferably 50 to 80 ° C. The reaction system is maintained at a temperature of usually 50 to 90 ° C., preferably 70 to 90 ° C., and allowed to react for 4 to 20 hours.
• a polymerization solvent and a monomer component are charged into a reaction vessel, a polymerization initiator is added in an inert gas atmosphere such as nitrogen gas, and the reaction start temperature is usually 40 to 100 ° C., preferably 50 to 80 ° C.
• the reaction system is maintained at a temperature of usually 50 to 90 ° C., preferably 70 to 90 ° C., and allowed to react for 4 to 20 hours.
• the copolymer (A) is obtained, for example, by copolymerizing the monomer components including the monomers (a1) and (a2) described above, but may be a random copolymer or a block copolymer. Among these, a random copolymer is preferable.
• polymerization solvent used for the solution polymerization examples include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, Cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl a
• Examples of the polymerization initiator used for solution polymerization include azo initiators and peroxide initiators. Specific examples include azo compounds such as 2,2'-azobisisobutyronitrile and peroxides such as benzoyl peroxide and lauroyl peroxide. Among these, an azo compound is preferable. Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropyl).
• the polymerization initiator is usually in the range of 0.01 to 5 parts by mass, preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the monomer component that is a raw material monomer of the (meth) acrylic copolymer (A). Used in quantity. Moreover, you may add suitably a polymerization initiator, a chain transfer agent, a monomer component, and a polymerization solvent during the said polymerization reaction.
• the weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method of the (meth) acrylic copolymer (A) is usually from 400,000 to 3 million in terms of polystyrene, preferably 60 It is 10,000 to 2.5 million, more preferably 800,000 to 2,000,000, still more preferably 800,000 to 1.3 million.
• Mw weight average molecular weight measured by the gel permeation chromatography
• the molecular weight distribution (Mw / Mn) of the (meth) acrylic copolymer (A) measured by the GPC method is usually 15 or less, preferably 2 to 15, more preferably 4 to 13.
• the glass transition temperature (Tg) of the (meth) acrylic copolymer (A) can be calculated by, for example, the Fox formula from the monomer units constituting the copolymer and the content ratio thereof.
• the (meth) acrylic copolymer is used so that the glass transition temperature (Tg) determined by the Fox equation is usually ⁇ 80 to ⁇ 10 ° C., preferably ⁇ 80 to ⁇ 20 ° C., more preferably ⁇ 70 to ⁇ 30 ° C.
• a polymer (A) can be synthesized.
• a pressure-sensitive adhesive composition excellent in stress relaxation characteristics and durability and having excellent adhesiveness at room temperature is obtained. be able to.
• Tg is a glass transition temperature of the (meth) acrylic copolymer (A)
• Tg 1 , Tg 2 ,..., Tg m are glass transition temperatures of homopolymers composed of the respective monomers
• W 1 , W 2 ,..., W m are weight fractions of the structural units derived from the respective monomers in the copolymer (A).
• the charging ratio of each monomer to the total monomers at the time of copolymer synthesis can be used.
• combined on the conditions mentioned above is measured on the conditions mentioned above, for example.
• the content of the (meth) acrylic copolymer (A) is usually 60 to 99.99% by mass, preferably 100 to 99.99% by mass, preferably 100% by mass of the solid content excluding the organic solvent in the composition. Is 70 to 99.95% by mass, particularly preferably 80 to 99.90% by mass.
• the content of the (meth) acrylic copolymer (A) is in the above range, the performance as an adhesive is balanced and the adhesive properties are excellent.
• the pressure-sensitive adhesive composition of the present invention further contains a crosslinking agent (B).
• the crosslinking agent (B) is particularly limited as long as it is a component capable of causing a crosslinking reaction with the crosslinking functional group derived from the crosslinking functional group-containing monomer (a2) of the (meth) acrylic copolymer (A).
• an isocyanate compound (B1), a metal chelate compound (B2), and an epoxy compound (B3) can be mentioned.
• a crosslinking agent (B) may be used individually by 1 type, and may use 2 or more types.
• the content of the cross-linking agent (B) is usually 0.01 to 5 parts by mass, preferably 0.00 with respect to 100 parts by mass of the (meth) acrylic copolymer (A). 05 to 2.5 parts by mass, more preferably 0.1 to 1 part by mass. When the content is within the above range, it is preferable in terms of easy balance between durability and stress relaxation characteristics.
• Isocyanate compound (B1) an isocyanate compound having 2 or more isocyanate groups in one molecule is usually used.
• a crosslinked body (network polymer) can be formed by crosslinking the (meth) acrylic copolymer (A) with the isocyanate compound (B1).
• the number of isocyanate groups in the isocyanate compound (B1) is usually 2 or more, preferably 2 to 8, and more preferably 3 to 6. When the number of isocyanate groups is within the above range, it is preferable from the viewpoint of the crosslinking reaction efficiency between the (meth) acrylic copolymer (A) and the isocyanate compound (B1) and the flexibility of the pressure-sensitive adhesive layer.
• diisocyanate compound having 2 isocyanate groups in one molecule examples include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
• Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl
• aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate.
• alicyclic diisocyanates include alicyclic rings having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
• Group diisocyanates are examples of alicyclic rings having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
• aromatic diisocyanate examples include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
• isocyanate compound having 3 or more isocyanate groups in one molecule examples include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specific examples include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4 ', 4 "-triphenylmethane triisocyanate.
• Examples of the isocyanate compound (B1) include multimers (for example, dimers or trimers, biurets, isocyanurates), derivatives (for example, many) of the above isocyanate compounds having 2 or 3 or more isocyanate groups. Addition reaction product of a dihydric alcohol and two or more molecules of a diisocyanate compound), and a polymer.
• polyhydric alcohol in the derivative examples include trivalent or higher alcohols such as trimethylolpropane, glycerin and pentaerythritol as low molecular weight polyhydric alcohols; high molecular weight polyhydric alcohols such as polyether polyols, Examples include polyester polyol, acrylic polyol, polybutadiene polyol, and polyisoprene polyol.
• isocyanate compounds include diphenylmethane diisocyanate trimer, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate or tolylene diisocyanate biuret or isocyanurate, trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate.
• Reaction product for example, a trimolecular adduct of tolylene diisocyanate or xylylene diisocyanate
• reaction product of trimethylolpropane and hexamethylene diisocyanate for example, a trimolecular adduct of hexamethylene diisocyanate
• polyether polyisocyanate for example, a polyether polyisocyanate
• Polyester polyisocyanate is mentioned.
• isocyanate compounds (B1) reaction products of trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate (L-45 manufactured by Soken Chemical Co., Ltd., Soken Chemical Co., Ltd.) can improve the aging property.
• TD-75 isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate (TSE-100 manufactured by Asahi Kasei Corporation, 2050 manufactured by Nippon Polyurethane Industry Co., Ltd.).
• An isocyanate compound (B1) may be used individually by 1 type, and may use 2 or more types.
• Metal chelate compound (B2) examples include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium, alkoxide, acetylacetone, and ethyl acetoacetate. Examples include a coordinated compound.
• an aluminum chelate compound (M-12AT manufactured by Soken Chemical Co., Ltd.) is particularly preferable. Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethyl acetoacetate / diisopropylate, aluminum trisethyl acetoacetate, and aluminum trisacetylacetonate.
• a metal chelate compound (B2) may be used individually by 1 type, and may use 2 or more types.
• the metal chelate compound (B2) crosslinks the (meth) acrylic copolymer (A) by coordination bond (pseudocrosslinking).
• the metal chelate compound (B2) is used as the cross-linking agent (B)
• the cross-linking is maintained at room temperature, and the polymer exhibits cohesiveness. Shows greater flexibility.
• Epoxy compound (B3) an epoxy compound having 2 or more epoxy groups in one molecule is usually used.
• the pressure-sensitive adhesive composition of the present invention preferably further contains a silane coupling agent (C).
• a silane coupling agent (C) contributes to the point which adheres an adhesive layer firmly to adherends, such as a glass plate, and prevents peeling in a high-humidity heat environment.
• silane coupling agent (C) examples include polymerizable unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane Epoxy groups such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Containing silane coupling agent; amino such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Group-containing silane coupling Grayed
• a silane coupling agent having a functional group capable of forming a salt is preferable in that it is less likely to cause peeling in a wet and heat environment.
• the content of the silane coupling agent (C) is usually 1 part by mass or less, preferably 0.01 with respect to 100 parts by mass of the (meth) acrylic copolymer (A). To 1 part by mass, more preferably 0.05 to 0.5 part by mass. When the content is in the above range, peeling of the polarizing plate in a high humidity environment and bleeding of the silane coupling agent (C) in a high temperature environment tend to be prevented.
• the antistatic agent (D) can be used, for example, to reduce the surface resistance value of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
• examples of the antistatic agent (D) include a surfactant, an ionic compound, and a conductive polymer.
• surfactant examples include cationic surfactants having cationic groups such as quaternary ammonium salts, amide quaternary ammonium salts, pyridium salts, primary to tertiary amino groups; sulfonate groups, sulfate esters Anionic surfactants having an anionic group such as a base or a phosphate ester base; amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, amino acid sulfates, glycerin fatty acid esters
• Nonionic surfactants such as sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamines and alkyldiethanolamides It is done.
• the reactive type emulsifier which has a polymeric group is also mentioned as surfactant
• the polymeric surfactant which made high molecular weight the monomer component containing said surfactant or reactive emulsifier can also be used.
• the ionic compound is composed of a cation part and an anion part, and may be either solid or liquid at room temperature (23 ° C./50% RH).
• the cation portion constituting the ionic compound may be either an inorganic cation or an organic cation, or both.
• the inorganic cation alkali metal ions and alkaline earth metal ions are preferable, and Li + , Na + and K + having excellent antistatic properties are more preferable.
• organic cations include pyridinium cation, piperidinium cation, pyrrolidinium cation, pyrroline cation, pyrrole cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, pyrazoli Examples thereof include a nium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and derivatives thereof.
• the anion moiety constituting the ionic compound is not particularly limited as long as it can form an ionic compound by ionic bonding with the cation moiety.
• an anion containing a fluorine atom is preferable because it gives an ionic compound having a low melting point
• (F 2 SO 2 ) 2 N ⁇ and (CF 3 SO 2 ) 2 N ⁇ are particularly preferable, and deterioration of the polarizer (CF 3 SO 2 ) 2 N ⁇ is particularly preferable in that it is difficult to cause oxidization.
• Examples of the ionic compound include lithium bis (trifluoromethanesulfonyl) imide, lithium bis (difluorosulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methane, potassium bis (trifluoromethanesulfonyl) imide, potassium bis (difluorosulfonyl) imide, 1 -Ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (fluoro Sulfonyl) imide, 1-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide, tributylmethyla Monium bis
• the content of the antistatic agent (D) is usually 3 parts by mass or less, preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer (A). 3 parts by mass, more preferably 0.05 to 2.5 parts by mass.
• the pressure-sensitive adhesive composition of the present invention preferably contains an organic solvent (E) in order to adjust its applicability.
• an organic solvent the polymerization solvent demonstrated in the column of the (meth) acrylic-type copolymer (A) is mentioned.
• the pressure-sensitive adhesive composition can be prepared by mixing the polymer solution containing the (meth) acrylic copolymer (A) and the polymerization solvent obtained by the above copolymerization and the crosslinking agent (B). it can.
• the content of the organic solvent (E) is usually 50 to 90% by mass, preferably 60 to 85% by mass.
• solid content refers to all components excluding the organic solvent (E) among the components contained in the pressure-sensitive adhesive composition
• solid content concentration refers to the pressure-sensitive adhesive composition 100. The ratio of the said solid content with respect to the mass% is said.
• the pressure-sensitive adhesive composition of the present invention includes an antioxidant, a light stabilizer, a metal corrosion inhibitor, a tackifier, a plasticizer, a crosslinking accelerator, You may contain the 1 type (s) or 2 or more types selected from the (meth) acrylic-type polymer and rework agents other than A).
• the pressure-sensitive adhesive composition of the present invention is prepared by mixing the (meth) acrylic copolymer (A), the cross-linking agent (B), and other components as required by a conventionally known method. Can do.
• the cross-linking agent (B) and, if necessary, other components may be added to the polymer solution containing the polymer obtained when the (meth) acrylic copolymer (A) is synthesized. It is done.
• the pressure-sensitive adhesive composition of the present invention is suitable for use in bonding a substrate constituting a liquid crystal cell and a polarizer.
• a substrate constituting a liquid crystal cell and a polarizer Even when the thickness of the glass plate constituting the thinned liquid crystal cell is as small as about 0.05 to 1.0 mm, it is suitable for use in bonding the substrate and the polarizer.
• the gel fraction of the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition of the present invention is preferably 40% by mass or more, more preferably 40 to 95% by mass, and further preferably 45 to 90% by mass.
• the said gel fraction is a value measured about the adhesive extract
• the pressure-sensitive adhesive layer for polarizing plates of the present invention is formed from the above-mentioned pressure-sensitive adhesive composition.
• a pressure-sensitive adhesive layer having the following water vapor transmission rate can be formed.
• the pressure-sensitive adhesive layer of the present invention has a water vapor permeability of preferably 800 g / m 2 ⁇ day or less, more preferably 600 g / m 2 ⁇ day or less, and still more preferably 400 g / m 2 ⁇ day or less.
• the method for measuring the water vapor transmission rate will be described in detail in the Examples section below.
• the pressure-sensitive adhesive layer of the present invention can prevent the polarizer from contracting and the occurrence of cracks and the like even in a high humidity environment. Furthermore, since the deterioration of the iodine complex contained in the polarizer is also suppressed, the change in optical characteristics before and after the durability test is reduced.
• the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has a gel fraction of preferably 40% by mass or more, more preferably from the viewpoints of distortion suppression, cohesive strength, adhesive strength, and removability of the polarizing plate. It is 40 to 95% by mass, more preferably 45 to 90% by mass. When the gel fraction is in the above range, the pressure-sensitive adhesive layer exhibits excellent durability.
• the pressure-sensitive adhesive layer of the present invention specifically cross-links the (meth) acrylic copolymer (A) with the cross-linking agent (B) by, for example, advancing the crosslinking reaction in the above-mentioned pressure-sensitive adhesive composition. Is obtained.
• the conditions for forming the pressure-sensitive adhesive layer are, for example, as follows.
• the pressure-sensitive adhesive composition of the present invention is applied on a support and varies depending on the type of solvent, but is usually 50 to 150 ° C., preferably 60 to 100 ° C., usually 1 to 10 minutes, preferably 2 to 7 minutes. Then, the solvent is removed and a coating film is formed.
• the film thickness of the dried coating film is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m.
• the pressure-sensitive adhesive layer is preferably formed under the following conditions. After applying the pressure-sensitive adhesive composition of the present invention on a support and applying a cover film on the coating film formed under the above conditions, usually 3 days or more, preferably 7 to 10 days, usually 5 to 60 ° C., It is preferably cured in an environment of 15 to 40 ° C., usually 30 to 70% RH, preferably 40 to 70% RH. When crosslinking is performed under the aging conditions as described above, a crosslinked body (network polymer) can be efficiently formed.
• a predetermined thickness is obtained by a known method such as spin coating, knife coating, roll coating, bar coating, blade coating, die coating, or gravure coating.
• a method of applying and drying can be used.
• polyester films such as polyethylene terephthalate (PET); plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
• PET polyethylene terephthalate
• plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
• the pressure-sensitive adhesive sheet for polarizing plates of the present invention has a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive sheet include a double-sided pressure-sensitive adhesive sheet having only the pressure-sensitive adhesive layer, a base material, and a double-sided pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed on both surfaces of the base material, the base material, and one of the base materials.
• Examples thereof include a single-sided pressure-sensitive adhesive sheet having the above-mentioned pressure-sensitive adhesive layer formed on the surface, and a pressure-sensitive adhesive sheet having a peel-treated cover film attached to the surface of the pressure-sensitive adhesive sheet that is not in contact with the base material.
• polyester films such as polyethylene terephthalate (PET); plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
• PET polyethylene terephthalate
• plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
• the conditions for forming the pressure-sensitive adhesive layer are the same as the conditions described in the column [Plastic pressure-sensitive adhesive layer].
• the thickness of the pressure-sensitive adhesive layer is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m, from the viewpoint of maintaining the adhesive performance.
• the film thickness of the substrate and the cover film is not particularly limited, but is usually 10 to 125 ⁇ m, preferably 25 to 75 ⁇ m.
• the polarizing plate with the pressure-sensitive adhesive layer of the present invention has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention, which is directly laminated on at least one surface of a polarizer.
• polarizing plate is used to include “polarizing film”.
• the polarizing plate As the polarizing plate, a conventionally known polarizing film can be used.
• positioned on a polarizer is mentioned.
• the polarizer protective film since the pressure-sensitive adhesive layer is disposed in direct contact with the polarizer, the polarizer protective film is disposed only on one side of the polarizer, and the polarizer protective film is disposed on both sides of the polarizer. There is no configuration.
• Examples of the polarizer include a stretched film obtained by stretching a film made of a polyvinyl alcohol-based resin containing a polarizing component.
• Examples of the polyvinyl alcohol-based resin include saponified products of polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, and ethylene-vinyl acetate copolymer.
• Examples of the polarizing component include iodine or a dichroic dye.
• the polarizer protective film examples include a film made of a thermoplastic resin.
• the thermoplastic resin include cellulose resin such as triacetyl cellulose, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, cyclic polyolefin resin (norbornene) Resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and a mixture of two or more selected from these resins.
• cellulose resin such as triacetyl cellulose, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, cyclic polyolefin resin (norbornene) Resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and a mixture of two or more selected from these resins.
• the thickness of the polarizing plate is usually 10 to 200 ⁇ m, preferably 30 to 100 ⁇ m.
• a polarizing plate can be reduced in thickness.
• the pressure-sensitive adhesive layer is formed in direct contact with the polarizer.
• a polarizing plate with an adhesive layer of the present invention for example, a polarizer protective film, a polarizer, and the adhesive layer are laminated in this order, the adhesive layer, the polarizer protective film, the polarizer, and the above
• the cover film mentioned above may be arrange
• the method for forming the pressure-sensitive adhesive layer on the surface of the polarizer is not particularly limited.
• the method for applying the pressure-sensitive adhesive composition directly to the surface of the polarizer using a bar coater, drying and aging, the pressure-sensitive adhesive sheet for polarizing plate of the present invention There is a method in which the pressure-sensitive adhesive layer possessed by is transferred to the polarizer surface and aged.
• the conditions for drying and aging, the range of the gel fraction, and the like are the same as the conditions described in the section of [PSA layer for polarizing plate].
• the thickness of the pressure-sensitive adhesive layer is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m in terms of dry film thickness.
• the pressure-sensitive adhesive layer only needs to be formed in contact with the polarizer on at least one surface of the polarizer, and the pressure-sensitive adhesive layer is formed only on one side of the polarizer, and the pressure-sensitive adhesive is formed on both sides of the polarizer.
• the aspect in which a layer is formed is mentioned.
• the layer which has other functions, such as a protective layer, a glare-proof layer, a phase difference layer, a viewing angle improvement layer, for example may be laminated
• a liquid crystal element is produced by providing the polarizing plate with an adhesive layer of the present invention obtained as described above on the substrate surface of the liquid crystal cell.
• the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates.
• the substrate of the liquid crystal cell examples include a glass plate.
• the thickness of the substrate is usually 0.05 to 3 mm, preferably 0.2 to 1 mm.
• substrate can be suppressed. Therefore, even when the thickness of the substrate is small (eg, 1 mm or less, preferably 0.2 to 1 mm), the above-mentioned pressure-sensitive adhesive composition can be suitably used for bonding the polarizing plate and the substrate.
• HLC-8320GPC manufactured by Tosoh Corporation
• -GPC column configuration The following four columns (all manufactured by Tosoh Corporation) (1) TSKgel HxL-H (guard column) (2) TSKgel GMHxL (3) TSKgel GMHxL (4) TSKgel G2500HxL ⁇ Flow rate: 1.0 mL / min -Column temperature: 40 ° C Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran) ⁇ Mobile phase solvent: Tetrahydrofuran ⁇ Standard polystyrene conversion
• Example 1 (1) Preparation of pressure-sensitive adhesive composition
• the polymer solution obtained in Synthesis Example 1 solid content concentration 30% by mass
• 100 parts (solid content) of (meth) acrylic copolymer A1 contained in the solution As an isocyanate compound, 0.15 part (solid content) of “L-45” (solid content 45% by mass, ethyl acetate solution) manufactured by Soken Chemical Co., Ltd. and “A” manufactured by Soken Chemical Co., Ltd. as a silane coupling agent.
• Example 1 the pressure-sensitive adhesive composition was changed in the same manner as in Example 1 except that the polymer solution was changed to the polymer solution obtained in Synthesis Examples 2 to 8 and the blending composition was changed as shown in Table 2.
• the polarizing plate with an adhesive sheet and an adhesive layer was obtained.
• TD-75 is an isocyanate compound (manufactured by Soken Chemical Co., Ltd.), and the other antistatic agent is 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide.
• the polarizing plate with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples (laminated body composed of PET film / pressure-sensitive adhesive layer / polarizer / polarizer protective film) was cut into a size of 70 mm ⁇ 25 mm, and the test piece was cut. Produced.
• the PET film was peeled from the test piece, and a laminate composed of the pressure-sensitive adhesive layer / polarizer / polarizer protective film was laminated on one side of a 2 mm thick glass plate using a 2 kg roller, and the pressure-sensitive adhesive layer, the glass plate, I stuck it to touch.
• the obtained laminate was allowed to stand in an environment of 23 ° C./50% RH for 2 hours, and then the end of the polarizing plate was pulled at a speed of 300 mm / min in the 90 ° direction with respect to the glass plate surface, and the adhesive strength (peel strength) ) was measured.
• the water vapor transmission rate was measured as follows according to JIS Z0208.
• a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a thickness of 50 ⁇ m was prepared in the same manner as described in the column “(2) Preparation of pressure-sensitive adhesive sheet”.
• the PET film was peeled from this pressure-sensitive adhesive sheet, and a nonwoven fabric was bonded to both sides of the pressure-sensitive adhesive layer (the obtained laminate was referred to as “sheet A”), and cut according to the diameter of the moisture permeable cup.
• 10 g of calcium chloride was put in a moisture permeable cup (inner diameter 60 mm), and the cut sheet A, rubber packing, and cover ring were set and fixed with bolts.
• Water vapor transmission rate [g / m 2 ⁇ day] 240 ⁇ M / T ⁇ S M: Increased mass (mg) of the last two weighing intervals tested T: Time of the last two weighing intervals during the test (hours) S: Transmission area (cm 2 )
• g / m ⁇ 2 > * day is the meaning of g / m ⁇ 2 > / day.
• the polarizing plate with a pressure-sensitive adhesive layer obtained in the examples and comparative examples was cut into a size of 150 mm ⁇ 250 mm, and the test piece was cut. Produced.
• the PET film is peeled from the test piece, and a laminate composed of an adhesive layer / polarizer / polarizer protective film is laminated on one side of a 0.5 mm thick glass plate using a laminator roll. I stuck it so that it touched.
• the obtained laminate was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes to prepare a test plate.
• Optical test heat-resistant optical characteristics / humid heat-resistant optical characteristics test
• the polarizing plate with a pressure-sensitive adhesive layer obtained in the examples and comparative examples was cut into a size of 150 mm ⁇ 250 mm, and the test piece was cut. Produced.
• the PET film is peeled from the test piece, and using a laminator roll, the laminate composed of the pressure-sensitive adhesive layer / polarizer / polarizer protective film is perpendicular to the polarization axis on both sides of the 0.5 mm thick glass plate.
• the adhesive layer and the glass plate were attached so that they were in contact with each other.
• the obtained laminate was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes to prepare a test plate.
• Two similar test plates were prepared, and the test plate was allowed to stand for 500 hours at a temperature of 80 ° C./drying condition (heat resistance) or at a temperature of 60 ° C./humidity of 90% RH (humidity heat resistance), and haze.
• the total light transmittance was measured using a meter (HM-150 type: manufactured by Murakami Color Research Laboratory). The total light transmittance of the test plate before the durability test is 0%.
• the monomer that forms the (meth) acrylic copolymer As an example of the monomer that forms the (meth) acrylic copolymer, (1) As shown in the examples, in the example in which the monomer (a1) and the monomer (a2) are used at the specific ratio, the water vapor permeability is low ( (High hydrophobicity), excellent durability, and excellent optical properties. (2) As shown in Comparative Example 1, an example of using an acrylic acid alkyl ester without using a methacrylic acid alkyl ester, and (3) Comparative Example 2 As shown in the above, in the example in which the monomer (a1) and the monomer (a2) are not used in the specific ratio, the water vapor transmission rate is high (low hydrophobicity), and the durability and optical properties of the pressure-sensitive adhesive sheet are inferior. became.

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• 2015
  • 2015-06-15 JP JP2015120182A patent/JP2018127504A/ja active Pending
• 2016
  • 2016-05-30 WO PCT/JP2016/065854 patent/WO2016203935A1/ja active Application Filing
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