WO2023026687A1 - 粘着剤組成物、偏光板およびそれを用いた画像表示装置 - Google Patents

粘着剤組成物、偏光板およびそれを用いた画像表示装置 Download PDF

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WO2023026687A1
WO2023026687A1 PCT/JP2022/025980 JP2022025980W WO2023026687A1 WO 2023026687 A1 WO2023026687 A1 WO 2023026687A1 JP 2022025980 W JP2022025980 W JP 2022025980W WO 2023026687 A1 WO2023026687 A1 WO 2023026687A1
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Prior art keywords
sensitive adhesive
polarizing plate
pressure
adhesive composition
group
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PCT/JP2022/025980
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English (en)
French (fr)
Japanese (ja)
Inventor
翔平 杉山
雅人 藤田
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日東電工株式会社
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Priority to KR1020237044234A priority Critical patent/KR20240052727A/ko
Priority to CN202280057639.6A priority patent/CN117836387A/zh
Publication of WO2023026687A1 publication Critical patent/WO2023026687A1/ja

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    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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 a pressure-sensitive adhesive composition, a polarizing plate and an image display device using the same.
  • Image display devices represented by liquid crystal display devices and electroluminescence (EL) display devices are rapidly spreading.
  • EL electroluminescence
  • a polarizing plate is typically attached to a display panel via an adhesive layer.
  • a polarizing plate having an adhesive layer may be required to have reworkability in the manufacturing process as well as adhesion to the adherend.
  • a polarizing plate with an adhesive layer may be required to have reworkability in the manufacturing process as well as adhesion to the adherend.
  • the polarizer may be damaged during rework, and the yield may decrease.
  • through holes may be provided depending on the application in which the polarizing plate is used.
  • a polarizing plate used for applications such as smartphones may have a through hole provided in a portion corresponding to a camera section. This through hole partially reduces the area of the polarizing plate around the through hole. Therefore, stress tends to concentrate on that portion during rework, and the polarizing plate may be damaged. The thinner the polarizing plate, the greater the tendency.
  • the present invention has been made to solve the above-mentioned conventional problems, and the main purpose thereof is to provide a pressure-sensitive adhesive composition that has low resistance, excellent reworkability, and can suppress the occurrence of dents, and An object of the present invention is to provide a polarizing plate using the adhesive composition.
  • a pressure-sensitive adhesive composition includes a base polymer containing an alkoxy group-containing monomer as a monomer component, an antistatic agent, and a polyoxyethylene sorbitan fatty acid ester.
  • the total average number of ethylene oxide additions contained in this polyoxyethylene sorbitan fatty acid ester and the number of carbon atoms in the aliphatic hydrocarbon group satisfy the following formula: Total average addition number of ethylene oxide/carbon number of aliphatic hydrocarbon group ⁇ 0.4.
  • the sum of the average number of ethylene oxide additions is an integer of 1 or greater.
  • the aliphatic hydrocarbon group is a monovalent aliphatic hydrocarbon group having 5 to 20 carbon atoms.
  • the content of the polyoxyethylene sorbitan fatty acid ester is 0.005 to 5 parts by weight with respect to 100 parts by weight of the base polymer.
  • the base polymer contains 20 to 99 parts by weight of the alkoxy group-containing monomer with respect to 100 parts by weight of all monomer components.
  • the content of the antistatic agent in the pressure-sensitive adhesive composition is 10 parts by weight or less with respect to 100 parts by weight of the base polymer.
  • the alkoxy group-containing monomer is represented by the formula: (wherein R 1 is an alkyl group and n is an integer from 1 to 15).
  • the base polymer further contains a hydroxyl group-containing monomer as a monomer component.
  • the weight average molecular weight of the base polymer is 1-3 million.
  • the antistatic agent comprises lithium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide or tributylmethylammonium bis(trifluoromethanesulfonyl)imide.
  • the pressure-sensitive adhesive composition further contains a silane coupling agent.
  • a polarizing plate is provided in another situation of this invention. This polarizing plate includes a polarizer, a protective layer, and an adhesive layer formed using the adhesive composition in this order.
  • the pressure-sensitive adhesive layer has a surface resistance value of 5.0 ⁇ 10 9 ⁇ / ⁇ or less.
  • the humidification test is performed for 240 hours under conditions of a temperature of 60° C. and a humidity of 95% RH.
  • the protective layer is a solidified layer or hardened layer of a coating film of an organic solvent solution.
  • the protective layer has through holes.
  • an image display device is provided. This image display device includes the polarizing plate.
  • a pressure-sensitive adhesive composition having low resistance, excellent reworkability, and capable of suppressing the occurrence of dents, and a polarizing plate using the pressure-sensitive adhesive composition are provided.
  • a pressure-sensitive adhesive composition in which change in resistance due to the influence of humidification is suppressed is suppressed, and a polarizing plate using the pressure-sensitive adhesive composition.
  • FIG. 1 is a schematic cross-sectional view of a polarizer according to one embodiment of the invention
  • FIG. 1 is a schematic cross-sectional view of an image display device according to one embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view of an image display device according to one embodiment of the present invention
  • the adhesive composition of the embodiment of the present invention contains a base polymer containing an alkoxy group-containing monomer as a monomer component, an antistatic agent, and a polyoxyethylene sorbitan fatty acid ester.
  • the total average number of additions of ethylene oxide contained in this polyoxyethylene sorbitan fatty acid ester and the number of carbon atoms in the aliphatic hydrocarbon group satisfy the following formula.
  • A-1. Base Polymer As the base polymer, any suitable base polymer used as a base polymer for adhesives can be used. Examples thereof include (meth)acrylic polymers, urethane polymers, silicone polymers, and rubber polymers. A (meth)acrylic polymer is preferred. In this specification, a (meth)acrylic polymer as a base polymer may be referred to as a (meth)acrylic base polymer.
  • the glass transition temperature (Tg) of the base polymer is preferably -50°C or lower, more preferably -52°C or lower, and still more preferably -55°C or lower.
  • the Tg of the base polymer can be, for example, -75°C or higher.
  • the dielectric constant at 100 kHz of the base polymer is preferably 5.0 or higher, more preferably 5.5 or higher, still more preferably 6.0 or higher, particularly preferably 6.5 or higher, and more particularly Preferably it is 7.0 or more.
  • the dielectric constant of the base polymer can be, for example, 10.0 or less.
  • the base polymer contains an alkoxy group-containing monomer as a monomer component.
  • an alkoxy group-containing monomer as a monomer component, a base polymer having the above Tg and dielectric constant can be obtained.
  • Any appropriate monomer having an alkoxy group can be used as the alkoxy group-containing monomer.
  • Alkoxy group-containing monomers may be used alone or in combination of two or more.
  • Alkoxy groups are preferably linear alkoxy groups. If it is a straight-chain alkoxy group, the Tg and dielectric constant of the obtained (meth)acrylic base polymer can be within the above ranges.
  • Alkoxy group-containing monomers preferably include monomers represented by the formula: (wherein R 1 is an alkyl group and n is an integer from 1 to 15).
  • R 1 above is any suitable alkyl group, preferably a methyl group or an ethyl group.
  • alkoxy group-containing monomers include methoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.
  • the content of the alkoxy group-containing monomer in the base polymer is preferably 20 parts by weight to 99 parts by weight, more preferably 30 parts by weight to 90 parts by weight, and still more preferably 100 parts by weight of all monomer components. 30 to 60 parts by weight, more preferably 30 to 50 parts by weight. In one embodiment, the content of the alkoxy group-containing monomer in the base polymer is preferably 50 parts by weight to 99 parts by weight, more preferably 60 parts by weight to 99 parts by weight, based on 100 parts by weight of all monomer components. is.
  • the (meth)acrylic base polymer preferably contains a hydroxyl group-containing monomer as a monomer component.
  • Any suitable monomer having a hydroxyl group can be used as the hydroxyl group-containing monomer.
  • Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl ( meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)-methyl acrylate.
  • 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred, and 4-hydroxybutyl (meth)acrylate is more preferred. Only one hydroxyl group-containing monomer may be used, or two or more thereof may be used in combination.
  • the content of the hydroxyl group-containing monomer in the base polymer is preferably 1 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of all the monomer components.
  • the (meth)acrylic base polymer may contain an alkyl (meth)acrylate as a monomer component.
  • Alkyl (meth)acrylates include alkyl (meth)acrylates having a linear or branched alkyl group having 1 to 18 carbon atoms. The number of carbon atoms in the alkyl group is preferably 3-8, more preferably 3-6.
  • alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group and decyl group. , isodecyl group, dodecyl group, isomyristyl group, lauryl group, tridecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. Only one type of alkyl (meth)acrylate may be used, or two or more types may be used.
  • the alkyl (meth)acrylate in the base polymer can be used in any suitable amount.
  • the alkoxy group-containing monomer, the hydroxyl group-containing monomer, and any other monomer component may be used so that the total is 100 parts by weight.
  • the (meth)acrylic base polymer may further contain other monomer components as necessary. Any appropriate monomer component can be used as the other monomer component. Specifically, aromatic hydrocarbon group-containing monomers such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) ) Carboxyl group-containing monomers such as acrylates, itaconic acid, maleic acid, fumaric acid, crotonic acid, amino group-containing monomers such as N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylamide, N,N-dimethyl ( Amide group-containing monomers such as meth)acrylamide and N,N-diethyl (meth)acrylamide, nitrile group-containing monomers such as (meth)acrylonitrile, hexan
  • alkoxy group-containing monomer, the hydroxyl group-containing monomer, and any alkyl (meth)acrylate may be used so that the total is 100 parts by weight.
  • the (meth)acrylic base polymer has a weight average molecular weight Mw of preferably 1 million to 3 million, more preferably 2 million to 3 million, still more preferably 2 million to 2.8 million. If the weight-average molecular weight Mw is less than 1,000,000, the suppression of cracks may be insufficient. If the weight average molecular weight Mw exceeds 3,000,000, viscosity increase and/or gelation during polymer polymerization may occur.
  • antistatic agent Any appropriate antistatic agent can be used as the antistatic agent. Typical examples include inorganic cation salts and organic cation salts. Only one kind of antistatic agent may be used, or two or more kinds thereof may be used in combination.
  • An inorganic cation salt is specifically an inorganic cation-anion salt.
  • cations constituting the cation part of the inorganic cation salt representative examples thereof include alkali metal ions. Specific examples include lithium ions, sodium ions, and potassium ions. Lithium ion is preferred.
  • a preferred inorganic cation salt is therefore the lithium salt.
  • anions constituting the anion portion of the inorganic cation salt include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 3 C ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , NbF 6 ⁇ , TaF 6 ⁇ , (CN ) 2 N ⁇ , C 4 F 9 SO 3 ⁇ , C 3 F 7 COO ⁇ , (CF 3 SO 2 )(CF 3 CO)N ⁇ , —O 3 S(CF 2 ) 3 SO 3 ⁇ , and General formulas (1) to (4): (1): (C n F 2n+1 SO 2 ) 2 N ⁇ (n is an integer of 1 to 10
  • fluorine-containing imide anions include imide anions having a perfluoroalkyl group. Specific examples include (CF 3 SO 2 )(CF 3 CO)N ⁇ described above, and general formulas (1), (2) and (4): (1): (C n F 2n+1 SO 2 ) 2 N ⁇ (n is an integer of 1 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N ⁇ (m is an integer of 1 to 10), (4): (C p F 2p+1 SO 2 )N ⁇ (C q F 2q+1 SO 2 ), (p and q are integers from 1 to 10), The anion represented by is mentioned.
  • a preferred inorganic cation salt that may be used in embodiments of the present invention is lithium bis(trifluoromethanesulfonyl)imide.
  • the organic cation salt is specifically an organic cation-anion salt.
  • a cation constituting the cation part of the organic cation salt typically, an organic onium having an onium ion formed by substitution with an organic group can be mentioned.
  • onium in organic onium include nitrogen-containing onium, sulfur-containing onium, and phosphorus-containing onium. Nitrogen-containing onium and sulfur-containing onium are preferred.
  • Nitrogen-containing oniums include ammonium cations, piperidinium cations, pyrrolidinium cations, pyridinium cations, cations having a pyrroline skeleton, cations having a pyrrole skeleton, imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, Examples include pyrazolium cations and pyrazolinium cations.
  • sulfur-containing onium include sulfonium cations.
  • Examples of phosphorus-containing onium include phosphonium cations.
  • organic groups in the organic onium include alkyl groups, alkoxyl groups, and alkenyl groups.
  • preferred organic oniums include tetraalkylammonium cations (eg, tributylmethylammonium cations), alkylpiperidinium cations, and alkylpyrrolidinium cations.
  • the anions constituting the anion portion of the organic cation salt are as described for the anions constituting the anion portion of the inorganic cation salt.
  • Preferred organic cation salts that may be used in embodiments of the present invention are 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, tributylmethylammonium bis(trifluoromethanesulfonyl)imide.
  • the content of the antistatic agent in the pressure-sensitive adhesive composition is preferably 10 parts by weight or less, more preferably 7 parts by weight or less, and still more preferably 5 parts by weight or less with respect to 100 parts by weight of the base polymer. , particularly preferably 3 parts by weight or less.
  • an adhesive capable of forming an adhesive layer having a small surface resistance value for example, 5.0 ⁇ 10 9 ⁇ / ⁇ or less
  • a composition can be provided.
  • the use of a large amount of antistatic agent can suppress the occurrence of dents due to softening of the pressure-sensitive adhesive composition (resultingly formed pressure-sensitive adhesive layer).
  • the content of the antistatic agent may be, for example, 0.5 parts by weight or more. If the content of the antistatic agent is too small, the surface resistance value may not be lowered sufficiently.
  • the adhesive composition comprises a polyoxyethylene sorbitan fatty acid ester.
  • Polyoxyethylene sorbitan fatty acid ester has a polyethylene glycol structure in at least part of the hydroxyl group of sorbitan such as 1,4-anhydrosorbitol, 1,5-anhydrosorbitol and 1,4,3,6-dianhydrosorbitol. It refers to an ester of a terminal hydroxyl group of an ether obtained by introducing and a fatty acid.
  • the total average number of ethylene oxide additions contained in the polyoxyethylene sorbitan fatty acid ester and the number of carbon atoms in the aliphatic hydrocarbon group satisfy the following formula.
  • Polyoxyethylene sorbitan fatty acid ester can function as a surfactant.
  • the hydrophilic group of the polyoxyethylene sorbitan fatty acid ester is on the adherend side and the hydrophobic group is on the adhesive layer side at the interface with the adherend (e.g., glass). It can be unevenly distributed in a state where As a result, excessive increase in the adhesive strength of the adhesive layer can be suppressed, and reworkability can be improved.
  • the total average number of additions of ethylene oxide/the number of carbon atoms in the aliphatic hydrocarbon group is 0.4 or more, preferably 0.5 or more, more preferably 0.8 as described above. more preferably 1.0 or more, more preferably 1.2 or more, and particularly preferably 1.5 or more.
  • the total average number of additions of ethylene oxide/the number of carbon atoms of the aliphatic hydrocarbon group is, for example, 2.0 or less.
  • Polyoxyethylene sorbitan fatty acid esters of 1,4-anhydrosorbitol and/or 1,5-anhydrosorbitol are preferably used as polyoxyethylene sorbitan fatty acid esters.
  • polyoxyethylene sorbitan fatty acid esters represented by the following formulas (A) and (B) can be used. (wherein, x1, y1, z1, x2, y2, and z2 each independently represent an integer of 0 or greater, and R represents a monovalent aliphatic hydrocarbon group).
  • x1, y1, z1, x2, y2, and z2 each independently represent an integer of 0 or more.
  • x1, y1, z1, x2, y2, and z2 can be set to any suitable values such that the sum of the average number of additions of ethylene oxide/the number of carbon atoms in the aliphatic hydrocarbon group is 0.4 or more.
  • x1, y1, z1, x2, y2, and z2 are, for example, integers of 1 or more, preferably 2 or more.
  • the upper limits of x1, y1, z1, x2, y2, and z2 are not particularly limited, and the total average number of additions of ethylene oxide (for example, the above x1 + y1 + z1 or x2 + y2 + z2) is the total average number of additions of ethylene oxide/aliphatic hydrocarbon group may be any value as long as the value of the number of carbon atoms is within the above range.
  • the total average number of additions of ethylene oxide contained in the polyoxyethylene sorbitan fatty acid ester is the total number of average additions of ethylene oxide / any number of aliphatic hydrocarbon groups having 0.4 or more carbon atoms can be set to an appropriate value of
  • the total average number of ethylene oxide additions is preferably 1 or more, more preferably 7 or more, still more preferably 10 or more, even more preferably 15 or more, and particularly preferably 20 or more.
  • the upper limit of the total average addition number of ethylene oxide contained in the polyoxyethylene sorbitan fatty acid ester is not particularly limited, and is, for example, 50 or less, preferably 25 or less.
  • R represents a monovalent aliphatic hydrocarbon group.
  • the monovalent aliphatic hydrocarbon group includes any appropriate aliphatic hydrocarbon group such that the average number of additions of ethylene oxide/the number of carbon atoms in the aliphatic hydrocarbon group is 0.4 or more.
  • a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms can be used, preferably a monovalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, more preferably a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms. can be used, more preferably a monovalent aliphatic hydrocarbon group having 4 to 20 carbon atoms.
  • polyoxyethylene sorbitan fatty acid esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan monostea. rate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan triisostearate, and the like.
  • the content of polyoxyethylene sorbitan fatty acid ester can be set to any appropriate amount. It is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the base polymer. is. If the content of the polyoxyethylene sorbitan fatty acid ester is within the above range, the reworkability of the pressure-sensitive adhesive composition can be improved. If the content of the polyoxyethylene sorbitan fatty acid ester is less than 0.005 parts by weight, there is a possibility that sufficient reworkability cannot be obtained. If the content of the polyoxyethylene sorbitan fatty acid ester exceeds 5 parts by weight, there is a possibility that sufficient adhesive strength cannot be exhibited.
  • the adhesive composition may further contain additives.
  • additives include powders such as silane coupling agents, cross-linking agents, antioxidants, colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, Softeners, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, and foils.
  • a redox system with a reducing agent added may be employed within a controllable range.
  • the type, number, combination, content, etc. of additives can be set to any appropriate value depending on the purpose.
  • silane coupling agent can be used as the silane coupling agent.
  • the following advantages can be obtained by including a silane coupling agent.
  • a pressure-sensitive adhesive composition using a base polymer containing an alkoxy group-containing monomer has a high polarity, which may result in insufficient pressure-sensitive adhesiveness to a non-polar adherend.
  • Silane coupling agents typically include functional group-containing silane coupling agents.
  • Functional groups include, for example, epoxy group, mercapto group, amino group, isocyanate group, isocyanurate group, vinyl group, styryl group, acetoacetyl group, ureido group, thiourea group, (meth)acrylic group, heterocyclic group, acid Anhydride groups and combinations thereof are included.
  • Silane coupling agents may be used alone or in combination of two or more.
  • cross-linking agents examples include isocyanate-based cross-linking agents and peroxide-based cross-linking agents. Only one kind of the crosslinking agent may be used, or two or more kinds thereof may be used in combination.
  • antioxidants can be used as the antioxidant.
  • Antioxidants may be used alone or in combination of two or more. Inclusion of antioxidants may provide the following benefits.
  • Base polymers containing alkoxy group-containing monomers have a lower Tg and are softer. By containing an antioxidant, it is possible to suppress shrinkage due to oxidative deterioration from the end surfaces of the polarizing plate and the adhesive layer.
  • FIG. 1 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the invention.
  • the polarizing plate 100 typically includes a polarizer 10, a protective layer 20 provided on one side of the polarizer 10 (hereinafter also referred to as a first protective layer), and the polarizer 10 of the protective layer 20. It has an adhesive layer 40 provided on the opposite side and a protective layer 30 (hereinafter also referred to as a second protective layer) provided on the other side of the polarizer 10 .
  • the protective layer 30 may be omitted.
  • the pressure-sensitive adhesive layer 40 is provided as the outermost layer, and the polarizing plate can be attached to an image display device (substantially, an image display panel). Practically, it is preferable that a release film is temporarily attached to the surface of the adhesive layer 40 until the polarizing plate is used. By temporarily attaching the release film, it is possible to protect the pressure-sensitive adhesive layer and to form a roll of the polarizing plate.
  • the polarizing plate has a resistance value increase rate of 4000% or less, more preferably 2000% or less, and still more preferably 1000% or less in a humidification test represented by the following formula. , particularly preferably 500% or less.
  • Resistance value increase rate resistance value after humidification reliability test / initial resistance value x 100
  • the humidification test is performed for 240 hours under conditions of a temperature of 60° C. and a humidity of 95% RH.
  • a polarizing plate having excellent durability can be realized by setting the rate of increase in resistance value of the polarizing plate within such a range.
  • the polarizing plate according to the embodiment of the present invention may further contain other functional layers.
  • a representative example of such a functional layer is a retardation layer.
  • the optical properties for example, refractive index properties, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement position, etc. of the retardation layer can be appropriately set according to the purpose.
  • the polarizing plate according to the embodiment of the present invention may be sheet-shaped or elongated.
  • the term "long shape” means an elongated shape whose length is sufficiently long relative to its width, for example, an elongated shape whose length is 10 times or more, preferably 20 times or more, its width. include.
  • a long polarizing plate can be wound into a roll.
  • the polarizing plate has through holes.
  • the shape of the through hole may be circular, elliptical, triangular, quadrangular, pentagonal, hexagonal, or octagonal.
  • the through holes are provided at any appropriate positions depending on the purpose.
  • the through-holes may be provided substantially in the center of the longitudinal ends of the rectangular polarizing plate, may be provided at predetermined positions of the longitudinal ends, or may be provided at the corners of the polarizing plate. It may be provided at the ends of the rectangular polarizing plate in the short direction; it may be provided at the central portion of the polarizing plate having an irregular shape as a whole.
  • the thickness of the polarizing plate can be set to any appropriate value.
  • the thickness of the polarizing plate is, for example, 30 ⁇ m to 150 ⁇ m, preferably 40 ⁇ m to 100 ⁇ m, more preferably 50 ⁇ m to 80 ⁇ m.
  • Polarizer A polarizer is typically composed of a resin film containing a dichroic substance (typically iodine). Any appropriate resin film that can be used as a polarizer can be adopted as the resin film.
  • the resin film is typically a polyvinyl alcohol-based resin (hereinafter referred to as "PVA-based resin") film.
  • the resin film may be a single-layer resin film or a laminate of two or more layers.
  • a specific example of a polarizer composed of a single-layer resin film is a PVA-based resin film that has been dyed with iodine and stretched (typically, uniaxially stretched).
  • the dyeing with iodine is performed by, for example, immersing the PVA-based film in an aqueous iodine solution.
  • the draw ratio of the uniaxial drawing is preferably 3 to 7 times. Stretching may be performed after the dyeing treatment, or may be performed while dyeing. Moreover, you may dye after extending
  • the polarizer obtained using a laminate include a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate, or a resin substrate and the resin
  • a polarizer obtained by using a laminate with a PVA-based resin layer formed by coating on a substrate can be mentioned.
  • a polarizer obtained by using a laminate of a resin base material and a PVA-based resin layer formed by coating on the resin base material is obtained, for example, by applying a PVA-based resin solution to the resin base material and drying the resin base material.
  • a PVA-based resin layer thereon to obtain a laminate of a resin substrate and a PVA-based resin layer; stretching and dyeing the laminate to use the PVA-based resin layer as a polarizer; obtain.
  • a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin is formed on one side of the resin substrate.
  • Stretching typically includes immersing the laminate in an aqueous boric acid solution for stretching.
  • stretching may further include stretching the laminate in air at a high temperature (eg, 95° C. or higher) before stretching in an aqueous boric acid solution, if necessary.
  • the laminate is preferably subjected to drying shrinkage treatment in which the laminate is heated while being conveyed in the longitudinal direction to shrink the laminate by 2% or more in the width direction.
  • the manufacturing method of the present embodiment includes subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order.
  • auxiliary stretching it is possible to improve the crystallinity of PVA and achieve high optical properties even when PVA is coated on a thermoplastic resin.
  • by increasing the orientation of PVA in advance it is possible to prevent problems such as deterioration of orientation and dissolution of PVA when immersed in water in the subsequent dyeing process or stretching process, resulting in high optical properties.
  • the PVA-based resin layer when the PVA-based resin layer is immersed in a liquid, disturbance of the orientation of the polyvinyl alcohol molecules and deterioration of the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide.
  • This can improve the optical properties of the polarizer obtained through treatment steps such as dyeing treatment and underwater stretching treatment in which the laminate is immersed in a liquid.
  • the optical properties can be improved by shrinking the laminate in the width direction by drying shrinkage treatment.
  • the obtained resin substrate/polarizer laminate may be used as it is (that is, the resin substrate may be used as a protective layer for the polarizer), or the resin substrate may be peeled off from the resin substrate/polarizer laminate.
  • any appropriate protective layer may be laminated on the release surface according to the purpose. Details of such a polarizer manufacturing method are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 (Patent No. 5414738) and Japanese Patent No. 6470455. These publications are incorporated herein by reference in their entirety.
  • the thickness of the polarizer is preferably 1 ⁇ m to 15 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m, even more preferably 1 ⁇ m to 8 ⁇ m, and particularly preferably 2 ⁇ m to 5 ⁇ m.
  • the polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
  • the single transmittance of the polarizer is preferably 41.5% to 46.0%, more preferably 43.0% to 46.0%, still more preferably 44.5% to 46.0%. be.
  • the degree of polarization of the polarizer is preferably 97.0% or higher, more preferably 99.0% or higher, still more preferably 99.9% or higher.
  • First Protective Layer Protective layer 20 may be composed of any suitable resin.
  • it may be any suitable resin film, or it may be a solidified layer or a cured layer of a coating film of an organic solvent solution containing a resin.
  • the protective layer 20 is preferably a solidified layer or hardened layer of a coating film of an organic solvent solution containing a resin.
  • Organic solvent solutions are prepared using any suitable resin. Any appropriate resin can be used as the resin (base polymer). Only one type of resin may be used, or two or more types may be used in combination.
  • a resin having a glass transition temperature (Tg) of, for example, 85°C or higher and a weight average molecular weight Mw of, for example, 25000 or higher is used.
  • Tg glass transition temperature
  • Mw weight average molecular weight
  • the Tg of the resin is preferably 90° C. or higher, more preferably 100° C. or higher, even more preferably 110° C. or higher, and particularly preferably 120° C. or higher.
  • Tg can be, for example, 200° C. or less.
  • the Mw of the resin is preferably 30,000 or more, more preferably 35,000 or more, and still more preferably 40,000 or more. Mw can be, for example, 150,000 or less.
  • thermoplastic resin any suitable thermoplastic resin can be used as long as it can form a solidified product or a cured product (e.g., a thermoset product) of a coating film of an organic solvent solution and has the Tg and Mw as described above.
  • a thermosetting resin can be used.
  • Thermoplastic resins are preferred. Examples of thermoplastic resins include acrylic resins and epoxy resins. An acrylic resin and an epoxy resin may be used in combination.
  • Acrylic resins typically contain, as a main component, repeating units derived from (meth)acrylic acid ester-based monomers having a linear or branched structure.
  • (meth)acryl refers to acryl and/or methacryl.
  • the acrylic resin may contain repeating units derived from any appropriate comonomers depending on the purpose.
  • copolymerizable monomers include carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, aromatic ring-containing (meth)acrylates, and heterocyclic ring-containing vinyl monomers.
  • the acrylic resin is more than 50 parts by weight of a (meth)acrylic monomer and more than 0 parts by weight and less than 50 parts by weight of the monomer represented by formula (1) (hereinafter , may be referred to as a copolymer monomer) and a copolymer obtained by polymerizing a monomer mixture (hereinafter sometimes referred to as a boron-containing acrylic resin) including: (Wherein, X is a vinyl group, a (meth)acryl group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a group consisting of a carboxyl group Represents a selected functional group containing at least one reactive group, and R 1 and R 2 each independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or
  • a boron-containing acrylic resin typically has a repeating unit represented by the following formula.
  • the boron-containing acrylic resin has a substituent containing boron in the side chain (e.g., repeating unit k in the following formula). This can improve the adhesion between the polarizer and the protective layer.
  • the boron-containing substituent may be included continuously (that is, in blocks) in the boron-containing acrylic resin, or may be included randomly. (Wherein, R6 represents an arbitrary functional group, and j and k represent integers of 1 or more).
  • Any appropriate (meth)acrylic monomer can be used as the (meth)acrylic monomer.
  • Examples thereof include (meth)acrylic acid ester-based monomers having a linear or branched structure and (meth)acrylic acid ester-based monomers having a cyclic structure.
  • Examples of (meth)acrylic ester-based monomers having a linear or branched structure include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. isopropyl, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and the like. . Preferably, methyl (meth)acrylate is used.
  • the (meth)acrylic acid ester-based monomers may be used alone or in combination of two or more.
  • Examples of (meth)acrylic ester-based monomers having a cyclic structure include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, ( meth)dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, biphenyl (meth)acrylate, o-biphenyloxyethyl (meth)acrylate, o-biphenyloxyethoxy Ethyl (meth)acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth)acrylate, o-biphenyloxy-2-hydroxypropyl (meth)acrylate, p-biphenyloxy-2-hydroxypropyl (meth)acrylate ,
  • 1-adamantyl (meth)acrylate and dicyclopentanyl (meth)acrylate are used.
  • a polymer having a high glass transition temperature can be obtained by using these monomers. These monomers may be used alone or in combination of two or more.
  • a silsesquioxane compound having a (meth)acryloyl group may be used instead of the (meth)acrylate monomer.
  • a silsesquioxane compound By using a silsesquioxane compound, an acrylic polymer having a high glass transition temperature can be obtained.
  • Silsesquioxane compounds are known to have various skeleton structures, such as cage structures, ladder structures, and random structures. The silsesquioxane compound may have only one of these structures, or may have two or more. Silsesquioxane compounds may be used alone or in combination of two or more.
  • silsesquioxane compound containing a (meth)acryloyl group for example, Toagosei Co., Ltd. SQ series MAC grade and AC grade can be used.
  • MAC grade is a silsesquioxane compound containing a methacryloyl group, and specific examples thereof include MAC-SQ TM-100, MAC-SQ SI-20, MAC-SQ HDM, and the like.
  • AC grade is a silsesquioxane compound containing an acryloyl group, and specific examples thereof include AC-SQ TA-100 and AC-SQ SI-20.
  • the (meth)acrylic monomer is used in an amount exceeding 50 parts by weight with respect to 100 parts by weight of the monomer mixture.
  • Comonomer> A monomer represented by the above formula (1) is used as the comonomer. By using such a comonomer, a substituent containing boron is introduced into the side chain of the resulting polymer. Comonomers may be used alone or in combination of two or more.
  • aliphatic hydrocarbon group in the above formula (1) a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, 3 to 3 carbon atoms which may have a substituent 20 cyclic alkyl groups and alkenyl groups having 2 to 20 carbon atoms.
  • the aryl group include an optionally substituted phenyl group having 6 to 20 carbon atoms and a naphthyl group having 10 to 20 carbon atoms which may have a substituent.
  • the heterocyclic group includes a 5- or 6-membered ring group containing at least one optionally substituted heteroatom.
  • R 1 and R 2 may be linked together to form a ring.
  • R 1 and R 2 are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • Reactive groups contained in the functional group represented by X include vinyl group, (meth)acryl group, styryl group, (meth)acrylamide group, vinyl ether group, epoxy group, oxetane group, hydroxyl group, amino group, aldehyde group, and at least one selected from the group consisting of carboxyl groups.
  • the reactive groups are (meth)acryl and/or (meth)acrylamide groups.
  • the functional group represented by X is preferably a functional group represented by ZY-.
  • Z is selected from the group consisting of a vinyl group, a (meth)acryl group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
  • Y represents a phenylene group or an alkylene group.
  • the following compounds can be used as the comonomer.
  • the comonomer is used in a content of more than 0 parts by weight and less than 50 parts by weight with respect to 100 parts by weight of the monomer mixture. It is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, even more preferably 0.1 to 10 parts by weight, and particularly preferably 0.1 part by weight to 10 parts by weight. 5 to 5 parts by weight.
  • the acrylic resin has a repeating unit containing a ring structure selected from lactone ring units, glutaric anhydride units, glutarimide units, maleic anhydride units and maleimide (N-substituted maleimide) units.
  • the repeating unit containing a ring structure only one type may be included in the repeating unit of the acrylic resin, or two or more types may be included.
  • the lactone ring unit is preferably represented by the following general formula (2):
  • R 2 , R 3 and R 4 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • the organic residue may contain an oxygen atom.
  • the acrylic resin may contain only a single lactone ring unit, or may contain a plurality of lactone ring units in which R 2 , R 3 and R 4 in the general formula (2) are different. .
  • An acrylic resin having a lactone ring unit is described, for example, in JP-A-2008-181078, and the description of the publication is incorporated herein by reference.
  • the glutarimide unit is preferably represented by the following general formula (3):
  • R 11 and R 12 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms; R 13 is an alkyl group having 1 to 18 carbon atoms; or an aryl group having 6 to 10 carbon atoms.
  • R 11 and R 12 are each independently hydrogen or methyl, and R 13 is hydrogen, methyl, butyl or cyclohexyl. More preferably, R 11 is a methyl group, R 12 is hydrogen and R 13 is a methyl group.
  • the acrylic resin may contain only a single glutarimide unit, or may contain a plurality of glutarimide units in which R 11 , R 12 and R 13 in the general formula (3) are different. .
  • Acrylic resins having a glutarimide unit for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328334, JP-A-2006-337491, JP-A-2006-337492 JP-A-2006-337493 and JP-A-2006-337569, and the descriptions in these publications are incorporated herein by reference.
  • the glutaric anhydride unit the above explanation regarding the glutarimide unit applies, except that the nitrogen atom substituted by R 13 in the general formula (3) becomes an oxygen atom.
  • the structure is specified from the name, so a specific description is omitted.
  • the content of repeating units containing a ring structure in the acrylic resin is preferably 1 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, still more preferably 20 mol% to 30 mol%.
  • acrylic resin contains the repeating unit derived from said (meth)acrylic-type monomer as a main repeating unit.
  • Epoxy resin an epoxy resin having an aromatic ring is preferably used. Adhesion between the protective layer and the polarizer can be improved by using an epoxy resin having an aromatic ring as the epoxy resin. Furthermore, when the adhesive layer is arranged adjacent to the protective layer, the anchoring force of the adhesive layer can be improved.
  • epoxy resins having an aromatic ring examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin; phenol novolak epoxy resin, cresol novolak epoxy resin, hydroxybenzaldehyde phenol novolak Novolac type epoxy resins such as epoxy resins; polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, epoxidized polyvinylphenol, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and the like.
  • Bisphenol A type epoxy resin, biphenyl type epoxy resin, and bisphenol F type epoxy resin are preferably used.
  • Epoxy resins may be used alone or in combination of two or more.
  • the first protective layer can be formed by applying an organic solvent solution of the above resin to form a coating film, and solidifying or thermally curing the coating film.
  • organic solvent Any suitable organic solvent that can dissolve or uniformly disperse the acrylic resin or epoxy resin can be used as the organic solvent.
  • organic solvents include ethyl acetate, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone.
  • the resin concentration of the solution is preferably 3 to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, a uniform coating film can be formed.
  • the solution may be applied to any suitable base material or may be applied to a polarizer.
  • the solidified product (resin layer) of the coating film formed on the substrate is transferred to the polarizer.
  • the protective layer is directly formed on the polarizer by drying (solidifying) the applied film.
  • the solution is applied to the polarizer to form a protective layer directly on the polarizer.
  • the adhesive layer or pressure-sensitive adhesive layer required for transfer can be omitted, so the polarizing plate can be made even thinner.
  • Any appropriate method can be adopted as a method of applying the solution. Specific examples include roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and knife coating (comma coating, etc.).
  • the first protective layer can be formed by solidifying or thermally curing the applied film of the solution.
  • the heating temperature for solidification or heat curing is preferably 100°C or less, more preferably 50°C to 70°C. If the heating temperature is within this range, it is possible to prevent adverse effects on the polarizer.
  • the heating time can vary depending on the heating temperature. The heating time can be, for example, 1 minute to 10 minutes.
  • the first protective layer may contain any appropriate additive depending on the purpose.
  • additives include ultraviolet absorbers; leveling agents; antioxidants such as hindered phenol, phosphorus, and sulfur; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; Reinforcing materials such as carbon fiber; near-infrared absorbers; flame retardants such as tris(dibromopropyl) phosphate, triallyl phosphate, and antimony oxide; antistatic agents such as anionic, cationic, and nonionic surfactants; inorganic pigments , organic pigments, colorants such as dyes; organic fillers or inorganic fillers; resin modifiers; organic fillers or inorganic fillers; plasticizers; The type, number, combination, addition amount, etc. of additives can be appropriately set according to the purpose.
  • the thickness of the first protective layer is preferably 0.05 ⁇ m to 10 ⁇ m, more preferably 0.08 ⁇ m to 5 ⁇ m, even more preferably 0.1 ⁇ m to 1 ⁇ m, particularly preferably 0.2 ⁇ m to 0.7 ⁇ m. Since the first protective layer is a solidified layer or cured layer of a coating film of an organic solvent solution, the thickness can be made very thin (for example, 10 ⁇ m or less).
  • the second protective layer (protective layer 30) is formed of any suitable film that can be used as a protective layer for a polarizer.
  • the material that is the main component of the film include cellulose resins such as triacetyl cellulose (TAC), polyesters, polyvinyl alcohols, polycarbonates, polyamides, polyimides, polyethersulfones, polysulfones, Examples include transparent resins such as polystyrene, polynorbornene, polyolefin, (meth)acrylic, and acetate.
  • Thermosetting resins such as (meth)acrylic, urethane, (meth)acrylic urethane, epoxy, and silicone, or ultraviolet curable resins may also be used.
  • glassy polymers such as siloxane-based polymers can also be used.
  • polymer films described in JP-A-2001-343529 can also be used. Materials for this film include, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in a side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and nitrile group in a side chain.
  • the polymer film can be, for example, an extrudate of the resin composition.
  • the protective layer 30 is typically arranged on the viewing side.
  • the protective layer 30 may be subjected to surface treatment such as hard coat treatment, anti-reflection treatment, anti-sticking treatment, anti-glare treatment, etc., as required.
  • the thickness of the second protective layer is preferably 10 ⁇ m to 50 ⁇ m, more preferably 15 ⁇ m to 35 ⁇ m. In addition, when the surface treatment is performed, the thickness of the second protective layer is the thickness including the thickness of the surface treatment layer.
  • the adhesive layer 40 can be formed using the adhesive composition described in section A above.
  • the surface resistance value of the adhesive layer 40 is 5.0 ⁇ 10 9 ⁇ / ⁇ or less, preferably 1.0 ⁇ 10 9 ⁇ / ⁇ or less, more preferably 9.0 ⁇ 10 8 as described above. ⁇ / ⁇ or less, more preferably 8.0 ⁇ 10 8 ⁇ / ⁇ or less, even more preferably 7.0 ⁇ 10 8 ⁇ / ⁇ or less, particularly preferably 6.0 ⁇ 10 8 ⁇ / ⁇ or less.
  • the surface resistance value can be, for example, 1.0 ⁇ 10 7 ⁇ / ⁇ or more. According to the embodiment of the present invention, it is possible to realize a pressure-sensitive adhesive layer with a low surface resistance value despite a low antistatic agent content.
  • the adhesive strength of the adhesive layer to glass is preferably 1.0 N/25 mm or more, more preferably 1.5 N/25 mm or more, and still more preferably 2.0 N/25 mm or more. If the adhesive strength is within such a range, the adhesiveness to the image display panel is excellent and the reworkability is excellent. Adhesion can be, for example, 4.0 N/25 mm or less.
  • the thickness of the adhesive layer is preferably 2 ⁇ m to 55 ⁇ m, more preferably 2 ⁇ m to 30 ⁇ m, still more preferably 5 ⁇ m to 25 ⁇ m, and particularly preferably 10 ⁇ m to 20 ⁇ m.
  • An image display device includes the polarizing plate described above. Accordingly, embodiments of the present invention include image display devices using such polarizing plates. Typical examples of image display devices include liquid crystal display devices and electroluminescence (EL) display devices (eg, organic EL display devices and inorganic EL display devices). In one embodiment, the image display device is a narrow frame (preferably bezelless) image display device or an in-cell image display device. In such an image display device, the effects of the embodiments of the present invention are remarkable.
  • EL electroluminescence
  • FIG. 2 is a schematic cross-sectional view of an image display device according to an embodiment of the invention.
  • This image display 300 is an in-cell liquid crystal display device.
  • the in-cell liquid crystal cell 200 includes a liquid crystal layer 90 containing liquid crystal molecules that are homogeneously aligned in the absence of an electric field, and a first transparent substrate 71 and a second transparent substrate 72 that sandwich the liquid crystal layer 90 on both sides.
  • a touch sensor section 61 is provided between the liquid crystal layer 90 and the first transparent substrate 71
  • a driving electrode/sensor section 62 is provided between the liquid crystal layer 50 and the second transparent substrate 72 .
  • the in-cell liquid crystal cell has a touch sensor portion 61 and a driving electrode/sensor portion 62 inside the liquid crystal cell, and does not have a touch sensor portion outside the liquid crystal cell. That is, no conductive layer (having a surface resistance of 1 ⁇ 10 13 ⁇ / ⁇ or less) is provided on the viewing side of the first transparent substrate 41 of the in-cell liquid crystal cell.
  • the touch sensor section 61 is arranged between the polarizer 10 and the liquid crystal layer 90, and can usually be formed on the first transparent substrate 71 as a transparent electrode pattern.
  • a transparent electrode pattern can also be formed on the drive electrode/sensor portion 62 by any appropriate method.
  • the transparent electrode pattern is normally electrically connected to a lead wire (not shown) formed at the end of the transparent substrate, and the lead wire is connected to a controller IC (not shown).
  • the shape of the transparent electrode pattern any shape such as a stripe shape, a rhombus shape, or the like can be adopted in addition to the comb shape, depending on the application.
  • the height of the transparent electrode pattern is, for example, 10 nm to 100 nm, and the width is 0.1 mm to 5 mm.
  • a conducting structure 51 can be provided on the side surface of at least one layer of the polarizing plate 100 .
  • the conductive structure 51 connects the side surface of at least one layer of the polarizing plate 100 to another suitable location, thereby suppressing the generation of static electricity.
  • Materials forming the conductive structure 51 include conductive pastes such as silver, gold or other metal pastes, conductive adhesives, or any other suitable conductive material may be used.
  • the conducting structure 51 can also be formed in a linear shape extending from the side surface of at least one layer of the polarizing plate 100 .
  • Thickness A thickness of 10 ⁇ m or less was measured using an interferometric film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD-3000”). A thickness exceeding 10 ⁇ m was measured using a digital gauge (manufactured by PEACOCK, trade name “DGN-255”).
  • ESD test The polarizing plates (polarizing plates with adhesive layer) obtained in Examples and Comparative Examples were cut into 70 mm x 150 mm pieces, and bonded to a liquid crystal panel via an adhesive layer. Next, a silver paste was applied to the side surface of the bonded polarizing plate with an adhesive layer so as to cover the entire thickness direction of the side surface of the polarizing plate with an adhesive layer, and connected to an external ground electrode. Next, on the surface of the pressure-sensitive adhesive layer-attached polarizing plate, a static electricity generator, ESD (ESD-8012A, manufactured by SANKI) was used (applied voltage 15 kV) to draw a circle every second in the plane of the polarizing plate.
  • ESD ESD-8012A, manufactured by SANKI
  • Non-alkali glass adhesive strength test The prepared polarizing plate (polarizing plate with adhesive layer) was cut into a size of 25 mm ⁇ 50 mm so that the absorption axis of the polarizer was parallel to the long side.
  • the polarizing plate was laminated to non-alkaline glass (manufactured by Corning, trade name "EG-XG") having a thickness of 170 mm ⁇ 50 mm ⁇ 0.7 mm using a laminator. Then, autoclave treatment was performed at 50° C. and 0.5 MPa for 15 minutes to adhere the adhesive layer to the glass.
  • EG-XG non-alkaline glass
  • the (meth)acrylic base polymer A1 had a Tg of ⁇ 53° C. and a dielectric constant of 5.7.
  • Polyvinyl alcohol degree of polymerization: 4,200, degree of saponification: 99.2 mol% and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOSEFIMER Z410") mixed at 9:1: 100 weight of PVA-based resin 13 parts by weight of potassium iodide was added to parts by weight, and dissolved in water to prepare an aqueous PVA solution (coating solution). The above PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60° C. to form a PVA-based resin layer having a thickness of 13 ⁇ m, thereby producing a laminate.
  • the obtained laminate was uniaxially stretched 2.4 times at the free end in the machine direction (longitudinal direction) between rolls with different peripheral speeds in an oven at 130° C. (in-air auxiliary stretching treatment).
  • the laminate was immersed in an insolubilizing bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40° C. for 30 seconds (insolubilizing treatment).
  • the finally obtained polarizer is added to a dyeing bath (iodine aqueous solution obtained by blending iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C.
  • the film was uniaxially stretched so that the total draw ratio was 5.5 times (underwater stretching treatment).
  • the laminate was immersed in a washing bath (aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 20° C. (washing treatment).
  • washing treatment aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water
  • drying treatment while drying in an oven kept at 90° C., it was brought into contact with a heating roll made of SUS whose surface temperature was kept at 75° C. for about 2 seconds
  • the shrinkage ratio in the width direction of the laminate due to the drying shrinkage treatment was 5.2%.
  • a polarizer having a thickness of 7 ⁇ m was formed on the resin substrate.
  • HC-TAC film (second protective layer) as a protective layer is placed on the surface of the polarizer obtained above (the surface opposite to the resin base material) via an ultraviolet curable adhesive. pasted together. Specifically, the curable adhesive was applied so as to have a total thickness of 1.0 ⁇ m, and was bonded using a roll machine. After that, UV rays were applied from the protective layer side to cure the adhesive.
  • the HC-TAC film is a film in which a hard coat (HC) layer (thickness 7 ⁇ m) is formed on a triacetyl cellulose (TAC) film (thickness 25 ⁇ m), and is attached so that the TAC film faces the polarizer side. Matched.
  • Methyl methacrylate (MMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "methyl methacrylate monomer”) 97.0 parts, 3.0 parts of the copolymerization monomer represented by the above general formula (1e), polymerization initiation
  • an agent trade name “2,2′-azobis(isobutyronitrile)” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • a polymerization reaction was carried out for 5.5 hours while heating at 70° C. in a nitrogen atmosphere to obtain a boron-containing acrylic resin solution (solid concentration: 33%).
  • the resulting boron-containing acrylic polymer had a Tg of 110°C and an Mw of 80,000. 20 parts of the obtained boron-containing acrylic resin was dissolved in 80 parts of methyl ethyl ketone to obtain a resin solution (20%). Next, the resin substrate is peeled off, and a resin solution is applied to the surface from which the resin substrate has been peeled off using a wire bar. A protective layer (first protective layer) configured as a solidified product was formed to obtain a polarizing plate.
  • Antistatic agent 1 lithium bis(trifluoromethanesulfonyl)imide (LiTFSi) , trade name: LiTFSi30EA, manufactured by Mitsubishi Materials Corporation) 3 parts, benzoyl peroxide as a cross-linking agent (trade name: Nyper BMT 40SV, manufactured by NOF Corporation) 0.3 parts, isocyanate-based cross-linking agent (trade name: Takenate D160N, manufactured by Mitsui Chemicals Co., Ltd.) 0.2 parts, polyoxyethylene sorbitan fatty acid ester (trade name: Rhodol TW-L120, manufactured by Kao Corporation) 0.03 parts, antioxidant (trade name: Irganox 1010, Hindered 0.3 part of a phenolic adhesive (manufactured by BASF Japan Ltd.) was blended to prepare a solution of an acrylic pressure-sensitive adhesive composition.
  • antioxidant trade name: Irganox 1010, Hindered 0.3 part of a phenolic adhesive (manufactured by BA
  • Example 2 and 3 A polarizing plate with an adhesive layer was produced in the same manner as in Example 1 except that the amount of the antistatic agent added was changed to the amount shown in Table 1.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Examples 4-6 A polarizing plate with an adhesive layer was produced in the same manner as in Examples 1 to 3, except that (meth)acrylic base polymer A2 was used instead of (meth)acrylic base polymer A1.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Examples 7-9 A polarizing plate with an adhesive layer was produced in the same manner as in Examples 1 to 3, except that (meth)acrylic base polymer A3 was used instead of (meth)acrylic base polymer A1.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Example 10 Polarized light with adhesive layer in the same manner as in Example 1 except that (meth)acrylic base polymer A4 was used instead of (meth)acrylic base polymer A1 and the amount of the antistatic agent added was 2 parts. A plate was made. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Example 11 The pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 except that the (meth)acrylic base polymer A5 was used in place of the (meth)acrylic base polymer A1 and the amount of the antistatic agent added was 1.5 parts. A polarizing plate was prepared. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Example 12 A polarizing plate with an adhesive layer was produced in the same manner as in Example 7, except that the amount of the antistatic agent added was 0.1 parts.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Example 13 In the same manner as in Example 12, except that 0.2 parts of silane coupling agent 1 (trade name: A-100, manufactured by Soken Chemical Co., Ltd., an acetoacetyl group-containing silane coupling agent) was further added to the adhesive composition. A polarizing plate with an adhesive layer was produced. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • silane coupling agent 1 trade name: A-100, manufactured by Soken Chemical Co., Ltd., an acetoacetyl group-containing silane coupling agent
  • Example 14 In the same manner as in Example 7, except that 0.03 parts of silane coupling agent 1 (trade name: A-100, manufactured by Soken Chemical Co., Ltd., an acetoacetyl group-containing silane coupling agent) was further added to the adhesive composition. A polarizing plate with an adhesive layer was produced. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • silane coupling agent 1 trade name: A-100, manufactured by Soken Chemical Co., Ltd., an acetoacetyl group-containing silane coupling agent
  • Example 15 In the same manner as in Example 7, except that 0.2 parts of silane coupling agent 1 (trade name: A-100, manufactured by Soken Chemical Co., Ltd., an acetoacetyl group-containing silane coupling agent) was further added to the adhesive composition. A polarizing plate with an adhesive layer was produced. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • silane coupling agent 1 trade name: A-100, manufactured by Soken Chemical Co., Ltd., an acetoacetyl group-containing silane coupling agent
  • Example 16 A polarizing plate with an adhesive layer was prepared in the same manner as in Example 15 except that 0.2 parts of silane coupling agent 2 (trade name: X41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.) was added instead of silane coupling agent 1. was made. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • silane coupling agent 2 trade name: X41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 17 A polarizing plate with an adhesive layer was prepared in the same manner as in Example 15 except that 0.2 parts of silane coupling agent 3 (trade name: X41-1056, manufactured by Shin-Etsu Chemical Co., Ltd.) was added instead of silane coupling agent 1. was made. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • silane coupling agent 3 trade name: X41-1056, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 18 Example 15 except that 0.2 parts of silane coupling agent 4 (trade name: KBM403, manufactured by Shin-Etsu Silicone Co., Ltd., a silane coupling agent having an epoxy group as an organic functional group) was added instead of silane coupling agent 1.
  • a polarizing plate with an adhesive layer was produced in the same manner as in the above.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Example 19 A polarizing plate with an adhesive layer was produced in the same manner as in Example 7 except that 3 parts of antistatic agent 2 (trade name: Elexel AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of antistatic agent 1.
  • antistatic agent 2 trade name: Elexel AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Example 20 Implemented except that 8.5 parts of antistatic agent 3 (tributylmethylammonium bis(trifluoromethanesulfonyl)imide (TBMA-TFSI), trade name: FC-4400, manufactured by Orwell) was used instead of antistatic agent 1.
  • antistatic agent 3 tributylmethylammonium bis(trifluoromethanesulfonyl)imide (TBMA-TFSI), trade name: FC-4400, manufactured by Orwell
  • FC-4400 trade name: FC-4400
  • Example 21 The pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 except that the (meth)acrylic base polymer A6 was used instead of the (meth)acrylic base polymer A1 and the amount of the antistatic agent added was 0.8 parts. A polarizing plate was prepared. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Example 7 Example 7 except that an acrylic adhesive (trade name: SK2137, manufactured by Soken Kagaku Co., Ltd.) was used instead of the (meth)acrylic base polymer A3, and that the amount of the antistatic agent added was 12 parts.
  • a polarizing plate with an adhesive layer was produced in the same manner as in the above.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Comparative Example 3 A polarizing plate with an adhesive layer was produced in the same manner as in Comparative Example 1, except that 24 parts of Antistatic Agent 3 was used instead of Antistatic Agent 1.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Example 4 A polarizing plate with an adhesive layer was produced in the same manner as in Example 13, except that 0.03 part of rework improver 1 (trade name: Silyl SAT10, manufactured by Kaneka Corporation) was used instead of polyoxyethylene sorbitan fatty acid ester. .
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Comparative Example 5 A polarizing plate with an adhesive layer was produced in the same manner as in Comparative Example 4, except that 0.03 part of rework improver 2 (trade name: Rheodol O-106V, manufactured by Kao Corporation) was used instead of rework improver 1. .
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Comparative Example 6 A polarizing plate with an adhesive layer was produced in the same manner as in Comparative Example 4, except that the amount of rework improver 2 added was changed to 1 part.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Comparative Example 7 A pressure-sensitive adhesive layer-attached polarizing plate was produced in the same manner as in Comparative Example 6, except that Rework Improver 3 (trade name: Rhodol SP-L110, manufactured by Kao Corporation) was used instead of Rework Improver 2. The pressure-sensitive adhesive layer-attached polarizing plate thus obtained was subjected to the above evaluations (2) to (5). Table 1 shows the results.
  • Rework Improver 3 trade name: Rhodol SP-L110, manufactured by Kao Corporation
  • the polarizing plate of the present invention is suitably used for image display devices such as liquid crystal display devices, organic EL display devices and inorganic EL display devices.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)
PCT/JP2022/025980 2021-08-27 2022-06-29 粘着剤組成物、偏光板およびそれを用いた画像表示装置 WO2023026687A1 (ja)

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CN202280057639.6A CN117836387A (zh) 2021-08-27 2022-06-29 粘合剂组合物、偏振片及使用了该偏振片的图像显示装置

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JP2012502128A (ja) * 2008-09-04 2012-01-26 ビーエーエスエフ ソシエタス・ヨーロピア グリセリンモノステアレートの存在下での沈殿重合
CN106832104A (zh) * 2017-01-11 2017-06-13 无锡海特新材料研究院有限公司 耐高温铝箔用聚丙烯酸酯压敏胶乳液及其用途和制法
JP2018525450A (ja) * 2015-05-18 2018-09-06 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ポリマー及びそのポリマーを含む組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012502128A (ja) * 2008-09-04 2012-01-26 ビーエーエスエフ ソシエタス・ヨーロピア グリセリンモノステアレートの存在下での沈殿重合
JP2018525450A (ja) * 2015-05-18 2018-09-06 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ポリマー及びそのポリマーを含む組成物
CN106832104A (zh) * 2017-01-11 2017-06-13 无锡海特新材料研究院有限公司 耐高温铝箔用聚丙烯酸酯压敏胶乳液及其用途和制法

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