CN107011834B - Adhesive composition, adhesive member, optical member, and electronic member - Google Patents

Adhesive composition, adhesive member, optical member, and electronic member Download PDF

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Publication number
CN107011834B
CN107011834B CN201710060214.1A CN201710060214A CN107011834B CN 107011834 B CN107011834 B CN 107011834B CN 201710060214 A CN201710060214 A CN 201710060214A CN 107011834 B CN107011834 B CN 107011834B
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weight
adhesive composition
meth
acrylate
polymer
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CN107011834A (en
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佐佐木翔悟
徐创矢
设乐浩司
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Nitto Denko Corp
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Nitto Denko Corp
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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
    • C09J133/06—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
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic 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
    • C09J7/00—Adhesives in the form of films or foils
    • 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
    • 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
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

The invention relates to an adhesive composition, an adhesive member, an optical member, and an electronic member. The adhesive composition of the present invention comprises a polymer (A) having a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms as an alkyl ester moiety and a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule, wherein when the molar content ratio of NCO groups in the adhesive composition is [ NCO ], the molar content ratio of epoxy groups in the adhesive composition is [ epoxy groups ], the molar content ratio of OH groups in the adhesive composition is [ OH ], and the molar content ratio of COOH groups in the adhesive composition is [ COOH ] ([ NCO + ] [ epoxy ]/([ OH ] + [ COOH ]) < 0.05.

Description

Adhesive composition, adhesive member, optical member, and electronic member
Technical Field
The present invention relates to an adhesive composition, an adhesive member having an adhesive layer formed from the adhesive composition, an optical member and an electronic member each including the adhesive member.
Background
In touch panels using LCDs, lens units of cameras, optical members such as electronic devices, and electronic members, an adhesive film may be attached to an exposed surface side in order to impart rigidity and impact resistance (for example, patent document 1). Such adhesive films generally have a substrate layer and an adhesive layer.
In the optical member and the electronic member described above, a load based on the pressing force may be applied in various cases such as during assembly, processing, transportation, and use, and the optical member and the electronic member may be damaged by the applied load.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-234460
Disclosure of Invention
Problems to be solved by the invention
The materials for forming the pressure-sensitive adhesive layer provided on such a stress dispersion film have been studied with attention to the use of a stress dispersion film having excellent stress dispersibility as the pressure-sensitive adhesive film.
The invention provides an adhesive composition for forming an adhesive layer with excellent stress dispersibility, an adhesive member with the adhesive layer formed by the adhesive composition, an optical member and an electronic member with the adhesive member.
Means for solving the problems
The adhesive composition of the present invention comprises a polymer (A) having a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with a carbon number of 1 to 20 as an alkyl ester moiety and a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in a molecule,
[ NCO ] + [ epoxy group ]/([ OH ] + [ COOH ]) <0.05 when the molar content ratio of NCO groups in the adhesive composition is [ NCO ], the molar content ratio of epoxy groups in the adhesive composition is [ epoxy group ], the molar content ratio of OH groups in the adhesive composition is [ OH ], and the molar content ratio of COOH groups in the adhesive composition is [ COOH ].
In one embodiment, the adhesive composition of the present invention contains an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having a functionality of 2 or more.
In one embodiment, the adhesive composition of the present invention comprises a polymer (B) having a monomer unit derived from a (meth) acrylate ester having an alicyclic structure represented by the general formula (1) and having a weight average molecular weight of 1000 or more and less than 30000.
CH2＝C(R1)COOR2…(1)
(in the general formula (1), R1Is a hydrogen atom or a methyl group, R2Is a hydrocarbon group having an alicyclic structure. )
In one embodiment, the adhesive layer formed from the adhesive composition has a loss tangent tan δ of 0.10 or more in the entire temperature range of-40 ℃ to 150 ℃.
The adhesive member of the present invention has an adhesive layer formed from the adhesive composition.
The optical member of the present invention includes the adhesive member.
The electronic component of the present invention includes the adhesive member.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an adhesive composition for forming an adhesive layer having excellent stress dispersibility, an adhesive member having an adhesive layer formed from the adhesive composition, an optical member and an electronic member each including the adhesive member.
Drawings
Fig. 1 is a schematic cross-sectional view of an adhesive member according to an embodiment of the present invention.
Description of the reference numerals
10 base material
20 adhesive layer
30 isolating film
100 adhesive member
Detailed Description
In the present specification, the expression "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", and the expression "(meth) acrylate" means "acrylate and/or methacrylate". In the present specification, when the expression "weight" is used, the expression "mass" may be used instead of SI-based unit representing weight.
In the case where the expression "monomer unit (a) derived from (a)" is used in the present specification, the monomer unit (a) is a structural unit formed by breaking an unsaturated double bond of the monomer (a) by polymerization. The structural unit in which the unsaturated double bond is cleaved by polymerization is a structural unit of "-RpRqC-CRrRs-" in which the unsaturated double bond "C ═ C" in the structure of "RpRqC ═ CRrRs" (Rp, Rq, Rr, Rs are any suitable groups bonded to carbon atoms by single bonds) is cleaved by polymerization.
In the present specification, the content ratio of the monomer unit in the polymer can be known by, for example, various structural analyses (for example, NMR and the like) of the polymer. Further, without performing various structural analyses as described above, the content ratio of the monomer unit derived from each monomer calculated based on the amount of each monomer used in producing the polymer can be used as the content ratio of the monomer unit in the polymer. That is, the content ratio of a certain monomer (m) in all monomer components used in producing a polymer may be treated as the content ratio of a monomer unit derived from the monomer (m) in the polymer.
Adhesive composition
The adhesive composition of the present invention comprises a polymer (A) having a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with a carbon number of 1 to 20 as an alkyl ester moiety and a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule.
The content ratio of the polymer (a) in the pressure-sensitive adhesive composition of the present invention is preferably 80 to 100% by weight, more preferably 85 to 100% by weight, even more preferably 90 to 100% by weight, particularly preferably 92.5 to 100% by weight, and most preferably 95 to 100% by weight. When the content ratio of the polymer (a) in the pressure-sensitive adhesive composition of the present invention is in the above range, a pressure-sensitive adhesive composition that forms a pressure-sensitive adhesive layer having more excellent stress dispersibility can be provided.
The polymer (A) has a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with 1-20 carbon atoms as an alkyl ester moiety. The polymer (A) may have only 1 type of monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms as an alkyl ester moiety, or may have 2 or more types.
The content ratio of the monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms as an alkyl ester moiety in the polymer (a) is preferably 90 to 99.5% by weight, more preferably 91 to 99% by weight, still more preferably 92 to 98.5% by weight, particularly preferably 93 to 98.2% by weight, and most preferably 94 to 98% by weight. When the content ratio of the monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms as an alkyl ester portion in the polymer (a) is within the above range, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety include: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and the like.
The polymer (A) has a monomer unit (II) derived from a (meth) acrylate having OH groups and/or COOH groups in the molecule. The number of monomer units (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule in the polymer (a) may be only 1, or may be 2 or more. By providing the polymer (a) with a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
The content ratio of the monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule in the polymer (a) is preferably 0.5 to 10% by weight, more preferably 1 to 9% by weight, still more preferably 1.5 to 8% by weight, particularly preferably 1.8 to 7% by weight, and most preferably 2 to 6% by weight. When the content ratio of the monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule in the polymer (a) is in the above range, an adhesive composition forming an adhesive layer having more excellent stress dispersibility can be provided.
Examples of the (meth) acrylate having an OH group in the molecule include: 2-hydroxyethyl (meth) acrylate, 2-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) methacrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like.
Examples of the (meth) acrylate having a COOH group in the molecule include: (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and the like.
The polymer (a) may have a monomer unit (III) derived from another monomer. The monomer unit (III) derived from another monomer in the polymer (a) may be only 1 kind, or may be 2 or more kinds.
Examples of the other monomers include: cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, N-acryloyl morpholine, sulfonic group-containing monomers, phosphoric group-containing monomers, acid anhydride group-containing monomers, and the like.
In the adhesive composition of the present invention, ([ NCO ] + [ epoxy group ])/([ OH ] + [ COOH ]) <0.05 when the molar content ratio of NCO groups in the adhesive composition is [ NCO ], the molar content ratio of epoxy groups in the adhesive composition is [ epoxy group ], the molar content ratio of OH groups in the adhesive composition is [ OH ], and the molar content ratio of COOH groups in the adhesive composition is [ COOH ]. By setting ([ NCO ] + [ epoxy group ])/([ OH ] + [ COOH ]) in the above range, an adhesive composition capable of forming an adhesive layer having excellent stress dispersibility can be provided. When no NCO group is present in the adhesive composition of the present invention, [ NCO ] ═ 0, and when no epoxy group is present in the adhesive composition of the present invention, [ epoxy group ] ═ 0. Namely, ([ NCO ] + [ epoxy ])/([ OH ] + [ COOH ]), the lower limit value is 0.
The adhesive composition of the present invention preferably contains an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having a functionality of 2 or more. The number of the organic polyisocyanate-based crosslinking agent and/or epoxy-based crosslinking agent having 2 or more functions which may be contained in the adhesive composition of the present invention may be only 1, or may be 2 or more.
The total content ratio of the 2-or more-functional organic polyisocyanate crosslinking agent and the epoxy crosslinking agent in the adhesive composition of the present invention is preferably 0.001 to 0.4 parts by weight, more preferably 0.0025 to 0.3 parts by weight, further preferably 0.005 to 0.2 parts by weight, particularly preferably 0.0075 to 0.15 parts by weight, and most preferably 0.01 to 0.1 parts by weight, based on 100 parts by weight of the polymer (a). When the total content ratio of the organic polyisocyanate-based crosslinking agent having 2 or more functions and the epoxy-based crosslinking agent in the adhesive composition of the present invention is in the above range with respect to 100 parts by weight of the polymer (a), an adhesive composition capable of forming an adhesive layer having more excellent stress dispersibility can be provided.
Examples of the organic polyisocyanate-based crosslinking agent having 2 or more functions include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; aromatic isocyanates such as 2, 4-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, and xylylene diisocyanate; isocyanate adducts such as trimethylolpropane/tolylene diisocyanate trimer adducts (e.g., Nippon Polyurethane Industry co., ltd., product name "CORONATE L"), trimethylolpropane/hexamethylene diisocyanate trimer adducts (e.g., Nippon Polyurethane Industry co., product name "CORONATE HL"), isocyanurate bodies of hexamethylene diisocyanate (e.g., Nippon Polyurethane Industry co., product name "CORONATE ″), and the like; and the like.
Examples of the epoxy crosslinking agent include: bisphenol a, an epichlorohydrin-type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diaminoglycidylamine, N' -tetraglycidyl-m-xylenediamine (for example, product name "tetrald-X" manufactured by mitsubishi gas chemical corporation), 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane (for example, product name "tetrald-C" manufactured by mitsubishi gas chemical corporation), and the like.
The adhesive composition of the present invention may include a polymer (B) having a monomer unit derived from an alicyclic structure-containing (meth) acrylate represented by the general formula (1) and having a weight average molecular weight of 1000 or more and less than 30000.
CH2＝C(R1)COOR2…(1)
(in the general formula (1), R1Is a hydrogen atom or a methyl group, R2Is a hydrocarbon group having an alicyclic structure. )
The number of the polymers (B) may be only 1, or may be 2 or more.
The weight average molecular weight of the polymer (B) is preferably 1000 to 30000, more preferably 1250 to 25000, further preferably 1500 to 20000, particularly preferably 1750 to 15000, and most preferably 2000 to 10000. By making the weight average molecular weight of the polymer (B) within the above range, it is possible to provide an adhesive composition that forms an adhesive layer having more excellent stress dispersibility even if the amount of the crosslinking agent is increased.
The content ratio of the polymer (B) in the adhesive composition of the present invention is preferably 0.5 to 50 parts by weight, more preferably 1 to 45 parts by weight, even more preferably 2 to 40 parts by weight, particularly preferably 3 to 35 parts by weight, and most preferably 4 to 30 parts by weight, based on 100 parts by weight of the polymer (a). By setting the content ratio of the polymer (B) in the adhesive composition of the present invention within the above range with respect to 100 parts by weight of the polymer (a), an adhesive composition forming an adhesive layer having more excellent stress dispersibility can be provided even if the amount of the crosslinking agent is increased.
The content ratio of the monomer unit derived from the alicyclic structure-containing (meth) acrylate represented by the general formula (1) in the polymer (B) is preferably 40 to 99.5% by weight, more preferably 42.5 to 99% by weight, still more preferably 45 to 98.5% by weight, particularly preferably 47.5 to 98% by weight, and most preferably 50 to 97.5% by weight. By setting the content ratio of the monomer unit derived from the alicyclic structure-containing (meth) acrylate represented by the general formula (1) in the polymer (B) within the above range, an adhesive composition forming an adhesive layer having more excellent stress dispersibility can be provided even if the amount of the crosslinking agent is increased.
Examples of the alicyclic structure-containing (meth) acrylate represented by the above general formula (1) include: cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl methacrylate, dicyclopentanyloxyethyl acrylate, tricyclopentanyl methacrylate, tricyclopentanyl acrylate, 1-adamantyl methacrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, and the like.
The polymer (B) may have a monomer unit (IV) derived from other monomer. The number of the monomer units (IV) derived from other monomers in the polymer (B) may be only 1, or may be 2 or more.
Examples of other monomers that may be contained in the polymer (B) include: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and the like.
The polymer (a) and the polymer (B) can be produced by any appropriate method within a range not impairing the effects of the present invention. Examples of such a production method include: solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (active energy ray polymerization), and the like. Among these production methods, solution polymerization is preferable from the viewpoint of cost and productivity. The polymer (a) obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like. The polymer (B) obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.
Examples of the method of solution polymerization include a method of dissolving a monomer component, a polymerization initiator, and the like in a solvent, and heating and polymerizing the solution to obtain a polymer solution.
The heating temperature in the heating polymerization in the solution polymerization is, for example, 50 to 90 ℃. The heating time in the solution polymerization is, for example, 1 to 24 hours.
As the solvent used in the solution polymerization, any appropriate solvent may be used within a range not impairing the effects of the present invention. Examples of such solvents include: aromatic hydrocarbons such as toluene, benzene, and xylene; esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and organic solvents, and the like. The number of the solvents may be only 1, or 2 or more.
A polymerization initiator may be used for producing the polymer (a) or the polymer (B). Such a polymerization initiator may be only 1 kind, or may be 2 or more kinds. Examples of such a polymerization initiator include: azo initiators such as 2,2 ' -azobisisobutyronitrile, 2 ' -azobis (2-amidinopropane) dihydrochloride, 2 ' -azobis [2- (5-methyl-2-imidazolin-2-yl) propane ] dihydrochloride, 2 ' -azobis (2-methylpropionamidine) disulfate, 2 ' -azobis (N, N ' -dimethyleneisobutylamidine), and 2,2 ' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] hydrate (Wako pure chemical industries, Ltd., VA-057); persulfates such as potassium persulfate and ammonium persulfate; peroxide initiators such as di (2-ethylhexyl) peroxycarbonate, di (4-tert-butylcyclohexyl) peroxycarbonate, di-sec-butyl peroxycarbonate, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, tert-butyl peroxyisobutyrate, 1-di (tert-hexyl peroxy) cyclohexane, tert-butyl hydroperoxide, and hydrogen peroxide; redox initiators comprising a combination of a peroxide and a reducing agent, such as a combination of persulfate and sodium bisulfite and a combination of a peroxide and sodium ascorbate; and the like.
As for the amount of the polymerization initiator, any appropriate amount may be employed within a range not impairing the effects of the present invention. Such an amount is preferably 0.01 to 5 parts by weight per 100 parts by weight of the monomer component.
In the production of the polymer (a) and the polymer (B), a chain transfer agent may be used. Such a chain transfer agent may be only 1 kind, or may be 2 or more kinds. Examples of such a chain transfer agent include: lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, methyl thioglycolate, 2-ethylhexyl thioglycolate, 2, 3-dimercapto-1-propanol, and the like.
The amount of the chain transfer agent may be any appropriate amount within a range not impairing the effects of the present invention. Such an amount is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the monomer component.
In the production of the polymer (a) and the polymer (B), any other suitable additive that can be generally used in polymerization reactions can be used.
The adhesive composition of the invention may comprise a crosslinking catalyst. As the crosslinking catalyst, any suitable crosslinking catalyst may be used within a range not impairing the effects of the present invention. Examples of such a crosslinking catalyst include: metal-based crosslinking catalysts (particularly tin-based crosslinking catalysts) such as tetra-n-butyl titanate, tetra-isopropyl titanate, iron acetylacetonate, butyl tin oxide, and dioctyltin laurate. The crosslinking catalyst may be only 1 kind or 2 or more kinds.
The amount of the crosslinking catalyst to be used may be any appropriate amount within a range not impairing the effects of the present invention. Such an amount is preferably 0.001 to 0.05 parts by weight per 100 parts by weight of the monomer component, for example.
The adhesive composition of the present invention may contain any other suitable additive within a range not impairing the effects of the present invention. Examples of such other additives include: silane coupling agents, crosslinking retarders, emulsifiers, colorants, powders such as pigments, dyes, surfactants, plasticizers, adhesion imparting agents, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic fillers, organic fillers, metal powders, granules, foils, and the like. Such other additives may be only 1 kind or 2 or more kinds.
In the adhesive composition of the present invention, it is preferable that the loss tangent tan δ of the adhesive layer formed by curing the adhesive composition is 0.10 or more over the entire temperature range of-40 to 150 ℃. By setting the loss tangent tan delta to 0.10 or more in the whole temperature range of-40 ℃ to 150 ℃, the adhesive composition can be provided which forms an adhesive layer with more excellent stress dispersion. The method for measuring the loss tangent tan δ will be described later.
In the adhesive composition of the present invention, the upper limit of the loss tangent tan δ of the adhesive layer formed by curing the adhesive composition is preferably 2.40 or less, more preferably 2.20 or less, further preferably 2.00 or less, and particularly preferably 1.80 or less, over the entire temperature range of-40 ℃ to 150 ℃. When the upper limit of the loss tangent tan δ is within the above range, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
The lower limit of the loss tangent tan δ of the pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition in the pressure-sensitive adhesive composition of the present invention is preferably 0.12 or more, more preferably 0.14 or more, still more preferably 0.16 or more, and particularly preferably 0.18 or more, over the entire temperature range of-40 ℃ to 150 ℃. When the lower limit of the loss tangent tan δ is within the above range, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
Adhesive Member of
The adhesive member of the present invention has an adhesive layer formed of the adhesive composition of the present invention.
The adhesive member of the present invention may be formed of only the adhesive layer, or may contain the adhesive layer and other members.
In the pressure-sensitive adhesive member of the present invention, when the pressure-sensitive adhesive layer is exposed as the outermost layer, an arbitrary appropriate release film (release sheet) may be provided on the exposed surface side. The separator (release sheet) may also serve as a substrate described later.
The adhesive layer is formed from the adhesive composition of the present invention. For example, the adhesive composition of the present invention is applied to any appropriate substrate, and dried as necessary to form an adhesive layer on the substrate. Then, if the substrate is peeled off, the adhesive member of the present invention formed of only the adhesive layer can be obtained. In addition, for example, the adhesive composition of the present invention is applied to any appropriate substrate, dried as necessary, and an adhesive layer is formed on the substrate, and the substrate is left as it is, thereby obtaining an adhesive member including the adhesive layer and the substrate. For example, the adhesive composition of the present invention is applied to an arbitrary appropriate substrate, dried as necessary, and formed into an adhesive layer on the substrate, and the substrate is peeled off to place the adhesive layer on another member (for example, another substrate), thereby obtaining an adhesive member including the adhesive layer and the substrate. In addition, for example, the adhesive composition of the present invention is applied to any appropriate substrate, dried as necessary, to form an adhesive layer on the substrate, and the adhesive layer formed on the substrate is transferred to another member (for example, another substrate), thereby obtaining an adhesive member including the adhesive layer and the substrate.
Examples of the method for applying the adhesive composition include: roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.
The substrate may be formed of a single layer or a plurality of layers. The substrate may be stretched.
The thickness of the substrate may be set to any appropriate thickness according to the application. From the viewpoint of sufficiently exhibiting the effect of the present invention, the thickness of the base material is preferably 4 to 500 μm, more preferably 10 to 400 μm, still more preferably 15 to 350 μm, and particularly preferably 20 to 300 μm.
As the material of the substrate, any suitable material may be used depending on the application. Examples of such materials include: plastic, paper, metal film, nonwoven fabric, and the like. Among such materials, plastic is preferable in terms of further exhibiting the effects of the present invention.
Examples of the plastic include: polyester-based resins, polyolefin-based resins, polyamide-based resins, polyimide-based resins, and the like. Examples of the polyester resin include: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. Examples of the polyolefin-based resin include: homopolymers of olefin monomers, copolymers of olefin monomers, and the like. Specific examples of the polyolefin-based resin include: homopolymerizing propylene; block, random, graft, and other propylene copolymers containing an ethylene component as a copolymer component; reactive TPO; ethylene polymers of low density, high density, linear low density, ultra low density, and the like; ethylene copolymers such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl methacrylate copolymers; and the like. Among these plastics, a polyester resin is preferable, and polyethylene terephthalate is more preferable, from the viewpoint of further exhibiting the effects of the present invention.
The substrate may contain any suitable additive as required. Examples of additives that may be contained in the base material include: antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The kind, number, and amount of the additives that can be contained in the base material can be appropriately set according to the purpose.
Fig. 1 is a schematic cross-sectional view of an adhesive member according to an embodiment of the present invention. In fig. 1, an adhesive member 100 of the present invention is formed of a substrate 10, an adhesive layer 20, and a separator 30.
Optical and electronic Components
The adhesive member of the present invention has an adhesive layer excellent in stress dispersibility. Therefore, the resin composition can be suitably used as a protective material for the purpose of protecting an optical member and an electronic member from an impact from the outside. That is, the optical member of the present invention includes the adhesive member of the present invention. The electronic component of the present invention includes the adhesive member of the present invention.
[ examples ]
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples at all. The test and evaluation methods in examples and the like are as follows. In the case where "part" is described, unless otherwise specified, "part by weight" is meant, and in the case where "%" is described, "wt%" is meant, unless otherwise specified.
< measurement of weight average molecular weight >
The weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus (HLC-8220GPC) manufactured by TOSOH CORPORATION. The weight average molecular weight (Mw) is determined by a polystyrene equivalent.
The measurement conditions are as follows.
Sample concentration: 0.2 wt% (THF solution)
Sample injection amount: 10 μ l of eluate
Flow rate of THF: 0.6 ml/min
Measuring temperature: 40 deg.C
Sample column: TSKguardcolumn SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 roots)
Reference column: TSKgelSuperH-RC (1 root)
A detector: differential Refractometer (RI)
< preparation of pressure-sensitive adhesive sheet >
The pressure-sensitive adhesive composition obtained by applying a pressure-sensitive adhesive composition onto a release-treated surface of a 38 μm thick polyester film (trade name: MRF, manufactured by Mitsubishi chemical polyester Co., Ltd.) whose one surface was release-treated with silicone so that the thickness after drying became 50 μm by a fountain roll was cured at a drying temperature of 130 ℃ for a drying time of 3 minutes and dried. In this manner, an adhesive layer is formed on the substrate. Then, a 38 μm thick polyester film (trade name: MRF, manufactured by Mitsubishi chemical polyester Co., Ltd.) having one surface thereof treated with a release treatment was coated on the surface of the pressure-sensitive adhesive layer so that the release-treated surface of the film was on the pressure-sensitive adhesive layer side. In this manner, a pressure-sensitive adhesive sheet was produced.
< measurement of glass transition temperature (Tg), storage modulus, loss modulus, tan delta >
The measurement was carried out by the following method using a dynamic viscoelasticity measuring apparatus (ARES, manufactured by Rheometrics).
Only the pressure-sensitive adhesive layer was taken out of the obtained pressure-sensitive adhesive sheet and laminated to form a thickness of about 2mm, and the sheet was punched out to 7.9mm in diameter to prepare cylindrical pellets as a sample for measurement. The measurement sample was fixed to a jig having a parallel plate diameter of 7.9mm, and the temperature dependence of the storage modulus G 'and the loss modulus G "was measured by the dynamic viscoelasticity measuring apparatus, and tan δ was calculated as tan δ ═ G"/G'. The temperature at which the obtained tan δ curve becomes maximum was defined as the glass transition temperature (Tg) (° c).
The measurement conditions are as follows.
And (3) determination: shear mode
Temperature range: -70 ℃ to 150 DEG C
Temperature rise rate: 5 ℃ per minute
Frequency: 1Hz
[ production example 1 ]: (meth) acrylic acid-based Polymer (1)
To a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, 2-ethylhexyl acrylate (Nippon Shokubai co., ltd.): 100 parts by weight of 2-hydroxyethyl acrylate (manufactured by Toyo Synthesis Co., Ltd.): 4 parts by weight of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part by weight, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (1) solution (40% by weight) having a weight-average molecular weight of 55 ten thousand was prepared by conducting polymerization for 6 hours while keeping the liquid temperature in the flask at about 65 ℃ by introducing nitrogen gas while stirring slowly.
[ production example 2 ]: (meth) acrylic acid-based Polymer (2)
To a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, 2-ethylhexyl acrylate (Nippon Shokubai co., ltd.): 100 parts by weight of 4-hydroxybutyl acrylate (manufactured by Osaka organic chemical industries, Ltd.): 10 parts by weight, acrylic acid (manufactured by Toyo Synthesis Co., Ltd.): 0.02 part by weight of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part by weight, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (2) solution (40% by weight) having a weight-average molecular weight of 54 ten thousand was prepared by conducting polymerization for 6 hours while keeping the liquid temperature in the flask at about 65 ℃ by introducing nitrogen gas while stirring slowly.
[ production example 3 ]: (meth) acrylic acid-based Polymer (3)
Butyl acrylate (Nippon Shokubai co., ltd.): 99 parts by weight of 4-hydroxybutyl acrylate (manufactured by Osaka organic chemical Co., Ltd.): 1 part by weight of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 1 part by weight, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (3) solution (39% by weight) having a weight-average molecular weight of 160 ten thousand was prepared by conducting polymerization for 7 hours while keeping the liquid temperature in the flask at about 60 ℃ by introducing nitrogen gas while stirring slowly.
[ production example 4 ]: (meth) acrylic acid-based Polymer (4)
Butyl acrylate (Nippon Shokubai co., ltd.): 92 parts by weight, N-acryloyl morpholine (Kohjin co., manufactured by Ltd.): 5 parts by weight, acrylic acid (manufactured by Toyo Synthesis Co., Ltd.): 2.9 parts by weight of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.1 part by weight, ethyl acetate: 200 parts by weight of the (meth) acrylic polymer (4) having a weight-average molecular weight of 180 ten thousand was prepared as a solution (33% by weight) by conducting polymerization for 8 hours while introducing nitrogen gas while slowly stirring the solution and maintaining the liquid temperature in the flask at about 55 ℃.
[ production example 5 ]: (meth) acrylic acid Polymer (5)
Butyl acrylate (Nippon Shokubai co., ltd.): 95 parts by weight, acrylic acid (manufactured by Toyo Synthesis Co., Ltd.): 5 parts by weight of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part by weight, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (5) solution (40% by weight) having a weight-average molecular weight of 70 ten thousand was prepared by conducting polymerization for 10 hours while keeping the liquid temperature in the flask at about 63 ℃ by introducing nitrogen gas while stirring slowly.
[ production example 6 ]: (meth) acrylic polymer having an alicyclic structure (6)
The glass transition temperature of cyclohexyl methacrylate [ homopolymer (polycyclohexyl methacrylate) ] as a monomer component was measured: 66 ℃ C. ]: 95 parts by weight, acrylic acid: 5 parts by weight of 2-mercaptoethanol as a chain transfer agent: 3 parts by weight of 2, 2' -azobisisobutyronitrile as a polymerization initiator: 0.2 parts by weight, and toluene as a polymerization solvent: 103.2 parts by weight of the reaction solution was put into a separable flask, and stirred for 1 hour while introducing nitrogen gas. In this manner, after removing oxygen in the polymerization system, the temperature was raised to 70 ℃ to allow reaction for 3 hours, and further, the reaction was allowed to proceed at 75 ℃ for 2 hours to obtain a solution (50 wt%) of (meth) acrylic polymer (6) having a weight average molecular weight of 4000.
[ production example 6 ]: (meth) acrylic polymer (7) having an alicyclic structure
Into a 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, a condenser, and a dropping funnel, toluene: 100 parts by weight of dicyclopentyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi chemical Co., Ltd.): 60 parts by weight, Methyl Methacrylate (MMA): 40 parts by weight, and methyl thioglycolate as a chain transfer agent: 3.5 parts by weight. Then, after stirring at 70 ℃ for 1 hour under a nitrogen atmosphere, 2' -azobisisobutyronitrile: 0.2 part by weight, and reacted at 70 ℃ for 2 hours, then at 80 ℃ for 4 hours, and then at 90 ℃ for 1 hour to obtain a solution (51% by weight) of a (meth) acrylic polymer (7) having a weight average molecular weight of 4000.
[ example 1]
The solution of the (meth) acrylic polymer (1) was diluted with ethyl acetate so that the total solid content became 25 wt% with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and stirred with a disperser to obtain a pressure-sensitive adhesive composition (1) containing an acrylic resin. The results are shown in Table 1.
[ example 2 ]
To the solution of the (meth) acrylic polymer (1) were added: a binder composition (2) containing an acrylic resin was obtained by diluting 0.01 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and stirring with a disperser. The results are shown in Table 1.
[ example 3 ]
To the solution of the (meth) acrylic polymer (1) were added: a binder composition (3) containing an acrylic resin was obtained by diluting 0.1 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, based on 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and stirring with a disperser. The results are shown in Table 1.
[ example 4 ]
To the solution of the (meth) acrylic polymer (1) were added: a solution of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst, and 5 parts by weight of (meth) acrylic polymer (6) as a solid content were diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser, with respect to 100 parts by weight of the solid content of the solution of (meth) acrylic polymer (1), to obtain an adhesive composition (4) containing an acrylic resin. The results are shown in Table 1.
[ example 5 ]
To the solution of the (meth) acrylic polymer (1) were added: a solution of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst, and 5 parts by weight of (meth) acrylic polymer (6) as a solid content were diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser, with respect to 100 parts by weight of the solid content of the solution of (meth) acrylic polymer (1), to obtain an adhesive composition (5) containing an acrylic resin. The results are shown in Table 1.
[ example 6 ]
To the solution of the (meth) acrylic polymer (1) were added: a solution of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst, and 5 parts by weight of (meth) acrylic polymer (6) as a solid content were diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser, with respect to 100 parts by weight of the solid content of the solution of (meth) acrylic polymer (1), to obtain an adhesive composition (6) containing an acrylic resin. The results are shown in Table 1.
[ example 7 ]
To the solution of the (meth) acrylic polymer (1) were added: a solution of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst, and 5 parts by weight of (meth) acrylic polymer (7) in terms of solid content, based on 100 parts by weight of the solid content of the solution of (meth) acrylic polymer (1), was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser, to obtain an adhesive composition (7) containing an acrylic resin. The results are shown in Table 1.
[ example 8 ]
To the solution of the (meth) acrylic polymer (1) were added: a solution of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst, and 5 parts by weight of (meth) acrylic polymer (7) as a solid content were diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser, with respect to 100 parts by weight of the solid content of the solution of (meth) acrylic polymer (1), to obtain an adhesive composition (8) containing an acrylic resin. The results are shown in Table 1.
[ example 9 ]
The solution of the (meth) acrylic polymer (2) was diluted with ethyl acetate so that the total solid content became 25 wt% with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2), and stirred with a disperser to obtain a pressure-sensitive adhesive composition (9) containing an acrylic resin. The results are shown in Table 1.
[ example 10 ]
To the solution of the (meth) acrylic polymer (2) were added: based on 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2), 0.1 part by weight of CORONATE L (Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent in terms of solid content, 0.05 part by weight of TETRAD-C (Mitsubishi gas chemical Co., Ltd.) in terms of solid content, and 0.005 part by weight of ferric acetylacetonate (Nippon chemical Co., Ltd.) as a crosslinking catalyst in terms of solid content were diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser to obtain an acrylic resin-containing adhesive composition (10). The results are shown in Table 1.
[ example 11 ]
To the solution of the (meth) acrylic polymer (3) were added: a binder composition (11) containing an acrylic resin was obtained by diluting 0.02 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (3), and stirring with a disperser. The results are shown in Table 1.
[ example 12 ]
To the solution of the (meth) acrylic polymer (4) were added: a binder composition (12) containing an acrylic resin was obtained by diluting 0.3 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (4), and stirring with a disperser. The results are shown in Table 1.
[ example 13 ]
To the solution of the (meth) acrylic polymer (5) were added: the binder composition (13) containing an acrylic resin was obtained by diluting with ethyl acetate and stirring with a disperser so that the total solid content became 25 wt%, based on 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (5), 0.075 parts by weight in terms of solid content of tetra d-C (manufactured by mitsubishi gas chemical corporation) as a crosslinking agent, and 0.005 parts by weight in terms of solid content of iron acetylacetonate (manufactured by japan chemical industry co., ltd.) as a crosslinking catalyst. The results are shown in Table 1.
[ example 14 ]
To the solution of the (meth) acrylic polymer (5) were added: an adhesive composition (14) containing an acrylic resin was obtained by diluting a solution of a (meth) acrylic polymer (5) containing 100 parts by weight of the solid content, 0.075 part by weight of TETRAD-C (manufactured by Mitsubishi gas chemical Co., Ltd.) as a crosslinking agent in terms of solid content, 0.005 part by weight of ferric acetylacetonate (manufactured by Nippon chemical industries Co., Ltd.) as a crosslinking catalyst in terms of solid content, and 20 parts by weight of a solution of a (meth) acrylic polymer (6) in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, and stirring the diluted solution with a disperser. The results are shown in Table 1.
[ comparative example 1]
To the solution of the (meth) acrylic polymer (1) were added: a binder composition (C1) containing an acrylic resin was obtained by diluting 0.5 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and stirring with a disperser. The results are shown in Table 1.
[ comparative example 2 ]
To the solution of the (meth) acrylic polymer (2) were added: based on 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2), 0.45 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of solid content, 0.3 parts by weight of TETRAD-C (manufactured by mitsubishi gas chemical corporation) in terms of solid content, and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical Industry co., ltd.) as a crosslinking catalyst in terms of solid content were diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser to obtain an acrylic resin-containing adhesive composition (C2). The results are shown in Table 1.
[ Table 1]
Figure BDA0001218755390000231
[ example 15 ]
A polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (1) obtained in example 1, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 16 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (2) obtained in example 2, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 17 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (4) obtained in example 4, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 18 ]
A polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (7) obtained in example 7, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 19 ]
A polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (9) obtained in example 9, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 20 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (10) obtained in example 10, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 21 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (11) obtained in example 11, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 22 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (12) obtained in example 12, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 23 ]
A polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (13) obtained in example 13, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 24 ]
A polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (14) obtained in example 14, and the resultant was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member to obtain an optical member to which the pressure-sensitive adhesive sheet was attached.
[ example 25 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (1) obtained in example 1, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 26 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (2) obtained in example 2, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 27 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (4) obtained in example 4, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 28 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (7) obtained in example 7, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 29 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (9) obtained in example 9, and the resultant was attached to a conductive film (product of ritong electrical corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 30 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (10) obtained in example 10, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 31 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (11) obtained in example 11, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 32 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (12) obtained in example 12, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 33 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (13) obtained in example 13, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
[ example 34 ]
The polyester film was peeled from one surface of the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition (14) obtained in example 14, and the resultant was attached to a conductive film (product of Nindon electric Co., Ltd., trade name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component having a pressure-sensitive adhesive sheet attached thereto.
Industrial applicability
The adhesive member having the adhesive layer formed of the adhesive composition of the present invention can be suitably used as a protective material for the purpose of protecting, for example, an optical member, an electronic member from an impact from the outside, or the like.

Claims (5)

1. An adhesive composition comprising a polymer (A) having a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with a carbon number of 1 to 20 as an alkyl ester moiety and a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in a molecule,
[ NCO ] + [ epoxy group ]/([ OH ] + [ COOH ]) <0.05 when the molar content ratio of NCO groups in the adhesive composition is [ NCO ], the molar content ratio of epoxy groups in the adhesive composition is [ epoxy group ], the molar content ratio of OH groups in the adhesive composition is [ OH ], and the molar content ratio of COOH groups in the adhesive composition is [ COOH ],
the content ratio of the monomer unit (II) derived from a (meth) acrylate having OH groups and/or COOH groups in the molecule in the polymer (A) is 0.5 to 9% by weight,
the adhesive composition comprises a polymer (B) having a monomer unit derived from a (meth) acrylate ester having an alicyclic structure represented by the general formula (1) and a weight-average molecular weight of 1000 or more and less than 30000, wherein the content ratio of the monomer unit derived from the (meth) acrylate ester having an alicyclic structure represented by the general formula (1) in the polymer (B) is 40 to 99.5% by weight,
CH2＝C(R1)COOR2…(1)
in the general formula (1), R1Is a hydrogen atom or a methyl group, R2Is a hydrocarbon group having an alicyclic structure,
wherein a loss tangent tan delta of an adhesive layer formed from the adhesive composition in the whole temperature region of-40 ℃ to 150 ℃ is 0.10 or more,
the content ratio of the polymer (B) in the adhesive composition is 0.5 to 35 parts by weight based on 100 parts by weight of the polymer (A).
2. The adhesive composition according to claim 1, wherein the adhesive composition contains an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having a functionality of 2 or more.
3. An adhesive member having an adhesive layer formed of the adhesive composition of claim 1 or 2.
4. An optical member comprising the adhesive member according to claim 3.
5. An electronic component comprising the adhesive member according to claim 3.
CN201710060214.1A 2016-01-27 2017-01-24 Adhesive composition, adhesive member, optical member, and electronic member Active CN107011834B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014152198A (en) * 2013-02-05 2014-08-25 Soken Chem & Eng Co Ltd Adhesive sheet

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5063262B2 (en) * 2006-08-30 2012-10-31 Ｄｉｃ株式会社 Re-peeling adhesive sheet
JP5277553B2 (en) * 2007-03-23 2013-08-28 Ｄｉｃ株式会社 Image display module for electronic terminal and pressure sensitive adhesive sheet
JP5118880B2 (en) * 2007-05-08 2013-01-16 日東電工株式会社 Adhesive composition, and adhesive product and display using the same
JP2009256607A (en) * 2008-03-17 2009-11-05 Nitto Denko Corp Acrylic adhesive, acrylic adhesive layer, and acrylic adhesive tape or sheet
CN102352206A (en) * 2011-09-06 2012-02-15 烟台德邦电子材料有限公司 Pressure-sensitive adhesive for polaroid
US9127188B2 (en) * 2012-12-27 2015-09-08 Cheil Industries, Inc. Adhesive film and optical display including the same
KR101600654B1 (en) * 2012-12-28 2016-03-07 제일모직주식회사 Adhesive film for polarizing plate, adhesive composition for the same, polarizing plate comprising the same and optical display comprising the same
JP6216519B2 (en) * 2013-03-04 2017-10-18 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet
WO2015141381A1 (en) * 2014-03-18 2015-09-24 綜研化学株式会社 Adhesive composition for polarizing plate, adhesive sheet and polarizing plate with adhesive layer
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Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014152198A (en) * 2013-02-05 2014-08-25 Soken Chem & Eng Co Ltd Adhesive sheet

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