CN113831867B - 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
CN113831867B
CN113831867B CN202111137217.3A CN202111137217A CN113831867B CN 113831867 B CN113831867 B CN 113831867B CN 202111137217 A CN202111137217 A CN 202111137217A CN 113831867 B CN113831867 B CN 113831867B
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adhesive composition
weight
meth
adhesive
polymer
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CN113831867A (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
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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 application provides an adhesive composition, an adhesive member, an optical member, and an electronic member. Provided are 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 having the adhesive member, and an electronic member. The adhesive composition of the present application comprises a polymer (A) having monomer units derived from an alkyl (meth) acrylate, wherein the loss tangent tan delta of an adhesive layer formed by curing the adhesive composition in the entire temperature range of-40 ℃ to 150 ℃ is 0.10 or more.

Description

Adhesive composition, adhesive member, optical member, and electronic member
The present application is a divisional application of application having application date 2017, 1-25, application number 201710060531.3, and the name "adhesive composition, adhesive member, optical member, and electronic member".
Technical Field
The present application 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 having 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 the exposed surface side in order to impart rigidity and impact resistance (for example, patent document 1). Such an adhesive film generally has a base material 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.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2014-234460
Disclosure of Invention
Problems to be solved by the invention
A study has been made on a material for forming an adhesive layer provided on such a stress-dispersing film by using a stress-dispersing film having excellent stress dispersibility as an adhesive film.
The invention provides an adhesive composition for forming an adhesive layer with excellent stress dispersion, an adhesive member having an adhesive layer formed by the adhesive composition, an optical member having the adhesive member, and an electronic member.
Solution for solving the problem
The adhesive composition of the present invention comprises a polymer (A) having monomer units derived from an alkyl (meth) acrylate, wherein,
the adhesive layer formed by curing the adhesive composition has a loss tangent tan delta of 0.10 or more over the entire temperature range of 40 ℃ to 150 ℃.
In one embodiment, the monomer unit derived from the alkyl (meth) acrylate is a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety.
In one embodiment, the polymer (a) has a monomer unit (II) derived from a (meth) acrylate having an OH group and/or COOH group in the molecule.
In one embodiment, the adhesive composition of the present invention comprises a 2-functional or more organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent.
In one embodiment, an adhesive composition comprises a polymer and an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having 2 or more functions, wherein the polymer has a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group having 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, the molar content of the NCO group in the adhesive composition is [ NCO ], the molar content of the epoxy group in the adhesive composition is [ epoxy ], and the molar content of the OH group in the adhesive composition is [ OH ], and the molar content of the COOH group in the adhesive composition is [ COOH ], 0< ([ NCO ] + [ epoxy ])/(OH ] + [ COOH ]) 0.05.
In one embodiment, the adhesive composition of the present invention comprises 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.
CH 2 ＝C(R 1 )COOR 2 …(1)
(in the general formula (1), R 1 Is a hydrogen atom or methyl group, R 2 Is a hydrocarbon group having an alicyclic structure. )
The adhesive member of the present invention has an adhesive layer formed of the above 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, an adhesive composition forming an adhesive layer excellent in stress dispersibility, an adhesive member having an adhesive layer formed from the adhesive composition, an optical member having the adhesive member, and an electronic member can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view of an adhesive member according to one embodiment of the present invention.
Description of the reference numerals
10. Substrate material
20. Adhesive layer
30. Isolation 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) acrylic acid ester" means "acrylic acid ester and/or methacrylic acid ester". In the case where the expression "weight" is used in the present specification, the expression "weight" may be replaced with "mass" which is conventionally used as SI-based unit indicating weight.
In the present specification, the expression "monomer unit (a) derived from (a)" refers to a structural unit formed by cleavage of an unsaturated double bond of the monomer (a) by polymerization. The structural unit formed by cleavage of an unsaturated double bond by polymerization means a structural unit of "-RpRqC-CRrRs-" formed by cleavage of an unsaturated double bond "c=c" of a structure of "rprqc=crrrs" (Rp, rq, rr, rs is any suitable group bonded to a carbon atom by a single bond) by polymerization.
In the present specification, the content ratio of the monomer units in the polymer can be found by, for example, various structural analyses (for example, NMR and the like) of the polymer. In addition, even if the above-described various structural analyses are not performed, the content ratio of the monomer units derived from the various monomers calculated based on the amounts of the various monomers used in the production of the polymer may be used as the content ratio of the monomer units in the polymer. That is, the content ratio of a certain monomer (m) in all the monomer components used in the production of the polymer may be treated as the content ratio of the monomer units derived from the monomer (m) in the polymer.
Adhesive composition
The adhesive composition of the present invention comprises a polymer (a) having monomer units derived from an alkyl (meth) acrylate.
The content of the polymer (a) in the adhesive composition of the present invention is preferably 80 to 100 wt%, more preferably 85 to 100 wt%, even more preferably 90 to 100 wt%, particularly preferably 92.5 to 100 wt%, and most preferably 95 to 100 wt%. By setting the content ratio of the polymer (a) in the adhesive composition of the present invention within the above range, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
In the adhesive composition of the present invention, the loss tangent tan delta of an adhesive layer formed by curing the adhesive composition in the entire temperature range of-40 ℃ to 150 ℃ is 0.10 or more. By setting the loss tangent tan delta to 0.10 or more over the entire temperature range of-40 ℃ to 150 ℃, an adhesive composition that forms an adhesive layer excellent in stress dispersibility can be provided. The method for measuring the loss tangent tan δ will be described later.
The upper limit of the loss tangent tan δ of the adhesive layer formed by curing the adhesive composition in the entire temperature range of-40 to 150 ℃ is preferably 2.40 or less, more preferably 2.20 or less, further preferably 2.00 or less, particularly preferably 1.80 or less. When the upper limit of the loss tangent tan δ is within the above range, an adhesive composition for forming an adhesive layer having more excellent stress dispersibility can be provided.
In the adhesive composition of the present invention, the lower limit of the loss tangent tan δ of the adhesive layer formed by curing the adhesive composition in the entire temperature range of-40 to 150 ℃ is preferably 0.12 or more, more preferably 0.14 or more, still more preferably 0.16 or more, particularly preferably 0.18 or more. When the lower limit of the loss tangent tan δ is within the above range, an adhesive composition for forming an adhesive layer having more excellent stress dispersibility can be provided.
The polymer (A) has monomer units derived from an alkyl (meth) acrylate. The monomer units derived from the alkyl (meth) acrylate in the polymer (a) may be 1 or 2 or more.
The content ratio of the monomer unit derived from the alkyl (meth) acrylate in the polymer (a) is preferably 90 to 99.5 wt%, more preferably 91 to 99 wt%, still more preferably 92 to 98.5 wt%, particularly preferably 93 to 98.2 wt%, and most preferably 94 to 98 wt%. By setting the content ratio of the monomer unit derived from the alkyl (meth) acrylate in the polymer (a) within the above range, an adhesive composition forming an adhesive layer having more excellent stress dispersibility can be provided.
The above monomer unit derived from an alkyl (meth) acrylate may be any suitable monomer unit derived from an alkyl (meth) acrylate within a range that does not impair the effects of the present invention. From the viewpoint of further exhibiting the effects of the present invention, the monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety is preferable.
Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as the 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) preferably has a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule. The monomer units (II) derived from the (meth) acrylate having an OH group and/or a COOH group in the molecule in the polymer (A) may be only 1 kind or may be 2 or more kinds. By providing the polymer (a) with a monomer unit (II) derived from a (meth) acrylate having an OH group and/or COOH group in the molecule, an adhesive composition forming an adhesive layer having more excellent stress dispersibility can be provided.
The content ratio of the monomer unit (II) derived from the (meth) acrylate having an OH group and/or 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. By setting the content ratio of the monomer unit (II) derived from the (meth) acrylate having an OH group and/or COOH group in the molecule in the polymer (a) within the above-described range, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
Examples of the (meth) acrylate having an OH group in a 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-hydroxyethylvinyl 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: carboxylic ethyl (meth) acrylate, carboxylic pentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and the like.
The polymer (a) may have monomer units (III) derived from other monomers. The monomer units (III) derived from other monomers in the polymer (A) may be 1 or 2 or more.
Examples of the other monomer include: cyano-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-acryloylmorpholine, sulfo-containing monomers, phosphoric acid group-containing monomers, anhydride group-containing monomers, and the like.
The adhesive composition of the present invention preferably contains an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having 2 or more functions. The organic polyisocyanate-based crosslinking agent and/or the epoxy-based crosslinking agent which may be contained in the adhesive composition of the present invention may be 1 or 2 or more.
The total content of the above-mentioned 2-functional or more organic polyisocyanate-based crosslinking agent and epoxy-based crosslinking agent in the adhesive composition of the present invention is preferably 0.001 to 0.4 part by weight, more preferably 0.0025 to 0.3 part by weight, still more preferably 0.005 to 0.2 part by weight, particularly preferably 0.0075 to 0.15 part by weight, and most preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the polymer (a). By setting the total content ratio of the 2-functional or more organic polyisocyanate-based crosslinking agent and the epoxy-based crosslinking agent in the adhesive composition of the present invention to be within the above-described range with respect to 100 parts by weight of the polymer (a), an adhesive composition having an adhesive layer with 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-toluene diisocyanate, 4' -diphenylmethane diisocyanate, and xylyl diisocyanate; isocyanate adducts such as trimethylolpropane/toluene diisocyanate trimer adducts (e.g., nippon Polyurethane Industry co., ltd., trade name "cor onate L"), trimethylolpropane/hexamethylene diisocyanate trimer adducts (e.g., nippon Polyurethane Industry co., ltd., trade name "cor onate HL"), isocyanurate bodies of hexamethylene diisocyanate (e.g., nippon Polyurethane Industry co., ltd., trade name "cor onate HX"); etc.
Examples of the epoxy-based crosslinking agent include: bisphenol A, epichlorohydrin type epoxy resins, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine-based glycidyl amine, N, N, N ', N' -tetraglycidyl-m-xylylenediamine (for example, manufactured by Mitsubishi gas chemical Co., ltd., trade name "TETRAD-X"), 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane (for example, manufactured by Mitsubishi gas chemical Co., ltd., trade name "TETRAD-C"), and the like.
The adhesive composition of the present invention preferably comprises a polymer having a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group having 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 COOH group in the molecule, and an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having 2 or more functions, wherein the molar content ratio of the NCO group in the adhesive composition is [ NCO ], the molar content ratio of the epoxy group in the adhesive composition is [ epoxy ], and the molar content ratio of the OH group in the adhesive composition is [ OH ], and when the molar content ratio of the COOH group in the adhesive composition is [ COOH ], 0+ ([ NCO ] [ epoxy ] +/[ OH ] + [ COOH ]) 0.05. By setting ([ NCO ] + [ epoxy ])/([ OH ] + [ COOH ]) in the above-described range, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
The adhesive composition of the present invention may contain 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.
CH 2 ＝C(R 1 )COOR 2 …(1)
(in the general formula (1), R 1 Is a hydrogen atom or methyl group, R 2 Is a hydrocarbon group having an alicyclic structure. )
The number of the polymers (B) may be 1 or 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 setting the weight average molecular weight of the polymer (B) within the above range, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided even if the amount of the crosslinking agent is increased.
The content 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, still 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 to be within the above range relative to 100 parts by weight of the polymer (a), even if the amount of the crosslinking agent is increased, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
The content 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 wt%, more preferably 42.5 to 99 wt%, further preferably 45 to 98.5 wt%, particularly preferably 47.5 to 98 wt%, and most preferably 50 to 97.5 wt%. 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-described range, even if the amount of the crosslinking agent is increased, an adhesive composition that forms an adhesive layer having more excellent stress dispersibility can be provided.
Examples of the alicyclic structure-containing (meth) acrylate represented by the above general formula (1) include: cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxy ethyl methacrylate, dicyclopentyloxy ethyl acrylate, tricyclopentyl methacrylate, tricyclopentyl 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 monomer units (IV) derived from other monomers. The monomer units (IV) derived from other monomers in the polymer (B) may be 1 or 2 or more.
Examples of the other monomer that can 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) may be produced by any suitable method within a range that does not impair 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 viewpoints of cost and productivity. The polymer (A) may be any of random copolymer, block copolymer, alternating copolymer, graft copolymer, and the like. The polymer (B) may be any of random copolymer, block copolymer, alternating copolymer, graft copolymer, and the like.
Examples of the method of solution polymerization include a method of obtaining a polymer solution by dissolving a monomer component, a polymerization initiator, and the like in a solvent, heating, and polymerizing.
The heating temperature at the time of the heating polymerization in the solution polymerization is, for example, 50 to 90 ℃. The heating time in the solution polymerization may be, for example, 1 to 24 hours.
Any suitable solvent may be used as the solvent used in the solution polymerization within a range that does not impair 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. The number of solvents may be 1 or 2 or more.
The polymerization initiator may be used for the production of the polymer (a) and the polymer (B). The number of such polymerization initiators may be 1 or 2 or more. Examples of such a polymerization initiator include: azo-based 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 ' -dimethylene isobutyl amidine), 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] hydrate (manufactured by Wako pure chemical industries, ltd., VA-057); persulfates such as potassium persulfate and ammonium persulfate; peroxide-based initiators such as bis (2-ethylhexyl) peroxycarbonate, bis (4-t-butylcyclohexyl) peroxycarbonate, di-sec-butylperoxycarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate, bis (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1-bis (t-hexylperoxy) cyclohexane, t-butylhydroperoxide, and hydrogen peroxide; redox initiators comprising a combination of a persulfate and sodium bisulfite, a combination of a peroxide and sodium ascorbate, and a combination of a peroxide and a reducing agent; etc.
The amount of the polymerization initiator may be any suitable amount within a range that does not impair the effects of the present invention. The 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), a chain transfer agent may be used. The chain transfer agent may be 1 or 2 or more. Examples of such chain transfer agents include: lauryl mercaptan, glycidyl mercaptan, thioglycollic acid, 2-mercaptoethanol, thioglycollic acid, methyl thioglycolate, 2-ethylhexyl thioglycolate, 2, 3-dimercapto-1-propanol, and the like.
The amount of the chain transfer agent may be any suitable amount within a range that does not impair the effects of the present invention. The amount is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the monomer component, for example.
In the production of the polymer (a) and the polymer (B), any other suitable additive that can be generally used in polymerization reaction may be used.
The adhesive composition of the present invention may contain a crosslinking catalyst. As the crosslinking catalyst, any suitable crosslinking catalyst may be used within a range that does not impair 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, butyltin oxide, and dioctyltin laurate. The crosslinking catalyst may be 1 or 2 or more.
Any suitable amount of the crosslinking catalyst may be used within a range that does not impair the effects of the present invention. The amount is preferably, for example, 0.001 to 0.05 parts by weight based on 100 parts by weight of the monomer component.
The adhesive composition of the present invention may contain any suitable other additives within a range that does not impair the effects of the present invention. Examples of such other additives include: silane coupling agents, crosslinking retarders, emulsifiers, colorants, pigments and other powders, dyes, surfactants, plasticizers, adhesion imparting agents, surface lubricants, leveling agents, softeners, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic fillers, organic fillers, metal powders, particulates, foils and the like. Such other additives may be 1 or 2 or more.
B. adhesive Member
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 an adhesive layer, or may include an adhesive layer and other members.
In the pressure-sensitive adhesive member of the present invention, in the case where the pressure-sensitive adhesive layer is exposed as the outermost layer, any suitable separator (release sheet) may be provided on the exposed surface side. The separator (release sheet) may also serve as a base material 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 if necessary, dried to form an adhesive layer on the substrate. Then, if the base material is peeled off, the adhesive member of the present invention formed only of the adhesive layer can be obtained. 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 comprising the adhesive layer and the substrate. 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 peeled off to obtain an adhesive layer, which is then placed on another member (for example, another substrate), thereby obtaining an adhesive member comprising the adhesive layer and the substrate. 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 adhesive layer formed on the substrate is transferred to another member (for example, another substrate) to obtain 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 may be formed of multiple layers. The substrate may be stretched.
The thickness of the base material may be set to any appropriate thickness according to the application. From the viewpoint of sufficiently exhibiting the effects of the present invention, the thickness of the base material is preferably 4 μm to 500 μm, more preferably 10 μm to 400 μm, still more preferably 15 μm to 350 μm, particularly preferably 20 μm to 300 μm.
As the material of the base material, any appropriate material may be used depending on the application. Examples of such a material include: plastic, paper, metal film, nonwoven, and the like. Among these materials, plastics are preferable in that the effects of the present invention can be further exhibited.
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 resin include: homopolymers of olefin monomers, copolymers of olefin monomers, and the like. Specific examples of the polyolefin resin include: homo-polypropylene; propylene copolymers of block, random, graft and the like containing an ethylene component as a copolymerization component; reactive TPO; low density, high density, linear low density, ultra low density, etc.; ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, and other ethylene-based copolymers; etc. Among these, polyester resins are 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 additives as desired. Examples of the additive that may be contained in the base material include: antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The type, 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 one embodiment of the present invention. In fig. 1, an adhesive member 100 of the present invention is formed of a base material 10, an adhesive layer 20, and a release film 30.
C optical Member and electronic Member
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 protecting an optical member, an electronic member, and the like 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 further includes the adhesive component of the present invention.
Examples (example)
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The test and evaluation methods in examples and the like are as follows. Note that the term "part" refers to "part by weight" unless otherwise specified, and the term "%" refers to "% by weight" unless otherwise specified.
< determination of weight average molecular weight >
The weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus (HLC-8220 GPC) manufactured by TOSOH CORPORATION. The weight average molecular weight (Mw) was obtained by using a polystyrene equivalent.
The measurement conditions are as follows.
Sample concentration: 0.2 wt% (THF solution)
Sample injection amount: 10 μl of eluent
THF flow rate: 0.6 ml/min
Measuring temperature: 40 DEG C
Sample column: TSKguardcolumn SuperHZ-H (1 root) +TSKgel Super HZM-H (2 roots)
Reference column: TSKgelSuperH-RC (1 root)
A detector: differential Refractometer (RI)
< production of adhesive sheet >
The adhesive composition thus obtained was applied onto a release treated surface of a polyester film (trade name: MRF, mitsubishi chemical polyester Co., ltd.) having a thickness of 38 μm, which was release-treated on one surface with silicone, so that the thickness after drying became 50. Mu.m, by a fountain roll, and cured and dried at a drying temperature of 130℃for 3 minutes. In this way, an adhesive layer is formed on the substrate. Then, a polyester film (trade name: MRF, mitsubishi chemical polyester Co., ltd.) having a thickness of 38 μm, which was peeled off on one side with a silicone, was coated on the surface of the pressure-sensitive adhesive layer so that the peeled surface of the film was the pressure-sensitive adhesive layer side. In this manner, an adhesive sheet was produced.
< measurement of glass transition temperature (Tg), storage modulus, loss modulus, tan delta (loss tangent)
The measurement was performed by using a dynamic viscoelasticity measuring apparatus (ARES, manufactured by Rheometrics Co.) according to the following method.
Only the adhesive layer was removed from the obtained adhesive sheet, and laminated to a thickness of about 2mm, which was die-cut to a particle size of phi 7.9mm to prepare a columnar particle, which was used as a sample for measurement. The above measurement sample was fixed to a jig having a parallel plate of phi 7.9mm, and the temperature dependence of the storage modulus G 'and the loss modulus G "was measured by the dynamic viscoelasticity measurement device, and tan δ was calculated as tan δ=g"/G'. The temperature at which the tan delta curve obtained became extremely large was referred to as the glass transition temperature (Tg) (°c).
The measurement conditions are as follows.
And (3) measuring: shear mode
Temperature range: -70-150 DEG C
Heating rate: 5 ℃/min
Frequency: 1Hz
Production example 1: (meth) acrylic Polymer (1)
2-ethylhexyl acrylate (manufactured by Nippon Shokubai co., ltd.) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 100 parts by weight of 2-hydroxyethyl acrylate (manufactured by Toyama Synthesis Co., ltd.): 4 parts by weight of 2,2' -azobisisobutyronitrile (manufactured by Wako pure chemical industries, ltd.) as a polymerization initiator: 0.2 parts by weight of ethyl acetate: 156 parts by weight of a solution (40% by weight) of a (meth) acrylic polymer (1) having a weight-average molecular weight of 55 ten thousand was prepared by conducting polymerization for 6 hours while slowly stirring and introducing nitrogen gas, and maintaining the liquid temperature in the flask at around 65 ℃.
Production example 2: (meth) acrylic Polymer (2)
2-ethylhexyl acrylate (manufactured by Nippon Shokubai co., ltd.) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 100 parts by weight of 4-hydroxybutyl acrylate (manufactured by Osaka organic chemical Co., ltd.): 10 parts by weight of acrylic acid (manufactured by Toyama Synthesis Co., ltd.): 0.02 part by weight of 2,2' -azobisisobutyronitrile (manufactured by Wako pure chemical industries, ltd.) as a polymerization initiator: 0.2 parts by weight of ethyl acetate: 156 parts by weight of (meth) acrylic polymer (2) having a weight average molecular weight of 54 ten thousand was prepared by conducting polymerization reaction for 6 hours while slowly stirring and introducing nitrogen gas, and maintaining the liquid temperature in the flask at around 65 ℃.
Production example 3: (meth) acrylic Polymer (3)
Butyl acrylate (manufactured by Nippon Shokubai co., ltd.) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 99 parts by weight of 4-hydroxybutyl acrylate (manufactured by Osaka organic chemical Co., ltd.): 1 part by weight of 2,2' -azobisisobutyronitrile (manufactured by Wako pure chemical industries, ltd.) as a polymerization initiator: 1 part by weight of ethyl acetate: 156 parts by weight of (meth) acrylic polymer (3) having a weight average molecular weight of 160 ten thousand was prepared by conducting polymerization for 7 hours while stirring slowly and introducing nitrogen gas, and maintaining the liquid temperature in the flask at around 60 ℃.
Production example 4: (meth) acrylic Polymer (4)
Butyl acrylate (manufactured by Nippon Shokubai co., ltd.) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 92 parts by weight of N-acryloylmorpholine (Kohjin co., manufactured by Ltd.): 5 parts by weight of acrylic acid (manufactured by Toyama Synthesis Co., ltd.): 2.9 parts by weight of 2,2' -azobisisobutyronitrile (manufactured by Wako pure chemical industries, ltd.) as a polymerization initiator: 0.1 part by weight of ethyl acetate: 200 parts by weight of the (meth) acrylic polymer (4) having a weight average molecular weight of 180 ten thousand was prepared by conducting polymerization for 8 hours while stirring slowly and introducing nitrogen gas, and maintaining the liquid temperature in the flask at about 55 ℃.
Production example 5: (meth) acrylic Polymer (5)
Butyl acrylate (manufactured by Nippon Shokubai co., ltd.) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 95 parts by weight of acrylic acid (manufactured by eastern synthetic Co., ltd.): 5 parts by weight of 2,2' -azobisisobutyronitrile (manufactured by Wako pure chemical industries, ltd.) as a polymerization initiator: 0.2 parts by weight of ethyl acetate: 156 parts by weight of (meth) acrylic polymer (5) having a weight average molecular weight of 70 w was prepared by conducting polymerization for 10 hours while slowly stirring and introducing nitrogen gas, and maintaining the liquid temperature in the flask at about 63 ℃.
Production example 6: alicyclic structure-containing (meth) acrylic polymer (6)
Glass transition temperature of a cyclohexyl methacrylate [ homopolymer (polycyclohexyl methacrylate) ] as a monomer component: 66 ℃ ]:95 parts by weight of acrylic acid: 5 parts by weight of 2-mercaptoethanol as chain transfer agent: 3 parts by weight of 2,2' -azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight of toluene as a polymerization solvent: 103.2 parts by weight of the mixture was put into a separable flask, and the flask was stirred for 1 hour while introducing nitrogen gas. In this way, after oxygen in the polymerization system was removed, the temperature was raised to 70℃and the reaction was carried out for 3 hours, and further, the reaction was carried out at 75℃for 2 hours, whereby a solution (50% by weight) of (meth) acrylic polymer (6) having a weight average molecular weight of 4000 was obtained.
Production example 6: alicyclic structure-containing (meth) acrylic polymer (7)
Toluene was charged into a 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen inlet pipe, a condenser, and a dropping funnel: 100 parts by weight of dicyclohexyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi chemical Co., ltd.): 60 parts by weight of Methyl Methacrylate (MMA): 40 parts by weight of methyl thioglycolate as a chain transfer agent: 3.5 parts by weight. Then, after stirring at 70℃under a nitrogen atmosphere for 1 hour, 2' -azobisisobutyronitrile was charged as a polymerization initiator: 0.2 parts by weight, reacted at 70℃for 2 hours, then reacted at 80℃for 4 hours, and then reacted at 90℃for 1 hour to give a solution (51% by weight) of (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% by weight based on 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and stirred with a disperser to obtain an adhesive composition (1) containing an acrylic resin. The results are shown in Table 1.
[ example 2 ]
To a solution of the (meth) acrylic polymer (1), adding: the adhesive composition (2) containing an acrylic resin was obtained by diluting 100 parts by weight of the solid content of a solution of the (meth) acrylic polymer (1), 0.01 parts by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of the solid content, and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of the solid content with ethyl acetate so that the total solid content became 25% by weight, and stirring with a disperser. The results are shown in Table 1.
[ example 3 ]
To a solution of the (meth) acrylic polymer (1), adding: the adhesive composition (3) containing an acrylic resin was obtained by diluting 100 parts by weight of the solid content of a solution of the (meth) acrylic polymer (1), 0.1 part by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of the solid content, and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of the solid content with ethyl acetate so that the total solid content became 25% by weight, and stirring with a disperser. The results are shown in Table 1.
[ example 4 ]
To a solution of the (meth) acrylic polymer (1), adding: the adhesive composition (4) containing an acrylic resin was obtained by diluting a solution of 100 parts by weight of a (meth) acrylic polymer (1) solution in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with 0.05 parts by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of solid content, 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a (meth) acrylic polymer (6) solution in terms of solid content, and stirring with a disperser. The results are shown in Table 1.
[ example 5 ]
To a solution of the (meth) acrylic polymer (1), adding: the adhesive composition (5) containing an acrylic resin was obtained by diluting a solution of 100 parts by weight of a (meth) acrylic polymer (1) solution in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with 0.1 part by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of solid content, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a (meth) acrylic polymer (6) solution in terms of solid content, and stirring with a disperser. The results are shown in Table 1.
[ example 6 ]
To a solution of the (meth) acrylic polymer (1), adding: the adhesive composition (6) containing an acrylic resin was obtained by diluting a solution of 100 parts by weight of a (meth) acrylic polymer (1) solution in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with 0.3 parts by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of solid content, 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a (meth) acrylic polymer (6) solution in terms of solid content, and stirring with a disperser. The results are shown in Table 1.
Example 7
To a solution of the (meth) acrylic polymer (1), adding: the adhesive composition (7) containing an acrylic resin was obtained by diluting a solution of 100 parts by weight of a (meth) acrylic polymer (1) solution in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with 0.1 part by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of solid content, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a (meth) acrylic polymer (7) in terms of solid content, and stirring with a disperser. The results are shown in Table 1.
Example 8
To a solution of the (meth) acrylic polymer (1), adding: the adhesive composition (8) containing an acrylic resin was obtained by diluting a solution of 100 parts by weight of a (meth) acrylic polymer (1) solution in terms of solid content with ethyl acetate so that the total solid content became 25% by weight, with 0.3 parts by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of solid content, 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a (meth) acrylic polymer (7) in terms of solid content, and stirring with a disperser. 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% by weight based on 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2), and stirred with a disperser to obtain an adhesive composition (9) containing an acrylic resin. The results are shown in Table 1.
[ example 10 ]
To a solution of the (meth) acrylic polymer (2), adding: the adhesive composition (10) containing an acrylic resin was obtained by diluting 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 (2), 0.1 part by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent, 0.05 part by weight of tetra-C (mitsubishi gas chemical company, ltd.) as a solid content, and 0.005 part by weight of iron acetylacetonate (japan chemical industry, ltd.) as a crosslinking catalyst as a solid content, and stirring with a disperser. The results are shown in Table 1.
[ example 11 ]
To a solution of the (meth) acrylic polymer (3), adding: the adhesive composition (11) containing an acrylic resin was obtained by diluting 100 parts by weight of a solution of the (meth) acrylic polymer (3) with ethyl acetate so that the total solid content became 25% by weight, and stirring with a disperser, with respect to 100 parts by weight of a solid content of the solution, 0.02 parts by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst. The results are shown in Table 1.
[ example 12 ]
To a solution of the (meth) acrylic polymer (4), adding: the adhesive composition (12) containing an acrylic resin was obtained by diluting 100 parts by weight of the solid content of a solution of the (meth) acrylic polymer (4), 0.3 parts by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of the solid content, and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of the solid content with ethyl acetate so that the total solid content became 25% by weight, and stirring with a disperser. The results are shown in Table 1.
[ example 13 ]
To a solution of the (meth) acrylic polymer (5), adding: the adhesive composition (13) containing an acrylic resin was obtained by diluting 100 parts by weight of a solution of the (meth) acrylic polymer (5) with ethyl acetate so that the total solid content became 25% by weight, and stirring with a disperser, based on 100 parts by weight of the solid content of the solution, 0.075 parts by weight of tetra d-C (mitsubishi gas chemical Co., ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate (manufactured by Japanese chemical Co., ltd.) as a crosslinking catalyst, based on the solid content. The results are shown in Table 1.
[ example 14 ]
To a solution of the (meth) acrylic polymer (5), adding: the adhesive composition (14) containing an acrylic resin was obtained by diluting 100 parts by weight of a solution of the (meth) acrylic polymer (5) 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, 0.075 part by weight of tetra d-C (mitsubishi gas chemical Co., ltd.) as a crosslinking agent, 0.005 part by weight of iron acetylacetonate (manufactured by Japanese chemical Co., ltd.) as a crosslinking catalyst, and 20 parts by weight of a solution of the (meth) acrylic polymer (6), based on the solid content, and stirring with a disperser. The results are shown in Table 1.
Comparative example 1
To a solution of the (meth) acrylic polymer (1), adding: the adhesive composition (C1) containing an acrylic resin was obtained by diluting 100 parts by weight of the solid content of a solution of the (meth) acrylic polymer (1), 0.5 part by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent in terms of the solid content, and 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industry co.) as a crosslinking catalyst in terms of the solid content with ethyl acetate so that the total solid content became 25% by weight, and stirring with a disperser. The results are shown in Table 1.
Comparative example 2
To a solution of the (meth) acrylic polymer (2), adding: the adhesive composition (C2) containing an acrylic resin was obtained by diluting 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 (2), 0.45 parts by weight of CORONATE L (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent, 0.3 parts by weight of tetra d-C (mitsubishi gas chemical company, ltd.) as a solid content, and 0.005 parts by weight of iron acetylacetonate (japan chemical industry, ltd.) as a crosslinking catalyst as a solid content, and stirring with a dispersing machine. The results are shown in Table 1.
TABLE 1
[ example 15 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (1) obtained in example 1 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 16 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (2) obtained in example 2 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 17 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (4) obtained in example 4 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 18 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (7) obtained in example 7 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 19 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (9) obtained in example 9 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 20 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (10) obtained in example 10 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 21 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (11) obtained in example 11 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 22 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (12) obtained in example 12 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 23 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (13) obtained in example 13 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by the japanese electric company, co.) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 24 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (14) obtained in example 14 and attached to a polarizing plate (trade name "TEG1465DUHC" manufactured by nito corporation) as an optical member, to obtain an optical member to which the adhesive sheet was attached.
[ example 25 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (1) obtained in example 1 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 26 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (2) obtained in example 2 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 27 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (4) obtained in example 4 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 28 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (7) obtained in example 7 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 29 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (9) obtained in example 9 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 30 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (10) obtained in example 10 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 31 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (11) obtained in example 11 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 32 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (12) obtained in example 12 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 33 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (13) obtained in example 13 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
[ example 34 ]
The polyester film was peeled off from one surface of the adhesive sheet obtained from the adhesive composition (14) obtained in example 14 and attached to a conductive film (trade name "ELECRYSTA V L-TFMP" manufactured by Nito electric Co., ltd.) as an electronic component, to obtain an electronic component to which the adhesive sheet was attached.
Industrial applicability
The adhesive member having an 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) and a 2-functional or higher organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent, wherein the polymer (A) has a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety and a monomer unit (II) derived from a (meth) acrylate having an OH group in the molecule,
the ratio of the molar content of NCO groups in the adhesive composition is [ NCO ], the ratio of the molar content of epoxy groups in the adhesive composition is [ epoxy groups ], the ratio of the molar content of OH groups in the adhesive composition is [ OH ], the ratio of the molar content of COOH groups in the adhesive composition is [ COOH ], 0.01 ++epoxy groups/(OH ] + [ COOH ]) <0.05, the ratio of the content of the monomer unit (I) in the polymer (A) is 90 to 99.5 wt%, the ratio of the content of the monomer unit (II) in the polymer (A) is 0.5 to 10 wt%,
The adhesive composition further comprises a polymer (B) having a monomer unit derived from a (meth) acrylate 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,
CH 2 ＝C(R 1 )COOR 2 …(1)
in the general formula (1), R 1 Is a hydrogen atom or methyl group, R 2 Is a hydrocarbon group having an alicyclic structure,
wherein the adhesive composition has a loss tangent tan delta of 0.10 or more in an adhesive layer formed from the adhesive composition over the entire temperature range of-40 ℃ to 150 ℃,
the content of the polymer (B) is 0.5 to 5 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 comprises 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 according to claim 1 or 2.
4. An optical member provided with the adhesive member according to claim 3.
5. An electronic component provided with the adhesive member according to claim 3.
CN202111137217.3A 2016-01-27 2017-01-25 Adhesive composition, adhesive member, optical member, and electronic member Active CN113831867B (en)

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KR20220024129A (en) 2019-06-27 2022-03-03 닛토덴코 가부시키가이샤 Adhesive sheet and manufacturing method of adhesive sheet affixed parts

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TWI789344B (en) 2023-01-11
CN107011835A (en) 2017-08-04

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