CN108659732A - Adhesive composition, adhesive, bonding sheet and optical component - Google Patents
Adhesive composition, adhesive, bonding sheet and optical component Download PDFInfo
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- CN108659732A CN108659732A CN201810259178.6A CN201810259178A CN108659732A CN 108659732 A CN108659732 A CN 108659732A CN 201810259178 A CN201810259178 A CN 201810259178A CN 108659732 A CN108659732 A CN 108659732A
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- acrylic acid
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- acid series
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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
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- 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
-
- 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
- C08F220/14—Methyl esters, e.g. methyl (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
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- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- 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
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- 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
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- 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
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- 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
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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
- 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
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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- 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
- C09J2453/00—Presence of block copolymer
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- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
Abstract
A kind of adhesive composition of present invention offer, adhesive, bonding sheet and optical component, adhesive composition of the invention show outstanding constant load in the case where forming especially slim adhesive layer and remove patience.The adhesive composition of the present invention contains (methyl) acrylic acid series atactic polymer and (methyl) acrylic acid series triblock polymer, the weight average molecular weight (Mw) that (methyl) the acrylic acid series triblock polymer is measured by gel permeation chromatography is 3,000~30,000.
Description
Technical field
The present invention relates to a kind of adhesive composition, adhesive, bonding sheet and optical components.
Background technology
In the past, a large amount of research has been carried out to promote the performance of adhesive.For example, disclose has one kind in patent document 1
Adhesive addition polymer modification agent, it is outstanding for the intermiscibility of various polymer, it is had no when being added in various polymer
To gonorrhoea or segregation phenomena etc., it is also outstanding to modify effect.However, the inventors discovered that in the feelings for forming especially slim adhesive layer
Under condition, there is very big improvement leeway in existing adhesive composition.
[background technology document]
[patent document]
No. 4442923 bulletins of [patent document 1] Japanese Patent No.
Invention content
[problems to be solved by the invention]
The purpose of the present invention is to provide a kind of to show outstanding perseverance in the case where forming especially slim adhesive layer
Constant load removes the adhesive composition of patience (Fixed-load peel tolerance).It is further an object that
A kind of adhesive formed by this adhesive composition is provided.In turn, the purpose of the present invention is to provide one kind to have by this
The bonding sheet and optical component for the adhesive layer that kind adhesive composition is formed.
[means solved the problems, such as]
The research that the present inventor is made great efforts in order to solve described problem.As a result, the inventors discovered that：By using phase
(methyl) acrylic acid series triblock polymer low to molecular weight, triblock polymer is more present in surface in adhesive layer,
Patience is removed to obtain especially outstanding constant load.
Embodiments of the present invention are for example as described below.
[1] a kind of adhesive composition contains (methyl) acrylic acid series atactic polymer ((meth) acrylic-type
Random polymer) and (methyl) acrylic acid series triblock polymer, (methyl) the acrylic acid series triblock polymer is logical
It is 3,000~30,000 to cross the weight average molecular weight (Mw) that gel permeation chromatography measures.
[2] according to the adhesive composition described in [1], wherein the allotment of described (methyl) acrylic acid series triblock polymer
Amount is in relative to 100 mass parts of (methyl) acrylic acid series atactic polymer in the range of 1~49 mass parts.
[3] according to the adhesive composition described in [1] or [2], wherein described (methyl) acrylic acid series triblock polymer
With the structure using block [A] and block [B] represented by [A]-[B]-[A].
[4] adhesive composition according to any one of [1] to [3] further contains isocyanates system crosslinking agent.
[5] adhesive composition according to any one of [1] to [4], is used for optical applications.
[6] a kind of adhesive is formed by the adhesive composition described in any one of [1] to [5].
[7] a kind of bonding sheet, has base material and adhesive layer, and the adhesive layer utilizes viscous described in any one of [1] to [5]
Mixture composite is formed in at least one side of the base material.
[8] according to the bonding sheet described in [7], wherein the thickness of the adhesive layer is 15 μm or less.
[9] a kind of optical component, containing adhesive layer, the adhesive layer is by the adhesive group described in any one of [1] to [5]
Object is closed to be formed.
[10] according to the optical component described in [9], wherein the thickness of the adhesive layer is 15 μm or less.
[The effect of invention]
According to the present invention, it is possible to provide it is a kind of shown in the case where forming especially slim adhesive layer it is outstanding constant negative
Lotus removes the adhesive composition of patience.According to the present invention, a kind of bonding formed by this adhesive composition can also be provided
Agent.In turn, according to the present invention, a kind of bonding sheet and light of the adhesive layer for having and being formed by this adhesive composition can also be provided
Department of the Chinese Academy of Sciences's part.
Description of the drawings
Nothing
Specific implementation mode
In the following, illustrating the adhesive composition of one embodiment of the present invention, adhesive, bonding sheet and optical component.
In addition, in the present specification, the saying of " polymer " includes homopolymer (homopolymer) and copolymer
(copolymer), the saying of " polymerization " includes homopolymerization and copolymerization.In addition, also by the compound represented by formula (i), (i is that formula is compiled
Number) referred to as " compound (i) ".In turn, in the present specification, (methyl) acrylic acid refers to acrylic or methacrylic acid, (first
Base) acrylate refers to acrylate or methacrylate, (methyl) acryloyl group refers to acryloyl group or methacryl
Base.
[adhesive composition]
The adhesive composition of one embodiment of the present invention contains (methyl) acrylic acid series atactic polymer and (methyl)
Acrylic acid series triblock polymer.Here, (methyl) acrylic acid series triblock polymer is surveyed by gel permeation chromatography (GPC)
The weight average molecular weight (Mw) obtained is 3,000~30,000.
[1] (methyl) acrylic acid series atactic polymer
The composition of (methyl) acrylic acid series atactic polymer is not particularly limited.(methyl) acrylic acid series atactic polymer can
For (methyl) the acrylic acid series atactic polymer synthesized by general radical polymerization, or it is poly- by living radical
(methyl) acrylic acid series atactic polymer of legal synthesis.The weight that (methyl) acrylic acid series atactic polymer is measured by GPC method
Amount average molecular weight (Mw) is, for example, 100,000~3,000,000, preferably 150, and 000~2,000,000, more preferable 200,000
~2,000,000.The molecular weight distribution (Mw/Mn) that (methyl) acrylic acid series atactic polymer is measured by GPC method is for example,
30.0 hereinafter, it is preferred that 25.0 hereinafter, more preferable 20.0 or less.
＜ starting monomers ＞
It is main to use (methyl) acrylate as the starting monomer of (methyl) acrylic acid series atactic polymer, but also may be used
Further use monomer containing functional group and co-polymerized monomer etc. in addition to this.
《(methyl) acrylate》
As (methyl) acrylate, such as (methyl) alkyl acrylate, (methyl) alkyl acrylate oxygroup alkane can be enumerated
(methyl) acrylate of base ester, alkoxy polyalkyleneglycol list (methyl) acrylate, base containing ester ring type or aromatic rings.Its
In, remove (methyl) acrylate of hydroxyl, carboxylic (methyl) acrylate, amino-containing from (methyl) acrylate
(methyl) acrylate containing functional group such as (methyl) acrylate.
The carbon number preferably 1~20 of alkyl in (methyl) alkyl acrylate.As (methyl) alkyl acrylate, such as
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid isopropyl can be enumerated
Ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid third butyl ester (tert-butyl
(meth) acrylate), (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) propylene
Sour 2- ethylhexyls, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) acrylic acid
Hendecane base ester, (methyl) lauryl acrylate, (methyl) acrylic acid grease, the positive stearyl ester of (methyl) acrylic acid, (methyl) third
The different stearyl ester of olefin(e) acid (iso-stearyl (meth) acrylate), (methyl) acrylic acid didecyl.
As (methyl) alkoxyalkyl acrylate, such as (methyl) methoxyethyl methyl esters, (methyl) can be enumerated
Acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 3- methoxyl groups propyl ester, (methyl) third
Olefin(e) acid 3- ethyoxyls propyl ester, (methyl) acrylic acid 4- methoxybutyls, (methyl) acrylic acid 4- Ethoxybutyls.
As alkoxy polyalkyleneglycol list (methyl) acrylate, such as methoxyl group diethylene glycol list (first can be enumerated
Base) acrylate (Methoxydiethylene glycol mono (meth) acrylate), methoxyl group dipropylene glycol list (first
Base) acrylate, ethoxytriglycol list (methyl) acrylate (Ethoxydiethylene glycol mono (meth)
Acrylate), ethoxydiglycol list (methyl) acrylate, methoxy triethylene list (methyl) acrylate
(Methoxytriethylene glycol mono(meth)acrylate)。
As base containing ester ring type or (methyl) acrylate of aromatic rings, for example, can enumerate (methyl) cyclohexyl acrylate,
(methyl) benzyl acrylate, (methyl) phenyl acrylate.
Gross mass of the total usage amount of (methyl) acrylate relative to whole starting monomers, for example, 70~99.9 matter
Measure %, preferably 80~99.5 mass %, more preferable 89.95~98.95 mass %.
(methyl) acrylate can be used alone a kind of or use two or more.
《Monomer containing functional group》
As the monomer containing functional group, for example, can enumerate the monomer of hydroxyl, the monomer containing acidic group, amino-containing monomer,
The monomer of the monomer of amide-containing, the monomer of nitrogenous system's heterocycle, cyano-containing.As acidic group, for example, can enumerate carboxyl, anhydride group,
Phosphate, sulfate.
As the monomer of hydroxyl, such as it (methyl) acrylate of hydroxyl can be enumerated specifically can enumerate (first
Base) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 3- hydroxypropyl acrylates, (methyl) acrylic acid 4- hydroxy butyl esters, (methyl) acrylic acid 6- hydroxyls
(methyl) hydroxyalkyl acrylates such as own ester, (methyl) acrylic acid 8- hydroxyl monooctyl esters.In (methyl) hydroxyalkyl acrylates
The carbon number of alkyl is usually 2~8, and preferably 2~6.
As carboxylic monomer, such as (methyl) β-acryloxypropionic acid, (methyl) acrylic acid 5- carboxylic pentyl esters can be enumerated
(5-carboxypentyl (meth) acylate), succinic acid list (methyl) acryloyloxyethyl ester (Succinic acid
Mono (meth) acryloyloxyethyl ester), ω-carboxy-polycaprolactone list (methyl) acrylate, acrylic acid, methyl
Acrylic acid, itaconic acid, butenoic acid, fumaric acid, maleic acid.As the monomer containing anhydride group, such as maleic anhydride can be enumerated.As
The monomer of phosphorous acidic group, can be recited in side chain has (methyl) acrylic monomer of phosphate, as the monomer of sulfur-bearing acidic group,
Side chain, which can be recited in, has (methyl) acrylic monomer of sulfate.
As amino-containing monomer, such as (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid diethyl can be enumerated
Amino-containing (methyl) acrylate such as amino ethyl ester.
As the monomer of amide-containing, such as (methyl) acrylamide, N- methyl (methyl) acrylamide, N- second can be enumerated
Base (methyl) acrylamide, N- propyl (methyl) acrylamide, N- hexyls (methyl) acrylamide.List as nitrogenous system's heterocycle
Body, such as vinyl pyrrolidone, acryloyl morpholine, caprolactam can be enumerated.As the monomer of cyano-containing, such as
Cyano (methyl) acrylate, (methyl) acrylonitrile can be enumerated.
Gross mass of the total usage amount of monomer containing functional group relative to whole starting monomers, preferably 0~10 mass %, more
It is preferred that 0.05~5 mass %.
Monomer containing functional group can be used alone a kind of or use two or more.
《Co-polymerized monomer》
As co-polymerized monomer, for example, can enumerate styrene, methyl styrene, dimethyl styrene, trimethyl styrene,
The ring-alkylated styrenes such as propylstyrene, butylstyrene, hexyl styrene, heptyl styrene and octyl styrene, fluorobenzene ethene,
Chlorostyrene, bromstyrol, Dowspray 9, iodate styrene, nitre styrene, acetylbenzene ethylene and methoxy styrene etc.
Styrenic monomers, vinyl acetate.
Co-polymerized monomer can be used alone a kind of or use two or more.
[2] (methyl) acrylic acid series triblock polymer
The weight averaged molecular of (methyl) acrylic acid series triblock polymer used in the present invention measured by GPC method
It is 3,000~30,000 to measure (Mw).The weight average molecular weight (Mw) preferably 3,000~20,000, more preferable 3,000~
10,000.In addition, the molecular weight distribution (Mw/Mn) that (methyl) acrylic acid series atactic polymer is measured by GPC method is, for example, 1.5
Hereinafter, it is preferred that 1.4 hereinafter, more preferable 1.3 or less.
As described above, the inventors discovered that：By using low (methyl) the acrylic acid series three block polymerization of relative molecular weight
Object, triblock polymer is more present in surface in adhesive layer, to which the constant load stripping that can get especially outstanding is resistance to
Property.If the weight average molecular weight is excessive, the triblock polymer in adhesive layer significantly will not more be present in
Surface, accordingly, it is difficult to reach outstanding constant load stripping patience.On the other hand, if the weight average molecular weight is too small,
Then adhesive composition becomes cohesiveness deficiency, it is difficult to reach outstanding constant load stripping patience.
The synthetic method of (methyl) acrylic acid series triblock polymer used in the present invention is not particularly limited.(methyl)
Acrylic acid series triblock polymer can be to be polymerize by (methyl) acrylic acid series three block that general radical polymerization synthesizes
Object, or (methyl) acrylic acid series triblock polymer by living radical polymerization synthesis.
Triblock polymer can be manufactured using general active free radical polymerization.Wherein, with regard to the control of polymerisation
For easness this respect processed etc., can suitably it be manufactured by atom transfer radical polymerization.Atom transferred free radical
It is catalysis that polymerization, which is using organohalogen compounds or sulfonyl halogen compound as initiator and with metal complex (metal complex),
The polymerization of agent.In the case where manufacturing triblock polymer by living radical polymerization, it can enumerate and gradually add monomer
The method of unit, using pre-synthesis polymer as polymeric initiator and by method that next polymer blocks polymerize, pass through
Reaction comes the method etc. of the polymer blocks polymerizeing respectively bonding preferably by the method for monomeric unit gradually added
Manufacture triblock polymer.
(methyl) acrylic acid series triblock polymer for example also can be by Reversible Addition Fragmentation Chain Transfer (RAFT) polymerize
Synthesis.If polymerize using RAFT, it can more closely control the molecular weight of (methyl) acrylic acid series triblock polymer and divide
Son amount distribution.
RAFT polymerizations are so that the free-radical polymerised compound as starting monomer is polymerize in the presence of RAFT agent
Method.All starting monomers can be added at one time and be polymerize, after also a part of starting monomer being made to be polymerize, even
Continuous ground intermittently adds remaining monomer component and is polymerize.
＜ RAFT agent ＞
As RAFT agent, previous known compound can be used, be not particularly limited.As RAFT agent, such as can enumerate double
(thiocarbonyl) disulphide (Bis (thiocarbonyl) disulfide), dithioesters, trithiocarbonate
(Trithiocarbonate), the thiocarbonylthio compounds such as dithiocarbamate, xanthate acid.
Respectively, as bis- (thiocarbonyl) di-sulphide compounds (bis (thiocarbonyl) disulfide
Compound), such as tetraethylthiuram disulfide, tetramethylthiuram disulfide, bis- (n octylmercaptan bases can be enumerated
(octylmercapto)-thiocarbonyl) disulphide, bis- (n-dodecyl mercaptan base-thiocarbonyl) disulphide, bis- (benzyls
Base mercapto-thiocarbonyl) disulphide, bis- (butyl mercaptan base-thiocarbonyl) disulphide, bis- (third butanethiols
Base-thiocarbonyl) disulphide, bis- (n-heptyl mercaptan base-thiocarbonyl) disulphide, bis- (n-hexyl mercaptan bases-thio carbonyl
Base) disulphide, bis- (n-amylmercaptane base-thiocarbonyl) disulphide, bis- (n-nonyl mercapto-thiocarbonyl) curing
Object, bis- (positive decyl mercapto-thiocarbonyl) disulphide, bis- (third-lauryl mercaptan base-thiocarbonyl) curing
Object, bis- (n-tetradecane base mercapto-thiocarbonyl) disulphide, bis- (n-hexadecyl mercapto-thiocarbonyl) curing
Object, bis- (n-octadecane base mercapto-thiocarbonyl) disulphide etc.；
Make As dithioesters compounds, such as bis- sulphur (2-phenyl-2- of Ke Lie Lift 2- phenyl -2- Bing Ji Ben And
Propylbenzothioate), 4- cyano -4- (phenyl carbonyl mercapto) valeric acid, two sulphur of 2- cyano -2- propyl benzo
(2-Cyano-2-propylbenzodithioate) etc.；
As trithiocarbonic acid salt compound, such as three thio carbon of S- (2- cyano -2- propyl)-S- dodecyls can be enumerated
Hydrochlorate, 4- cyano -4- [(lauryl mercaptan base-thiocarbonyl) mercapto] valeric acid, three thio carbon of cyano methyl dodecyl
Hydrochlorate, 2- (lauryl mercaptan base thiocarbonyl mercapto) (dodecylthiocarbonothiolthio) -2- methyl-props
Sour, bis- [4- { ethyl -2- (ethoxy) amino carbonyl }-benzyl] trithiocarbonates etc.；
As dithio carbamate compounds, such as cyanogen methyl (phenyl) aminodithioformic acid can be enumerated
Ester, cyano methyl diphenyldithiocarbamic acid ester etc.；
As xanthate acid compound, such as xanthate can be enumerated etc..
Total amount 100 mass parts of the usage amount of RAFT agent relative to starting monomer, usually 0.05~20 mass parts, preferably
0.1~10 mass parts.If the usage amount of RAFT agent is the lower limiting value of the range or more, it is easy to control reaction, if it is
The upper limit value of the range is hereinafter, be then easy the weight average molecular weight of the polymer obtained being adjusted to the range.
RAFT polymerizations preferably carry out in the presence of polymerization initiator.As polymerization initiator, such as can enumerate general
Organic system polymerization initiator specifically can enumerate the peroxide such as benzoyl peroxide, lauroyl peroxide, 2,2'- azos
The azo-compounds such as bis-isobutyronitrile.Polymerization initiator can be used alone a kind of or use two or more.
Using the usage amount of polymerization initiator when polymerization initiator relative to 100 mass parts of starting monomer, usually 0.001
~2 mass parts, preferably 0.002~1 mass parts.In addition, relative to 1 mole of RAFT agent, the usage amount of polymerization initiator is usually
0.1~3000 mole, preferably 1~1000 mole.
＜ starting monomers ＞
The starting monomer of each block as composition (methyl) acrylic acid series triblock polymer, it is main to use (methyl) third
Olefin(e) acid ester, but monomer containing functional group and co-polymerized monomer etc. in addition to this can be also used in turn.As (methyl) acrylic acid
The example of ester, the monomer containing functional group and co-polymerized monomer can be enumerated and above in relation to (methyl) acrylic acid series atactic polymer
Starting monomer illustrated by the identical starting monomer of starting monomer.
＜ blocks constitute ＞
(methyl) acrylic acid series triblock polymer used in the present invention, which preferably has, utilizes block [A] and block [B]
Structure represented by [A]-[B]-[A].If using this composition, it is easy to show structure cohesiveness, that is to say, that i.e.
Just it is relatively low molecular weight, also can get high cohesion, thus, it is possible to obtain especially outstanding constant load removes patience.
The weight of block [A] is such as 10~90 mass %, preferably of (methyl) acrylic acid series triblock polymer entirety
20~80 mass %, more preferable 30~70 mass %.In addition, the weight of block [B] polymerize for (methyl) acrylic acid series three block
Such as 10~90 mass %, preferably 20~80 mass %, more preferable 30~70 mass % of object entirety.
The block [A] preferably comprises by general formula CH2=CY1-COOY2(Y1It is hydrogen atom or methyl, Y2It is carbon number 1~20
Alkyl) represented by monomer formed ingredient.In addition, the block [B] preferably comprises by general formula CH2=CY3-COOY4(Y3
It is hydrogen atom or methyl, Y4The alkyl of carbon number 1~20) represented by monomer formed ingredient.Moreover, in said case,
The more preferable Y2Carbon number be more than the Y4Carbon number.If using this composition, in adhesive layer, triblock polymer
More easily more it is present in surface, can get especially outstanding constant load and remove patience.
As the Y for meeting the condition2With Y4Combination, such as can enumerate such as combination recorded in table 1 below.In addition,
The record of the table is only to illustrate, it is not excluded that the combination other than these.
[table 1]
| Y2 | Y4 |
| Ethyl | Methyl |
| N-propyl | Methyl |
| Isopropyl | Methyl |
| Normal-butyl | Methyl |
| Isobutyl group | Methyl |
| Third butyl | Methyl |
| N-propyl | Ethyl |
| Isopropyl | Ethyl |
| Normal-butyl | N-propyl |
| Isobutyl group | N-propyl |
| Third butyl | N-propyl |
| Normal-butyl | Isopropyl |
| Isobutyl group | Isopropyl |
| Third butyl | Isopropyl |
(methyl) acrylic acid series three that the weight average molecular weight (Mw) measured by GPC method is 3,000~30,000 is embedding
The blending amount of section polymer is relative to 100 mass parts of (methyl) acrylic acid series atactic polymer, such as is set as 1~49 mass
Part, it is preferably set to 1~39 mass parts.If the blending amount of (methyl) acrylic acid series triblock polymer is adjusted to this model
It encloses, more excellent constant load stripping patience can be obtained.
In addition, the adhesive composition of the present invention also can further contain the three block polymerization outside the molecular weight ranges
Object, also can be further containing the block polymer other than triblock polymer.
[3] other ingredients
Adhesive composition also can further contain crosslinking agent, silane coupling agent, antistatic agent, organic solvent, anti-oxidant
Agent, light stabilizer, preventing metal corrosion agent, bonding imparting agent, plasticizer, crosslinking accelerator, nano-particle etc. are used as other ingredients.
＜ crosslinking agents ＞
As crosslinking agent, isocyanates based compound, epoxy based compound, metallo-chelate based compound etc. can be enumerated,
Just do not interfere that triblock polymer is more present in surface within the adhesive layer and that adhesive phase can be made to show is good
, it is preferable to use isocyanates system crosslinking agent for physical property this respect.
As isocyanates based compound, the isocyanates for being 2 or more usually using the isocyanates radix in 1 molecule
Compound.As isocyanate compound, such as aliphatic diisocyanate, alicyclic diisocyanate, aromatic series can be enumerated
Diisocyanate.As aliphatic diisocyanate, can enumerate diisocyanate second diester (Ethylene diisocyanate),
Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2- methyl-1s, 5- pentanes two are different
Cyanate, 3- methyl-1s, the carbon numbers 4 such as 5- pentane diisocyanates, 2,2,4- trimethyl -1,6- hexamethylene diisocyanates~
30 aliphatic diisocyanate.As alicyclic diisocyanate, it is different that isophorone diisocyanate, cyclopenta two can be enumerated
Cyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenation hexichol first
The alicyclic diisocyanate of the carbon numbers 7~30 such as alkane diisocyanate, hydrogenation tetramethylxylene diisocyanate.As fragrance
(cyclo) aliphatic diisocyanates, such as phenylene vulcabond can be enumerated, toluene di-isocyanate(TDI), xylylene diisocyanate, stretched
The carbon numbers such as naphthalene diisocyanate, diphenyl ether diisocyanate, '-diphenylmethane diisocyanate, diphenylpropane diisocyanate
8~30 aromatic diisocyanate.
The isocyanate compound for being 3 or more as the isocyanates radix in 1 molecule, for example, aromatic series can be enumerated
Polyisocyanate, aliphatic polymeric isocyanate, alicyclic polymeric isocyanate.Specifically, 2,4,6- tri- isocyanide of toluene can be enumerated
Acid esters, 1,3,5- benzene triisocyanate, 4,4', 4 "-triphenylmethane triisocyanates.In turn, as isocyanate compound, example
The trimer of '-diphenylmethane diisocyanate, polymethylene polyphenyl base polyisocyanate, hexa-methylene diisocyanate can such as be enumerated
The biuret body or chlorinated isocyanurates body of ester or toluene di-isocyanate(TDI), trimethylolpropane and toluene di-isocyanate(TDI) or benzene two
Reaction product (such as the three molecule additions of toluene di-isocyanate(TDI) or xylylene diisocyanate of methyl diisocyanate
Object), the reaction product of trimethylolpropane and hexamethylene diisocyanate (such as three points of hexamethylene diisocyanate
Sub- addition product), polyethers polyisocyanate, polyester polyisocyanate.
As epoxy based compound, for example, usually using the epoxy radix in 1 molecule be 2 or more epoxide.
Such as ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, glycerine three can be enumerated and shunk
Bis- (N, the N- 2-glycidyl aminomethyl) hexamethylenes of glycerin ether, 1,3-, N, N, N', N'- four glycidyl groups m-xylene diamine, N,
N, N', N'- four glycidyl group aminophenyl methane, triglycidyl group chlorinated isocyanurates, N, N- diglycidyl ammonia
Base phenyl glycidyl ether (m-N, N-diglycidylaminophenyl glycidyl ether), N, N- diglycidyls
Toluidines, N, N- diglycidylanilines.
As meal chelate compounds, such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium can be recited in
Equal polyvalent metal coordinations have the compound of alkoxide, acetylacetone,2,4-pentanedione, ethyl acetoacetate etc..Specifically, isopropyl can be enumerated
Aluminium alcoholates, the second aluminium butoxide, acetoacetate aluminium ethide diisopropyl ester, triacetyl acetic aluminium, praseodynium acid aluminium.
Conjunction of the crosslinking agent relative to (methyl) acrylic acid series atactic polymer and (methyl) acrylic acid series triblock polymer
It counts 100 mass parts and is in 0.01~5 mass parts, the range of preferably 0.01~2 mass parts, more preferable 0.01~1 mass parts.If
Crosslinking dose is included in the range, the balance of durability and stress retentivity can be obtained.
＜ silane coupling agents ＞
Silane coupling agent makes adhesive phase be adhered firmly to the adherend such as glass substrate, can prevent high humid and warm environment
Lower adhesive layer is peeled off, if combined with the block polymer, the promotion effect of durability is larger.
As silane coupling agent, such as can enumerate：Vinyltrimethoxysilane, vinyltriethoxysilane, methyl
The silane coupling agent of the unsaturated groups containing polymerism such as acryloyl group oxygen propyl trimethoxy silicane；3- glycidoxypropyl trimethoxies
Base silane, 3- glycidoxypropyls triethoxysilane, 3- glycidoxypropyls methyl dimethoxysilane, 3- glycidol oxygen
The silane coupling agents containing epoxy group such as ylmethyl diethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane；
3- TSL 8330s, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- amino-ethyls) -
The amino-containing silane coupling agent such as 3- aminopropylmethyldimethoxysilanes；3- r-chloropropyl trimethoxyl silanes etc. are halogen-containing
Silane coupling agent.
Wherein, for stress retentivity etc., the preferred silane coupling agent containing epoxy group.In the composition of the present invention
In, the content of silane coupling agent is relative to (methyl) acrylic acid series atactic polymer and (methyl) acrylic acid series triblock polymer
Total 100 mass parts, usually 1 is below mass part, preferably 0.01~1 mass parts, more preferable 0.05~0.5 mass parts.Such as
Fruit content is in the range, then having prevents silane coupling agent exudation under the peeling of high humid and warm environment lower adhesive layer or hot environment
Tendency.
＜ antistatic agents ＞
As antistatic agent, such as surfactant, ionic compound, electric conductive polymer can be enumerated.
As surfactant, such as can enumerate：Quarternary ammonium salt class, phenazopyridine salt, has amide quarternary ammonium salt class
The cationic surfactant of the cationics bases such as level-one~three-level amino；The tools such as sulfonate group, sulfate group, phosphate-based
There is the anionic surfactant of anionic property base；Alkyl betaines bases, alkyl imidazoline betaines, alkyl amine oxide
The amphoteric surfactantes such as class, amino acid sulfuric acid ester, glycerine fatty acid esters, sorbitan fatty acid ester class, polyoxy second
Allylic alkylation amine, polyoxyethylene alkyl amine fatty acid ester, N- ethoxy-N-2- hydroxyalkylamines, alkyldiethanolamine class
Equal nonionic surfactants.
In addition, as surfactant, the reactive emulsifier with polymerism base can be also enumerated, it is possible to use will contain
Polymer system surfactant made of the monomer component molecular weight of the surfactant or reactive emulsifier.
Ionic compound is made of cationic portion and anion portion, can be at room temperature solid under (23 DEG C/50%RH)
Shape is alternatively liquid.
Can be any in inorganic cation or organic cation as the cationic portion for constituting ionic compound
It is a or two.As inorganic cation, preferred as alkali ion and alkaline-earth metal ion, more preferable antistatic property
Outstanding Li+、Na+And K+.As organic cation, such as pyridylium, piperidines cation, pyrrolidines can be enumerated
Cation, pyrroles's cation moiety, pyrroles's cation, glyoxaline cation, tetrahydropyrimidine cation, dihydro-pyrimidin sun from
Son, pyrazoles cation, pyrazoles cation moiety, tetraalkylammonium cation, dialkyl matte cation, four alkane base phosphonium cations and
These derivative.
As constitute ionic compound anion portion, as long as can with cationic portion's ionic bonding and formed ionic
Compound, then there is no particular restriction.Specifically, F can be enumerated-、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、
ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(F2SO2)2N-、(CF3SO2)3C-、AsF6 -、
SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-And (CF3SO2)(CF3CO)N-。
As ionic compound, preferably bis- (trifyl) imide lis, bis- (two fluorosulfonyls) imide lis,
Three (trifyl) methane lithiums, bis- (trifyl) acid imide potassium, bis- (two fluorosulfonyls) acid imide potassium, 1- ethyls
Pyridine hexafluorophosphate, 1- butyl-pyridiniums hexafluorophosphate, 1- hexyl -4- picolines hexafluorophosphate, 1- octyls -
Bis- (fluorosulfonyl) acid imides of 4- picolines hexafluorophosphate, 1- octyl -4- picolines, 1- octyl -4- methyl pyrroles
It is bis- (trifyl) acid imides of pyridine, (N, N- diethyl-N- methyl-N- (2- methoxy ethyls) ammonium tetrafluoroborate, double
(trifyl) acid imide N, N- diethyl-N- methyl-N- (2- methoxy ethyls) ammonium, 1- octylpyridinium fluorine sulfoniums acyl are sub-
Amine (1-Octylpyridinium fluorosulfoniumimide), 1- octyl -3- picolines, trifluoro sulfonium acid imide.
As electric conductive polymer, such as polythiophene, polyaniline, polypyrrole and these derivative can be enumerated.
In the present compositions, the content of antistatic agent is relative to (methyl) acrylic acid series atactic polymer and (first
Base) acrylic acid series triblock polymer total 100 mass parts, usually 3 is below mass part, preferably 0.01~3 mass parts, more
It is preferred that 0.05~2.5 mass parts.
＜ organic solvents ＞
The adhesive composition of the present invention not necessarily contains solvent, but can also contain organic solvent to adjust adhesive group
Close the coating of object.In the adhesive composition of the present invention, the content of organic solvent is usually 50~90 mass %, and preferably 60
~85 mass %.In addition, in the present specification, " solid content ingredient " refers to containing in ingredient in adhesive composition removing institute
The whole components of organic solvent are stated, " solid content constituent concentration " refers to the solid content ingredient relative to adhesive composition 100
The ratio of quality %.
The purposes of the adhesive composition of the present invention is without limitation.However, the inventors discovered that the adhesive combination of the present invention
Object can play outstanding performance when forming especially slim adhesive layer.Therefore, adhesive composition of the invention is used in optics
It is particularly useful on the way.As optical applications, for example, can enumerate various display devices (liquid crystal display device, organic EL display device,
Display device of electronic paper etc.), touch panel, camera, microscope etc..
[adhesive]
The adhesive of the present invention is formed by described adhesive composition.The gel fraction of described adhesive has no special limit
Determine, usually 80 mass % or less.The gel fraction is the value that the condition recorded for example, by embodiment measures.
[bonding sheet]
The present invention bonding sheet include：Two sides bonding sheet only has and is formed in release-treated cover film (below also referred to as
For isolation film) on adhesive phase；Two sides bonding sheet has base material and is formed in the described adhesive layer on base material two sides (in institute
In the case of stating, base material is also known as core material)；Single side bonding sheet, the described adhesive with base material and the one side for being formed in base material
Layer；And bonding sheet, have release-treated cover film in the face paste of the adhesive phase of these bonding sheets not connected with base material.
As base material and cover film, such as can enumerate：The polyester films such as polyethylene terephthalate (PET)；Makrolon,
The polyolefin films such as polyethylene, polypropylene, vinyl-vinyl acetate copolymer, polarizer, phase difference film, optical diffusion film, brightness enhancement film
Etc. plastic films and glass.In addition, plastic film and glass made of various additives or multiple laminated layers can be used in plastic film and glass
Glass.In addition, in the present specification, " polarizer " is used with the meaning for containing " light polarizing film ".
Especially in the case where the base material is used for such as optical applications, suitable for using optically with the transparency
Woven fabric, non-woven fabrics, metal evaporation can be used especially in the case where not requiring the transparency to wait in plastic film as described
Piece, metallic sieve, other arbitrary base materials.
As the coating method of adhesive composition, following method can be used：By all perception methods such as method of spin coating,
Knife coating, rolling method, rod coating method, scraper for coating method, mould mouth rubbing method, gravure coating process, with the side as specific thicknesses
Formula is coated, dries.
The thickness of adhesive layer has no the special upper limit, such as is set as 30 μm hereinafter, being preferably set to 25 μm hereinafter, being more preferably set as
20 μm hereinafter, be further preferably set as 15 μm hereinafter, being particularly preferably set as 12 μm or less.As described above, the adhesive of the present invention
Composition can play especially outstanding performance when forming slim adhesive layer.Therefore, in the case where adhesive layer is thin layer, with
It is compared using the case where previous composition, performance difference is apparent.
[optical component]
The optical component of the present invention contains the adhesive layer formed by adhesive composition.The forming method of the adhesive layer or
Thickness with it is described identical.
As the example of optical component, polarizer, liquid crystal cell, camera, microscope etc. can be enumerated.For example, polarizer contains
There is the adhesive phase of polarisation plate body and lamination in at least one side of the polarisation plate body.
[embodiment]
Hereinafter, the present invention is further illustrated based on embodiment, but the present invention is not limited to these embodiments.Following
Embodiment etc. record in, as long as not specified, then " part " refers to " mass parts ".
[Mw、Mn]
For (methyl) acrylic acid series atactic polymer and (methyl) acrylic acid series triblock polymer, pass through gel infiltration
Chromatography (GPC method) finds out weight average molecular weight (Mw) and number average molecular weight (Mn) under the following conditions.
Measurement device：HLC-8320GPC (Tosoh (share) manufactures)
GPC tubing strings are constituted：Four columns connection (all being manufactured by Tosoh (share)) below
(1) TSKgel HxL-H (protection tubing string)
(2)TSKgel GMHxL
(3)TSKgel GMHxL
(4)TSKgel G2500HxL
Flow velocity：1.0mL/min
Tubing string temperature：40℃
Sample concentration：1.5% (w/v) (being diluted using tetrahydrofuran)
Mobile phase solvent：Tetrahydrofuran
Standard polystyren converts
[synthesis of (methyl) acrylic acid series atactic polymer]
[synthesis example 1~3]
In the reaction unit for having blender, reflux cooler, thermometer and nitrogen ingress pipe, added with the ratio of table 2
Enter n-butyl acrylate (BA), acrylic acid (AA), 2- hydroxy ethyl methacrylates (2HEA), methacrylate (MA), and adds
Enter 100 parts of ethyl acetate, import nitrogen on one side, is warming up to 80 DEG C on one side.Then, third butyl peroxy pivalate is added
0.1 part, under nitrogen atmosphere, with 80 DEG C of progress, 6 hours polymerisations.After reaction, be diluted using ethyl acetate and
Prepare the polymer solution of 30 mass % of solid content constituent concentration.By the characteristic one of (methyl) acrylic acid series copolymer obtained
And it is shown in table 2.
[table 2]
[synthesis of (methyl) acrylic block polymer]
[synthesis example 4]
In the flask for having agitating device, nitrogen ingress pipe, thermometer and the cooling tube that flows back, methacrylate is added
50 parts by weight, bis- 10 parts by weight of [4- { ethyl -2- (ethoxy) amino carbonyl }-benzyl] trithiocarbonate, on one side to flask
Interior middle importing nitrogen, is heated to 80 DEG C by the content of flask on one side.Then, nitrogen displacement will be sufficiently carried out
AIBN0.03 parts by weight are added to while stirring in flask, and 80 DEG C can be maintained with the temperature of the content in flask
Mode carries out heating and cooling in 2 hours.105 DEG C of non-volatile contents of the acrylic acid series polymeric compounds obtained by this method are
99.5%.Secondly, it after the temperature of the content in flask is warming up to 90 DEG C, lasts 1 hour and 50 weight of butyl acrylate is added dropwise
Part.Later, in such a way that the temperature of the content in flask can maintain 90 DEG C, heating and cooling in 3 hours are carried out, finally
Add 25 parts by weight of ethyl acetate.
(methyl) acrylic acid series triblock polymer MBM1 is obtained in this way.By the characteristic of triblock polymer MBM1
It is shown in following Table 3.
[table 3]
| Referred to as | Composition | Mw | Mw/Mn | |
| Synthesis example 4 | MBM1 | MA-BA-MA=25-50-25 | 9,700 | 1.3 |
| Synthesis example 5 | MBM2 | MA-BA-MA=25-50-25 | 3,500 | 1.3 |
| Synthesis example 6 | MBM3 | MA-BA-MA=25-50-25 | 24,800 | 1.3 |
| Synthesis example 7 | MBM4 | MA-BA-MA=25-50-25 | 2,500 | 1.3 |
| Synthesis example 8 | MBM5 | MA-BA-MA=25-50-25 | 84,200 | 1.3 |
| Synthesis example 9 | BMB1 | BA-MA-BA=25-50-25 | 8,400 | 1.3 |
| Synthesis example 10 | M-B | MA-BA=50-50 | 10,700 | 1.2 |
[synthesis example 5~8]
The weight average molecular weight of the polymer finally obtained is set as described in Table 3, in addition to this, with synthesis example
4 identical modes are respectively synthesized (methyl) acrylic acid series triblock polymer MBM2~5.
[synthesis example 9]
The ordering in launching for changing monomer, is set as described in Table 3 by the weight average molecular weight of the polymer finally obtained,
In addition to this, in a manner of identical with synthesis example 4, (methyl) acrylic acid series triblock polymer BMB1 is synthesized.
[synthesis example 10]
Will be bis- [4- { ethyl -2- (ethoxy) amino carbonyl }-benzyl] trithiocarbonate be changed to N- Methyl-N-phenyls
Aminodithioformic acid cyano methyl ester, in addition to this, in a manner of identical with synthesis example 4, synthesis (methyl) acrylic acid series two is embedding
Section polymer M-B.The characteristic of diblock polymer M-B is shown in the table 3.
[Examples 1 to 10 and comparative example 1~6]
By obtained in synthesis example 1~10 (methyl) acrylic acid series polymeric compounds and as isocyanates system crosslinking agent
Coronate L (manufacture of Tosoh limited liability companies), combination and ratio as described in table 4 below and table 5 are mixed,
Obtain adhesive composition.
For each adhesive composition obtained, shown in the thickness of the adhesive layer after drying such as table 4 and table 5 in a manner of
It is adjusted and is coated on light stripping film, after being dried, being transferred to the PET film that thickness is 25 μm, (Lumirror, Toray are public
Department's manufacture).In this way bonding sheet is manufactured in formation adhesive layer on base material.The thickness of adhesive layer is shown in table 4 together
And table 5.
[gel fraction]
The adhesive phase 0.1g being put into sample bottle obtained in embodiment etc. is added ethyl acetate 30cc, makes bonding
After oxidant layer is impregnated with 24 hours, the content of the sample bottle is filtered separation using the stainless steel woven wire of 200 purposes,
Dry weight will be set as with 100 DEG C of residue weights after 2 hours dry on woven wire.Obtained weight is used to measure
Value calculates gel fraction according to following formula.Result is shown in the table 4 and table 5 together.
Gel fraction (%)=100 × (dry weight/the adhesive phase weight taken)
[bonding force]
Use is with bonding sheet made of described program, under the conditions of 25 DEG C/50%RH, makes the viscous of exposing using the roller of 2kg
Conjunction level crimps (attaching) in SUS plates.It is stood after attaching after twenty minutes, by bonding sheet in 180 ° of 25 DEG C/50%RH, peel angle
Under conditions of, it is removed from SUS plates with peeling rate 300mm/min, measures the peeling force (bonding force) of the adhesive phase of bonding sheet.
Result is shown in the table 4 and table 5 together.
[retentivity]
Retentivity is carried out according to JIS Z 1541, is 20mm width by bonding sheet severing, with the area phase of 20 × 20mm
The mode connect is attached at stainless steel plate, applies the load of 1Kg under conditions of 80 DEG C of temperature, whether there is or not fall when observation is placed 1 hour
It falls.Result is shown in the table 4 and table 5 together.
[constant load stripping patience]
By the adhesive layer face paste of exposing together in the stainless steel substrate configured in a manner of positive and negative and horizontal direction parallel
Lower face side.Secondly, in the end of the length direction one end for the test piece for being attached at stainless steel substrate, with to below vertical direction
Side applies the state of load, places 60 minutes, measures the distance of the peeling on the length direction of test piece at this time (mm) or until falls
Until time (min).Load is set as 200g when measuring temperature is 40 DEG C, and 100g is set as at 80 DEG C.By result together table
It is shown in the table 4 and table 5.
[analysis of result]
In Examples 1 to 10, by using containing (methyl) acrylic acid series atactic polymer and passing through hydrogel permeation layer
The bonding of (methyl) acrylic acid series triblock polymer that the weight average molecular weight (Mw) that analysis method measures is 3,000~30,000
Agent composition can reach outstanding bonding force, retentivity and constant load stripping patience.In contrast, in comparative example 1~6
In, use the viscous of (methyl) the acrylic acid series triblock polymer for being 3,000~30,000 without weight average molecular weight (Mw)
Mixture composite, therefore, result are that at least one aspect that bonding force or constant load are removed in patience is not outstanding.It therefore, can be bright
Prepared adhesive composition is better than adhesive composition prepared in comparative example 1~6 in true Examples 1 to 10 10.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of adhesive composition, which is characterized in that contain (methyl) acrylic acid series atactic polymer and (methyl) acrylic acid
It is triblock polymer, the weight average that (methyl) the acrylic acid series triblock polymer is measured by gel permeation chromatography
Molecular weight (Mw) is 3,000~30,000.
2. adhesive composition according to claim 1, which is characterized in that (methyl) the acrylic acid series three block polymerization
The blending amount of object is in relative to 100 mass parts of (methyl) acrylic acid series atactic polymer in the range of 1~49 mass parts.
3. adhesive composition according to claim 1 or 2, which is characterized in that (methyl) the acrylic acid series three block
Polymer, which has, utilizes the structure of block [A] and block [B] represented by [A]-[B]-[A].
4. adhesive composition according to any one of claim 1 to 3, which is characterized in that further contain isocyanic acid
Ester system crosslinking agent.
5. adhesive composition according to any one of claim 1 to 4, which is characterized in that be used for optical applications.
6. a kind of adhesive, which is characterized in that formed by the adhesive composition described in any one of claim 1 to 5.
7. a kind of bonding sheet, which is characterized in that include：
Base material；And
Adhesive layer is formed in at least one side of the base material using the adhesive composition described in any one of claim 1 to 5
On.
8. bonding sheet according to claim 7, which is characterized in that the thickness of the adhesive layer is 15 μm or less.
9. a kind of optical component, which is characterized in that containing adhesive layer, the adhesive layer is described in any one of claim 1 to 5
Adhesive composition formed.
10. optical component according to claim 9, which is characterized in that the thickness of the adhesive layer is 15 μm or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017062437A JP6850175B2 (en) | 2017-03-28 | 2017-03-28 | Adhesive compositions, adhesives, adhesive sheets, and optics |
| JP2017-062437 | 2017-03-28 |
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| Publication Number | Publication Date |
|---|---|
| CN108659732A true CN108659732A (en) | 2018-10-16 |
| CN108659732B CN108659732B (en) | 2021-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810259178.6A Active CN108659732B (en) | 2017-03-28 | 2018-03-27 | Adhesive composition, adhesive sheet, and optical member |
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| Country | Link |
|---|---|
| JP (1) | JP6850175B2 (en) |
| KR (1) | KR102433205B1 (en) |
| CN (1) | CN108659732B (en) |
| TW (1) | TWI766971B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7484158B2 (en) | 2019-12-20 | 2024-05-16 | Dic株式会社 | Adhesive sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1312658A2 (en) * | 2001-11-16 | 2003-05-21 | tesa AG | Oriented acrylate blockcopolymer |
| CN101113190A (en) * | 2006-07-25 | 2008-01-30 | 蒂萨股份公司 | Bimodal acrylate adhesive mass for gluing low energy and rough surfaces |
| CN102533169A (en) * | 2010-11-12 | 2012-07-04 | 琳得科株式会社 | Acrylate adhesive composition, acrylate adhesive and optical component with adhesive layer |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4442923B2 (en) | 2002-07-04 | 2010-03-31 | 日東電工株式会社 | Polymer modifier and method for producing the same |
| JP4092152B2 (en) * | 2002-07-25 | 2008-05-28 | 日東電工株式会社 | Adhesive optical film, optical film adhesive composition and image display device |
| US20060084755A1 (en) * | 2004-10-19 | 2006-04-20 | Good David J | Reactive hot melt adhesive with block acrylic copolymer |
| WO2011152511A1 (en) * | 2010-06-04 | 2011-12-08 | 株式会社クラレ | Pressure-sensitive adhesive composition for optical film |
| JP2013142131A (en) * | 2012-01-11 | 2013-07-22 | Dainippon Printing Co Ltd | Pressure-sensitive adhesive composition for triacetyl cellulose, as well as laminate using the same, optical film and optical element |
| JP6056434B2 (en) * | 2012-12-07 | 2017-01-11 | 大日本印刷株式会社 | Adhesive composition and surface protective film |
| CN107207683B (en) * | 2015-01-27 | 2020-03-31 | 株式会社可乐丽 | Acrylic block copolymer and adhesive composition |
| JP6412453B2 (en) * | 2015-03-26 | 2018-10-24 | 積水化学工業株式会社 | Adhesive composition and adhesive tape |
-
2017
- 2017-03-28 JP JP2017062437A patent/JP6850175B2/en active Active
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2018
- 2018-03-23 KR KR1020180033993A patent/KR102433205B1/en active IP Right Grant
- 2018-03-27 CN CN201810259178.6A patent/CN108659732B/en active Active
- 2018-03-27 TW TW107110571A patent/TWI766971B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1312658A2 (en) * | 2001-11-16 | 2003-05-21 | tesa AG | Oriented acrylate blockcopolymer |
| CN101113190A (en) * | 2006-07-25 | 2008-01-30 | 蒂萨股份公司 | Bimodal acrylate adhesive mass for gluing low energy and rough surfaces |
| CN102533169A (en) * | 2010-11-12 | 2012-07-04 | 琳得科株式会社 | Acrylate adhesive composition, acrylate adhesive and optical component with adhesive layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018165295A (en) | 2018-10-25 |
| KR20180109720A (en) | 2018-10-08 |
| CN108659732B (en) | 2021-01-15 |
| TWI766971B (en) | 2022-06-11 |
| TW201840784A (en) | 2018-11-16 |
| JP6850175B2 (en) | 2021-03-31 |
| KR102433205B1 (en) | 2022-08-16 |
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