CN105745296A - Pressure-sensitive adhesive composition and process for manufacturing pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive composition and process for manufacturing pressure-sensitive adhesive sheet Download PDF

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Publication number
CN105745296A
CN105745296A CN201480063124.2A CN201480063124A CN105745296A CN 105745296 A CN105745296 A CN 105745296A CN 201480063124 A CN201480063124 A CN 201480063124A CN 105745296 A CN105745296 A CN 105745296A
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Prior art keywords
composition
adhesion agent
agent composition
weight
silyl groups
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山口征太郎
大高翔
宫田壮
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Lintec Corp
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Lintec 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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    • C09J2433/00—Presence of (meth)acrylic polymer
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    • C09J2475/00—Presence of polyurethane

Abstract

Provided are: a pressure-sensitive adhesive composition which exhibits excellent constant-load-bearing properties and so on even in a case where the amount of a curing catalyst blended is small or even in a case where no curing catalyst is blended; and a process for manufacturing a pressure-sensitive adhesive sheet using said pressure-sensitive adhesive composition. A pressure-sensitive adhesive composition which comprises a silyl -terminated polymer (A), a (meth)acrylic ester copolymer (B), and a tackifier resin (C), and a pressure-sensitive adhesive sheet using said pressure-sensitive adhesive composition, wherein: the silyl-terminated polymer (A) is a silyl-terminated polymer having a prescribed structure; the (meth)acrylic ester copolymer (B) contains copolymerized units derived from a carboxyl-containing vinyl monomer; and the amount of a curing catalyst (D) blended is 0 to 0.1wt% relative to the total amount of the components (A) to (C).

Description

The manufacture method of adhesion agent composition and adhesive sheet
Technical field
The present invention relates to the manufacture method of a kind of adhesion agent composition and adhesive sheet.Even if being a small amount of particularly to the addition of a kind of curing catalysts, even if or when being not added with curing catalysts, the manufacture method of the adhesion agent composition that still can obtain good constant load etc. and the adhesive sheet using this adhesion agent composition and being formed.
Background technology
In the past, adhesive sheet, owing to having by compressing the advantage that can easily be attached at adherend, was therefore used as display label or electronic component adhesives etc. in many fields.
At this, this adhesive sheet then except good adhesion strength, also require when for bonding plane even across when imposing mechanical load for a long time, still will not peel off or produce skew in acceleration ground, and there is good constant load.
It is therefoie, for example, in order to promote anti-exclusion, motion has the two sides adhesion zone (such as, patent documentation 1) of the constant load with regulation.
More specifically, disclose a kind of two sides adhesion zone, its two sides adhesion zone used for the fixed clamp display panels and backlight framework in adhesion flexible printed circuit substrate, and the maximum with the loss angle tangent (tan δ) under frequency 1Hz is present in the temperature province of-40～-22 DEG C, gel fraction is 15～45%.
Additionally, motion goes out the adhesive sheet (such as, patent documentation 2) using terminal silyl groups (silyl) polymer comprising regulation to be formed as the adhesion agent composition of host.
More specifically, disclose a kind of adhesive sheet, it is characterized in that, main chain will be evenly mixed in or side chain will have amino-formate bond and/or urea key, and terminal silyl groups polymer 100 mass parts of hydrolyzable silyl group is contained in end, tackifying resin 10～150 mass parts, select free boron trifluoride and/or its complex, after fluoride compound 0.001～10 mass parts in the group that the alkali metal salt of fluorization agent and fluorine class mineral acid is constituted and the sticker predecessor that formed coat the surface with base material or plate substrate, by making this terminal silyl groups polymer cure, and this sticker predecessor is made adhering agent layer.
Prior art literature
Patent documentation
Patent documentation 1: No. 4645074 publications (claim) of Japanese Patent No.
Patent documentation 2:WO2010/038715 publication (claim)
Summary of the invention
The technical problem to be solved in the present invention
But, though the two sides adhesion zone that patent documentation 1 is recorded has a degree of constant load, but owing to the gel fraction of adhering agent layer is relatively low, therefore when being processed into roll shape, then there will be with time process, the adhesion agent composition constituting adhering agent layer has the problem easily oozed out from the side.Therefore, though attempting adding considerable cross-linking agent in adhesion agent composition and improving cohesiveness, but there will be the new problem that adhesiveness is extremely low.
In addition, in the adhesive sheet that patent documentation 2 is recorded, then must add the fluorine compounds such as boron trifluoride or fluorization agent as the reactive curing catalysts in order to improve the terminal silyl groups in terminal silyl groups polymer using ormal weight, therefore occur manufacturing cost and uprise, react and become to be difficult to control to, and there is the problem that operability becomes difficulty according to the kind of curing catalysts.
Therefore, the present application people are in view of the above circumstances, through meticulous effort, find acrylic copolymer and the tackifying resin by terminal silyl groups polymer being added regulation, even if the addition of curing catalysts is a small amount of, or when being not added with curing catalysts, still can obtain good constant load etc., and then complete the present invention.
That is, it is an object of the invention to provide a kind of when maintain good adherence characteristic, the effective manufacture method of the adhesion agent composition that can obtain good constant load and the adhesive sheet using this adhesion agent composition and being formed.
Solve the technological means of technical problem
nullAccording to the present invention，A kind of adhesion agent composition is provided，And then above-mentioned problem points can be solved: this adhesion agent composition，It is the terminal silyl groups polymer including at least (A) composition、(B) tackifying resin of (methyl) acrylate copolymer of composition and (C) composition，It is characterized by that the terminal silyl groups polymer of (A) composition for have poly (oxyalkylene) based structures in main chain，And in a part or the side chain of main chain, there is amino-formate bond and urea key、Or any of which，And two ends in main chain have the hydrolyzable silyl group represented by following formula (1)，(B) (methyl) acrylate copolymer of composition has the co-polymeric share from carboxylic vinyl monomer，And relative to the total amount of (A)～(C) composition，(D) addition of the curing catalysts of composition is 0 or more than 0、And 0.1 weight % value below；
[chemical formula 1]
In formula (1), X1And X2Independently be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
Namely, the adhesion agent composition of the present invention, the tackifying resin of acrylic copolymer and (C) composition by the terminal silyl groups polymer of (A) composition being added the regulation of (B) composition, even if being reduced as far as the addition of the curing catalysts of (D) composition, (B) acrylic copolymer of the regulation of composition still can play the catalytic effect in the reaction of hydrolyzable silyl group, and play good adherence characteristic simultaneously.
Therefore, in adhesive sheet, even if the addition of curing catalysts is a small amount of, or when being not added with curing catalysts, still when maintaining respective good adherence characteristic, good constant load can be obtained.
In addition, (A) the terminal silyl groups polymer of composition owing to having the hydrolyzable silyl group represented by formula (1) at main chain two end, therefore (A) composition crosslink density each other is adjusted to suitable scope, and the balance between adhesion strength and cohesiveness in adhesion agent composition can be better.
Further, the adhesion agent composition obtained, owing to having polyoxy alkylidene (polyoxyalkylene) structure in main chain, therefore can be given the flexibility of appropriateness by the terminal silyl groups polymer of (A) composition.
Additionally, when constituting the adhesion agent composition of the present invention, the addition of the curing catalysts of (D) composition is relative to the total amount of (A)～(C) composition, it is preferred to 0 weight %.
Constitute by being made this, then need not make the interpolation operation of the curing catalysts that hydrolyzable silyl group react, manufacturing cost and raising operability can be forced down further.
In addition, when constituting the adhesion agent composition of the present invention, relative to terminal silyl groups polymer 100 weight portion of (A) composition, the addition of (methyl) acrylate copolymer of (B) composition is preferably the value within the scope of 5～100 weight portions.
Constitute by being made this, the balance between the adhesion strength in adhesion agent composition and cohesiveness can be made better.
Additionally, when constituting the adhesion agent composition of the present invention, relative to terminal silyl groups polymer 100 weight portion of (A) composition, the addition of the tackifying resin of (C) composition is preferably the value within the scope of 50～140 weight portions.
Constitute by being made this, the balance between the adhesion strength in adhesion agent composition and cohesiveness can be made better.
Additionally, when constituting the adhesion agent composition of the present invention, the weight average molecular weight of the terminal silyl groups polymer of (A) composition is preferably 15,000～200, the value in 000 scope.
Constituted by this, the balance between in adhesion agent composition and flexibility, adhesion strength and cohesiveness can be made better.
Additionally, when constituting the adhesion agent composition of the present invention, the carboxylic vinyl monomer that (methyl) acrylate copolymer of (B) composition uses when carrying out copolymerization is preferably (methyl) acrylic monomers.
Constituted by this, the reactivity of hydrolyzable silyl group caused by (methyl) acrylate copolymer can be improved further.
In addition, when constituting the adhesion agent composition of the present invention, (B) carboxylic vinyl monomer when (methyl) acrylate copolymer of composition carries out copolymerization make consumption relative to whole monomer component 100 weight %, it is preferred to the value within the scope of 0.1～50 weight %.
Consisting of this, not only the polymerization of (methyl) acrylate copolymer becomes easy, and can make the reactivity of this hydrolyzable silyl group caused by (methyl) acrylate copolymer, or the adhesiveness of adhesion agent composition stably promotes.
Additionally, when constituting the adhesion agent composition of the present invention, the tackifying resin of (C) composition is preferably terpene phenolic resinoid.
Constituted by this, can easily the glass transition temperature of the adhesion agent composition obtained be regulated in suitable scope, when maintaining good adherence characteristic, better constant load can be obtained.
Additionally, the manufacture method that another form is a kind of adhesive sheet of the present invention, it for possessing the manufacture method of the adhesive sheet of the adhering agent layer being made up of adhesion agent composition on the two sides of base material or one side, and comprises following operation (1)～(3).
null(1) operation of adhesion agent composition is prepared: this adhesion agent composition is the terminal silyl groups polymer including at least (A) composition、(B) (methyl) acrylate copolymer of composition、And the adhesion agent composition of the tackifying resin of (C) composition，Wherein the terminal silyl groups polymer of (A) composition for have poly (oxyalkylene) based structures in main chain，And at a part or the side chain of main chain, there is amino-formate bond and urea key、Or any of which，And two ends in main chain have the hydrolyzable silyl group represented by following formula (1)，(B) (methyl) acrylate copolymer of composition has the co-polymeric share from carboxylic vinyl monomer，And，Total amount relative to (A)～(C) composition，(D) addition of the curing catalysts of composition is 0 or more than 0、And 0.1 weight % value below，
[chemical formula 2]
In formula (1), X1And X2Standing alone as hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20；
(2) adhesion agent composition is laminated in two sides or the one side of base material, and makes the operation of the adhesive sheet possessing the adhering agent layer being made up of uncured adhesion agent composition；
(3) heating adhesion agent composition, and make and possess by the operation of the adhesive sheet solidifying the adhering agent layer that adhesion agent composition is constituted.
Namely, the adhesive sheet of the present invention is in adhesion agent composition, the tackifying resin of acrylic copolymer and (C) composition by the terminal silyl groups polymer of (A) composition being added the regulation of (B) composition, even if being reduced as far as the addition of the curing catalysts of (D) composition, (B) acrylic copolymer of the regulation of composition still can play the catalytic effect in the reaction of hydrolyzable silyl group, and can play good adhesiveness simultaneously.
Therefore, in adhesive sheet, even if the addition of curing catalysts is a small amount of, or when being not added with curing catalysts, still can when maintaining each good adhesiveness, it is thus achieved that good constant load, and thus can reduce the manufacturing cost of adhesive sheet, and be conducive to economic benefit.
In addition, (A) the terminal silyl groups polymer of composition owing to having the hydrolyzable silyl group represented by formula (1) at two ends of main chain, therefore the crosslink density that (A) composition is each other is adjusted to suitable scope, in adhesive sheet, the balance between the adhesion strength in adhesion agent composition and cohesiveness can be made better.
Further, the terminal silyl groups polymer of (A) composition owing to having poly (oxyalkylene) based structures in main chain, therefore in the adhesive sheet obtained, can give the flexibility of appropriateness.
Accompanying drawing explanation
Fig. 1 (a)～(b) respectively illustrates the synthetic method of the terminal silyl groups polymer of regulation and the reaction equation of curing reaction.
The FT-IR spectrum of Fig. 2 (a)～(b) respectively tackifying resin (non-hydrogenated terpene phenolic resinoid and completely hydriding terpene phenolic resin).
Fig. 3 (a)～(c) is the figure of the form for being described separately adhesive sheet.
Fig. 4 (a)～(d) is for for being described separately the manufacture method of adhesive sheet and the figure of type of service.
Detailed description of the invention
[the first embodiment]
nullFirst embodiment of the present invention is a kind of adhesion agent composition，It is the terminal silyl groups polymer including at least (A) composition、(B) (methyl) acrylate copolymer of composition、And the adhesion agent composition of the tackifying resin of (C) composition，It is characterized in that，(A) the terminal silyl groups polymer of composition has poly (oxyalkylene) based structures in main chain，And at a part or the side chain of main chain, there is amino-formate bond and urea key、Or any of which，And two ends at main chain have the hydrolyzable silyl group represented by following formula (1)，(B) (methyl) acrylate copolymer of composition has the co-polymeric share from carboxylic vinyl monomer，And，Total amount relative to (A)～(C) composition，(D) addition of the curing catalysts of composition is 0 or more than 0、And 0.1 weight % value below.
[chemical formula 3]
In formula (1), X1And X2Independent and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
Hereinafter, with reference to suitable accompanying drawing, the adhesion agent composition of first embodiment of the present invention is illustrated.
1. (A) composition: terminal silyl groups polymer
(1) basic comprising
(A) the terminal silyl groups polymer of composition, it is characterized in that, there is at main chain or side chain amino-formate bond and urea key or any of which, and at two ends of main chain, there is the hydrolyzable silyl group represented by above-mentioned formula (1) simultaneously.
Its reason is, due to this (A) composition have 2 officials represented by formula (1) can water-disintegrable terminal silyl groups, therefore tridimensional network can be effectively formed by (A) composition hydrolysis dehydrating condensation each other.
Therefore, by the combination with the tackifying resin of regulation, excellent adhesion strength can be played, when being used in adhesive sheet, good adhesiveness can be represented.
Additionally, be somebody's turn to do (A) composition owing to having 2 officials' water-disintegrable terminal silyl groups of energy represented by formula (1), the gel fraction in adhesion agent composition after being solidified by adjustment within the limits prescribed, can play excellent cohesiveness.
Therefore, even if adhesion agent composition is being applicable to adhesive sheet, and when being processed into the situation of roll, sticker still can be suppressed to pass through with the time and ooze out from the side.
Therefore, by using the terminal silyl groups polymer of regulation as (A) composition, the adhesion agent composition of balancing good between adhesion strength and cohesiveness can be obtained.
Additionally, in formula (1), the carbon number of the alkyl represented by R is 1～20, but from the hydrolysis good angle of dehydration condensation, more preferably 1～12, more preferably 1～3.
Additionally, in formula (1), X1Or X2During for alkoxyl, the carbon number in this alkoxyl is from being hydrolyzed the angle that dehydration condensation is good, it is preferred to 1～12, more preferably 1～3.
Additionally, this terminal silyl groups polymer is made up of the skeleton part of the end section specified Yu regulation.
In addition, about shown in Fig. 1 (a) using the carbamate prepolymer (diisocyanate cpd) represented by formula (1) and the halosilyl represented by formula (2) as the concrete synthetic method of the terminal silyl groups polymer represented by the formula (3) of raw material, then illustrate in this second embodiment.
First, the concrete structure of the end section in the terminal silyl groups polymer represented by the formula in Fig. 1 (a) (3) is such as shown in following formula (2)～(8) (end section-A～G).
[chemical formula 4]
In formula (2), R2And R3For carbon number 1～20, it is preferred to the alkyl of carbon number 1～8, R, X1And X2Identical with the situation of formula (1), also it is identical content in following formula (3)～(8).
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
In formula (8), X3For alkylidene, X4Organic group for carbon number 1～20.
That is, terminal silyl groups polymer is by having this end section, as shown in Fig. 1 (b), curing reaction formed by dehydrating condensation not only can be made to produce, and the attaching for adherend can be made firmer.
Additionally, the skeleton of the main chain of the terminal silyl groups polymer represented by formula (3) in Fig. 1 (a) or side chain, it is characterised in that it is poly (oxyalkylene) based structures.
It reason for this is that, owing to passing through have poly (oxyalkylene) based structures in the molecule, and the adhesion agent composition obtained can give appropriateness flexibility, and can promote the attaching for adherend further.
Additionally, as the concrete example of this polyoxy alkylidene, can enumerate such as polyoxypropylene or polyoxyethylene etc..
In addition, (A) the terminal silyl groups polymer of the regulation of composition is such as shown in Fig. 1 (a), it is characterized in that, side chain does not have a hydrolyzable silyl group represented by formula (1), and for only having two terminal silyl groups polymer of hydrolyzable silyl group represented by formula (1) in two ends of main chain.
It reason for this is that, if this two terminal silyl groups polymer, (A) composition crosslink density each other is adjusted to suitable scope, and the balance adjustment of the adhesion strength in the adhesion agent composition after solidification and cohesiveness can be made to become easy.
In addition, as (A ') composition, comprise single terminal silyl groups polymer only in single end of main chain with hydrolyzable silyl group represented by formula (1) further, and by its addition relative to two terminal silyl groups polymer 100 weight portions, it is preferred to the value within the scope of 0.1～30 weight portion.
It reason for this is that, by two terminal silyl groups polymer are mixed single terminal silyl groups polymer with the scope of regulation, (A) composition crosslink density each other is adjusted to conveniently scope, and the balance adjustment of the adhesion strength in the adhesion agent composition after solidification and cohesiveness can be made to become to be more prone to.
That is, if the addition of single terminal silyl groups polymer becomes the value less than 0.1 weight portion, then cause having the situation that cannot fully obtain its additive effect.On the other hand, if the addition of single terminal silyl groups polymer becomes more than 30 weight portion, then can cause that (A) composition crosslink density each other excessively reduces, and have the situation being difficult to obtain the gel fraction of regulation.
Accordingly, with respect to two terminal silyl groups polymer 100 weight portions, the addition of single terminal silyl groups polymer is more preferably the value within the scope of 0.5～10 weight portion, the more preferably value within the scope of 1～5 weight portion.
But, even if owing to having confirmed that when only using two terminal silyl groups polymer, still can obtain the adhesion agent composition that adhesion strength is excellent, therefore when without especially desirable, angle from the simplification etc. of manufacturing process, preferably do not mix single terminal silyl groups polymer, and only use two terminal silyl groups polymer.
(2) weight average molecular weight
Additionally, the weight average molecular weight of the terminal silyl groups polymer of (A) composition is preferably 15,000～200, the value in 000 scope.
Its reason is, if become the value less than 15,000 due to the weight average molecular weight of this terminal silyl groups polymer, then cause that having molecular structure becomes close and cannot obtain sufficient adhesion strength, or viscosity becomes too low, solution the situation that processability when being coated with and cause sheet material is deteriorated.
On the other hand, if the weight average molecular weight of this terminal silyl groups polymer is beyond 200,000, causing having become apparent upon and cause fitness of process to reduce because of viscosity increase etc., crosslink density excessively reduces, and becomes the situation being difficult to regulate adhesion strength with the balance of cohesiveness.
Therefore, it is more preferably 20,000～150 with the weight average molecular weight by the terminal silyl groups polymer of (A) composition, the value in 000 scope, the more preferably value in 30,000～100,000 scope.
Additionally, the known molecular weight measurement device that the weight average molecular weight of the terminal silyl groups polymer of (A) composition can use gel permeation chromatography (GPC) etc. measures.
In addition, when adding above-mentioned (A ') composition, the weight average molecular weight of (A ') composition can be identical with (A) composition.
(3) addition
Additionally, relative to the total amount 100 weight % of adhesion agent composition, the addition of the terminal silyl groups polymer of (A) composition is preferably the value within the scope of 20～90 weight %.
It reason for this is that, if the addition of terminal silyl groups polymer becomes less than 20 weight %, the absolute magnitude of (A) composition overall relative to adhesion agent composition becomes very few, and has the situation becoming to be difficult to obtain abundant cohesiveness.
On the other hand, if the addition of this terminal silyl groups polymer is more than 90 weight %, then the absolute magnitude of overall relative to adhesion agent composition (A) composition becomes too much, has the situation becoming to be difficult to obtain abundant adhesion strength.
Accordingly, with respect to the total amount 100 weight % of adhesion agent composition, the addition of the terminal silyl groups polymer of (A) composition is more preferably the value within the scope of 25～85 weight %, more preferably the value within the scope of 30～80 weight %.
2. (B) composition: (methyl) acrylate copolymer
(1) kind 1
In addition, the kind of (methyl) acrylate copolymer is not particularly limited, as long as having the co-polymeric share from carboxylic vinyl monomer and other the co-polymeric share from (methyl) acrylate monomer or vinyl monomer etc., then can use (methyl) acrylate copolymer of any kind.
More specifically, as carboxylic vinyl monomer, one or two or more kinds the combination independent in acrylic acid, methacrylic acid, maleic acid, itaconic acid, monomethyl maleate, citraconic acid mono-methyl, acrylic acid 2-carboxyethyl, methacrylic acid 2-carboxyethyl, mono succinate (2-acryloyl oxoethyl ester), mono succinate (2-methacryl oxo ethyl ester) etc. can be enumerated.
On the other hand, (methyl) acrylate monomer or vinyl monomer etc. as other, can enumerate such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, acrylamide, (methyl) acrylic acid list methylamino ethyl ester, ethylene, propylene, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 3-hydroxybutyl, (methyl) acrylic acid 4-hydroxybutyl, hydroxybutyl vinyl ether, hydroxyethyl (methyl) acrylate, diethylene glycol monoacrylate, styrene, vinyl acetate, one or two or more kinds combination independent in acryloyl morpholine etc..
(2) kind 2
In addition, kind about (methyl) acrylate copolymer, carboxylic vinyl monomer when (methyl) acrylate copolymer carries out copolymerization make consumption, for full monomer component 100 weight %, it is preferred to the value within the scope of 0.1～50 weight %.
It reason for this is that, consumption is made by what so control carboxylic vinyl monomer, not only the polymerization of (methyl) acrylate copolymer becomes easy, and the reactivity of hydrolyzable silyl group that this (methyl) acrylate copolymer causes or the adhesiveness of adhesion agent composition can be made stably to promote.
Therefore, carboxylic vinyl monomer when (methyl) acrylate copolymer carries out copolymerization make consumption relative to full monomer component 100 weight %, the more preferably value within the scope of 1～30 weight %, it is preferred that the value within the scope of 3～15 weight %.
(3) weight average molecular weight
Additionally, the weight average molecular weight of (methyl) acrylate copolymer of (B) composition is preferably 1,000～3, the value in 000,000 scope.
It reason for this is that, is somebody's turn to do (methyl) if the weight average molecular weight of the acrylate copolymer value less than 1,000, then causes the significantly reduced situation of adhesiveness having adhesion agent composition.
On the other hand, it is somebody's turn to do (methyl) if the weight average molecular weight of acrylate copolymer is beyond 3,000, when 000, then cause that the intermiscibility having with the terminal silyl groups polymer of (A) composition significantly reduces, polymerization time becomes long, and becomes to be readily decomposed to the situation of low-molecular-weight thing.
Therefore, the weight average molecular weight of (methyl) acrylate copolymer of (B) composition is more preferably 5,000～2, the value in 000,000 scope, more preferably the value in 10,000～1,500,000 scope.
(4) addition
Additionally, relative to terminal silyl groups polymer 100 weight portion of (A) composition, the addition of (methyl) acrylate copolymer of (B) composition is preferably the value within the scope of 5～100 weight portions.
It reason for this is that, by the addition of (methyl) acrylate copolymer is set to the value within the scope of this, can obtain the adhesion agent composition of balancing good between adhesion strength and cohesiveness.
That is, be somebody's turn to do (methyl) if the addition of acrylate copolymer becomes less than 5 weight portion, then the reactivity of hydrolyzable silyl group significantly reduces, and therefore causes the situation that the cohesiveness having adhesion agent composition reduces.
On the other hand, it is somebody's turn to do (methyl) if the addition of acrylate copolymer is more than 100 weight portion, then causes there is the significantly reduced situation of the adhesiveness in adhesion agent composition.
Therefore, terminal silyl groups polymer 100 weight portion relative to (A) composition, the addition of (methyl) acrylate copolymer of (B) composition is more preferably the value within the scope of 5～70 weight portions, more preferably the value within the scope of 10～50 weight portions.
3. (C) composition: tackifying resin
(1) kind
In addition, the kind of tackifier resins is not particularly limited, can enumerate such as newtrex, newtrex ester, the rosin based resins such as rosin derivative, polyterpene resin, aromatic modified terpene resin and hydride thereof, terpene phenol resin, coumarone-indene resin (coumarone indeneresin), aliphatic category petroleum resinoid, fragrance same clan's Petropols and hydride thereof, aliphatic/aromatic copolymer Petropols, partial hydrogenation terpene phenolic resinoid, one or two or more kinds combination independent in the low molecule mass polymer of styrene or substituted phenylethylene etc..
It reason for this is that, these tackifying resins will not hinder the interaction of the terminal silyl groups polymer of the regulation with (A) composition, and adhesion agent composition can give excellent adhesion strength and cohesiveness.
Additionally, tackifying resin is more preferably terpene phenolic resinoid, more preferably complete hydriding terpene phenolic resin or partial hydrogenation terpene phenolic resinoid.
It reason for this is that, by comprising terpene phenolic resinoid, and the glass transition temperature of the terminal silyl groups polymer of easily adjustable (A) composition.
In addition, if hydriding terpene phenolic resin or partial hydrogenation terpene phenolic resinoid completely, then can become easier to the maximum of the loss angle tangent in the adhesion agent composition constituting adhering agent layer, namely glass transition temperature is adjusted to higher, and, even if the cohesiveness in adhesion agent composition is higher value, still can obtain good constant load.
At this, complete hydriding terpene phenolic resin is that partial hydrogenation terpene phenolic resinoid is by terpene phenolic resinoid is given the tackifying resin that partial hydrogenation obtains by terpene phenolic resinoid hydrogenates tackifying resin substantially completely that obtain.
And, terpene phenol resin has the double bond from terpenes and the aromatic ring double bond from phenols.
Therefore, complete hydriding terpene phenolic resin means the tackifying resin that two positions at terpenes position and phenol position completely or almost completely hydrogenate, partial hydrogenation terpene phenolic resinoid means the degree of hydrogenation at above-mentioned position and incomplete, and is only partially hydrogenated terpene phenolic resinoid.
Additionally, whether meet complete hydriding terpene phenolic resin, the FT-IR spectrum by fourier-transform infrared spectrophotometer (FT-IR) gained as be described hereinafter can be used to judge.
At this, use the FT-IR spectrum of the complete hydriding terpene phenolic resin shown in Fig. 2 (b), more specifically illustrate.
This, by the carbon-hydrogen link stretching vibration from methyl at about 2960cm-1Peak heights when being set to 100, from phenol position aromatic series carbon-to-carbon double bond stretching vibration at 1625-1575cm-1If peak heights less than 20%, then be considered as phenol position and completely or almost completely hydrogenate.
On the other hand, if during from peak heights more than 20% at phenol position, as shown in Fig. 2 (a), then phenol position and terpenes position almost unhydrided non-hydrogenated terpene phenolic resinoid it is judged as.
Additionally, the method for hydrogenation or reaction formation are not particularly limited, as complete hydriding terpene phenolic resin, for instance can enumerate and pacify the NH etc. that former chemistry (strain) is made.
(2) addition
Additionally, relative to terminal silyl groups polymer 100 weight portion of (A) composition, the addition of the tackifying resin of (C) composition is preferably the value within the scope of 50～140 weight portions.
It reason for this is that, is the value within the scope of this by the addition of tackifying resin, can obtain the adhesion agent composition of balancing good between adhesion strength and cohesiveness.
That is, if the addition of this tackifying resin is less than the value of 50 weight portions, then cause there is the situation becoming to be difficult to obtain abundant adhesion strength.
On the other hand, if the addition of this tackifying resin exceeds the value of 140 weight portions, then cause that there is cohesiveness reduces on the contrary, when adhesive sheet is processed into roll, the situation that adhesion agent composition oozes out with time process.
Therefore, terminal silyl groups polymer 100 weight portion relative to (A) composition, it is more preferably the value within the scope of 60～130 weight portions, more preferably the value within the scope of 70～120 weight portions with the addition of the tackifying resin of (C) composition.
4. (D) composition: curing catalysts
(1) kind
In addition, when constituting adhesion agent composition, substantially without the curing catalysts ((D) composition) for making hydrolyzable silyl group react, but when adding this curing catalysts, as this curing catalysts, it is preferred to select at least one in the group that free aluminum class catalyst, titanium class catalyst, zirconium class catalyst and boron trifluoride class catalyst constitute.
It reason for this is that, these curing catalysts can make the control of the terminal silyl groups polymer of (A) composition crosslink density each other become easy, and the adhesion strength in the adhesion agent composition after solidification and the balance between cohesiveness can be made better.
More specifically, as aluminum class catalyst, it is preferable that the alkoxide (alkoxide) of aluminum, aluminium chelate compound, aluminum chloride (III).
Additionally, as titanium class catalyst, it is preferable that the alkoxide of titanium, titanium chelate, titanium chloride (IV).
Additionally, as zirconium class catalyst, it is preferable that the alkoxide of zirconium, zirconium chelate, zirconium chloride (IV).
Further, as boron trifluoride class catalyst, it is preferable that amine complex or the alcohol complex of boron trifluoride are preferred.
(2) addition
In addition, (D) curing catalysts of composition can be without, can be 0, but during in order to promote curing reaction etc. and be added, relative to the total amount of (A)～(C) composition, its addition is preferably greater than 0 and 0.1 weight % value below.
It reason for this is that, if during value that this addition is more than 0.1 weight %, then causing that having manufacturing cost uprises, catalytic action becomes over, the situation that adhesion agent composition just first solidifies before coating base material.
Therefore, when adding the curing catalysts of (D) composition, relative to the total amount of (A)～(C) composition, its addition is more preferably higher than 0 and 0.01 weight % value below, is further preferably greater than 0 and 0.001 weight % value below.
5. (E) composition: silane coupler
(1) kind etc.
Additionally, when constituting adhesion agent composition, this adhesion agent composition preferably comprises the silane coupler of (E) composition.
It reason for this is that, by adding the silane coupler of ormal weight, then has the adhesion strength that not only can make adhesion agent composition or moisture-proof to promote, and can play the situation of the effect of crosslinking coagent as terminal silyl groups polymer simultaneously.
And, in order to effectively play the effect as crosslinking coagent, in various silane couplers, more preferably use the silane coupler with amino.
It reason for this is that, this has the silane coupler of amino, can play consistently the effect of crosslinking coagent as terminal silyl groups polymer, and the cohesiveness of adhesion agent composition can be adjusted to more suitable scope.
Therefore, as the suitable poly-silane coupler having amino, one or two or more kinds the combination independent in 3-TSL 8330, APTES, N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-APTES, N-phenyl-3-TSL 8330 etc. can be enumerated.
(2) addition
Additionally, when adding the silane coupler of (E) composition, relative to terminal silyl groups polymer 100 weight portion of (A) composition, the addition of this silane coupler is preferably the value within the scope of 0.01～1.0 weight portion.
It reason for this is that, if in this scope, can not only provide more cheap adhesion agent composition, can stably promote adhesion strength and the moisture-proof of adhesion agent composition simultaneously.
6. various additives
In addition, in adhesion agent composition, as composition other than the above, it is preferable that add and mix functional oligomerization thing, pigment, titanate coupling agent, aluminum coupling agent, the dryness wet goods such as the fire retardants such as the diluent such as thixotropic agent, isoparaffin such as dehydrant, filler, conductive material, thermally conductive materials, plasticizer, anhydride silica, the amide waxes such as such as ageing resistance inorganic agent, vinyl silane compound or calcium oxide, aluminium hydroxide, halogen fire retardant, phosphorus type flame retardant, silicone based flame retardant, organosilicon alkoxyl oligomer, acrylate oligomers.
In addition, when adding these additives, though it is different according to the kind of additive, it is added under the degree of effect of the present invention preferably in not undermining, terminal silyl groups polymer 100 weight portion relative to the regulation of (A) composition, its addition is preferably the value within the scope of 0.01～100 weight portion, more preferably the value within the scope of 0.01～70 weight portion, it is particularly preferred to be the value within the scope of 0.01～40 weight portion.
7. gel fraction
Additionally, when constituting adhesion agent composition, the gel fraction of adhering agent layer is preferably the value in 20～80% scopes.
It reason for this is that, by the gel fraction of adhering agent layer being set to the value within the scope of this, excellent cohesiveness can be played, will be provided with the adhesive sheet of adhering agent layer when being processed into roll, can suppress with the time through and constitute the adhesion agent composition of adhering agent layer and ooze out from the side.
That is, if the gel fraction of the adhering agent layer value less than 20%, then cause that having cohesiveness becomes too small, when being processed into roll, pass through with the time and constitute the situation that the adhesion agent composition of adhering agent layer oozes out from the side.
On the other hand, when the gel fraction of adhering agent layer becomes too high, then cause having the situation that cannot obtain abundant adhesion strength.
Therefore, the gel fraction of the adhering agent layer in adhesion agent composition is more preferably the value in 30～70% scopes, more preferably the value in 35～65% scopes.
In addition, after " gel fraction of adhering agent layer " refers to adhesion agent composition is coated base material, 23 DEG C, under 50%RH environment after 14 days Ageing Treatment (seasoning), using the sticker after this Ageing Treatment as measuring samples and by the gel fraction measured by infusion process.Measuring method about gel fraction more specifically is then recorded in embodiment 1 described later.
8. thickness
Additionally, the thickness of the adhering agent layer being made up of adhesion agent composition, it is often preferred that the value in 1～100 μ m, more preferably the value in 5～50 μ m.
It reason for this is that, if the thickness of this adhering agent layer is less than 1 μm, then causes having the situation that cannot obtain abundant adhesiveness etc., and on the contrary, if the thickness of adhering agent layer is more than 100 μm, then residual solvent becomes situation that is many and that have adhesiveness etc. easily to produce change.
9. form
Additionally, adhesive sheet can adopt various forms, for instance, as shown in Fig. 3 (a), it is preferable that the adhering agent layer 12 being made up of the adhesion agent composition of the present invention is formed at the one side of base material 10, and is made the form of the adhesive sheet 50 of one side.
If the form of this adhesive sheet 50, adhesion zone, display label or surface protection adhesive sheet etc. can be processed into, and be applicable to various uses.
Additionally, as shown in Fig. 3 (b), it is preferable that the adhering agent layer 12 (12a, 12b) being made up of the adhesion agent composition of the present invention is formed at the two sides of base material 10, and is made the form of two sides adhesive sheet 52.
If the form of this adhesive sheet 52, then can be suitably used in the purposes such as the temporarily fixing conveyor belt using electronic component sticky material or electronic component etc. of electronic component etc..
Further, as shown in Fig. 3 (c), it is preferably made the form of two sides adhesive sheet 54, the adhering agent layer 12 being made up of the adhesion agent composition of the present invention is formed in the one side of base material 10 by it, and on another side, forming the adhesion agent composition (include adhesive composite) different with the present invention, for instance other adhering agent layers (including bond layer) 18 being made up of acrylic compounds sticker, phenylethylene sticker, rubber-like sticker, silicone based sticker, epoxies bonding agent etc. form.
If the form of this adhesive sheet 54, then in the purposes of the fixing member etc. that can be suitable for being used in being fixed on substrate by electronic component.
At this; as the base material forming adhering agent layer, it may be preferable to enumerate such as by polyethylene, polypropylene, polyethylene terephthalate, PEN, polybutylene terephthalate (PBT), polyimides, Polyetherimide, polyether-ketone, polyether-ether-ketone, Merlon, polymethyl methacrylate, tri acetyl cellulose, poly-norborneol ester, vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl chloride, polyurethane acrylates, polyether sulfone, polyphenylene ether sulfone etc. the resin film that constitutes of resin.
And, the thickness of base material is not particularly limited, it is often preferred that 1～1, the value in 000 μ m, more preferably the value in 10～100 μ m.
10. peeling base (stripping film)
Fit the form of peeling base (stripping film) 22 additionally, the adhesive sheet of the present invention is preferably on the surface of adhering agent layer.
As this peeling base, the peeling base such as mylar such as polyethylene terephthalate, polybutylene terephthalate (PBT), PEN or the polyolefin film such as polypropylene, polyethylene being coated with the removers such as organic siliconresin and be provided with peel ply can be enumerated.
Additionally, the thickness of this peeling base, it is often preferred that the value in 20～150 μ m.
Additionally, by the difference that the peeling force in 2 peeling base arranges regulation, when peeling off the peeling base of low stripping force side, can prevent adhering agent layer from partly following.
[the second embodiment]
Second embodiment is the manufacture method of a kind of adhesive sheet, and it for possessing the manufacture method of the adhesive sheet of the adhering agent layer being made up of adhesion agent composition on the two sides of base material or one side, it is characterised in that comprises following operation (1)～(3).
null(1) operation of adhesion agent composition is prepared，This adhesion agent composition is the terminal silyl groups polymer including at least (A) composition、(B) (methyl) acrylate copolymer of composition、And the adhesion agent composition of the tackifying resin of (C) composition，Wherein the terminal silyl groups polymer of (A) composition has poly (oxyalkylene) based structures in main chain，And in a part or the side chain of main chain, there is amino-formate bond and urea key、Or any of which，And two ends in main chain have the hydrolyzable silyl group represented by following formula (1)，(B) (methyl) acrylate copolymer of composition has the co-polymeric share from carboxylic vinyl monomer，And，Total amount relative to (A)～(C) composition，(D) addition of the curing catalysts of composition is 0 or more than 0、And 0.1 weight % value below，
[chemical formula 11]
In formula (1), X1And X2Independent and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20；
(2) adhesion agent composition is laminated in two sides or the one side of base material, and makes the operation of the adhesive sheet possessing the adhering agent layer being made up of uncured adhesion agent composition；
(3) heating adhesion agent composition, and make and possess by the operation of the adhesive sheet solidifying the adhering agent layer that adhesion agent composition is constituted.
Hereinafter, with reference to Fig. 4 (a)～(d) etc., specifically describe the manufacture method of adhesive sheet about the second embodiment.
1. operation (1) (preparatory process of adhesion agent composition)
Tackifying resin that operation (1) comprises the terminal silyl groups polymer of (A) composition, (methyl) acrylate copolymer of (B) composition and (C) composition for preparation etc. and the operation of adhesion agent composition that formed.
At this, with reference to Fig. 1 (a), it is shown that the synthesis example of the terminal silyl groups polymer of (A) composition.
First, the end in molecular backbone or side chain prepared represented by Fig. 1 (a) Chinese style (1) has the carbamate prepolymer (diisocyanate cpd) of NCO.
Then, prepare the single end in molecule represented by Fig. 1 (a) Chinese style (2) and there is the active hydrogen-based can reacted with NCO, and there is in another end of molecule the silylating agent of the hydrolyzable silyl group represented by formula (1).
Then, carbamate prepolymer represented by Homogeneous phase mixing formula (1) and after the silylating agent represented by formula (2), such as, under nitrogen atmosphere, 80 DEG C, 1 hour when be heated reaction, the terminal silyl groups polymer represented by formula (3) can be obtained.
In addition, as shown in Fig. 1 (b), terminal silyl groups polymer represented by formula (3) is via the hydrolysis of the hydrolyzable silyl group represented by formula (1), then carries out the curing reaction that dehydrating condensation causes, can form tridimensional network.
Additionally, when the terminal silyl groups polymer represented by synthesis type (3), with the situation of Fig. 1 (a) on the contrary, silylating agent is while having NCO, the compound with regulation polymer backbone can active hydrogen-based.
In addition, be directed in the amino-formate bond on the main chain of the terminal silyl groups polymer of regulation or side chain or the reactive hydrogen in urea key, can illustrated in the first embodiment, replaced by organic group.
Therefore, allophanic acid ester bond is included in the category of amino-formate bond, and biuret linkage is included in the category of urea key.
Then, according to demand, with retarder thinner by after the terminal silyl groups polymer dilution of (A) composition obtained, under agitation, add (methyl) acrylate copolymer of (B) composition of ormal weight, and be made Homogeneous phase mixing liquid.
Then, to the mixed liquor obtained, the curing catalysts of the tackifying resin of (C) composition, (D) composition is added respectively with ormal weight, and after adding other additives again, stirring is to uniformly, further, according to the mode becoming required viscosity, add retarder thinner as required further, thus can obtain adhesion agent composition solution.
2. operation (2) (painting process of adhesion agent composition)
Operation (2), as shown in Fig. 4 (a), for the adhesion agent composition solution of acquisition is coated base material 10, and forms the operation of coating layer 12 '.
Additionally, as the method for coating adhesion agent composition solution, such as stick coating method, scraper for coating (knifecoating) method, rolling method, scraper plate coating (bladecoating) method, die coating methods, gravure coating process etc. can be enumerated.Furthermore it is preferred that after being coated with adhesion agent composition solution and forming coating layer 12 ', make solvent disperse and dry.
Now, the thickness of coating layer 12 ' is preferably the value in 1～100 μ m, more preferably the value in 5～50 μ m.
It reason for this is that, if coating layer 12 ' thickness cross thin, then cause having the situation that cannot obtain abundant adhesiveness etc., on the contrary, if blocked up time, then cause having the situation that residual solvent throws into question.
Additionally, in the generally preferable scope being located at 50～150 DEG C and 10 seconds～10 minutes of drying condition.
3. operation (3) (curing process of coating layer)
Operation (3) is for make the coating layer 12 ' of adhesion agent composition solidify, and is made the operation of adhering agent layer 12.
That is, as shown in Fig. 4 (b), it is preferable that the surface of the coating layer 12 ' of the one-tenth drying regime on base material 10 to be heated when stacking peeling base 22 process, thus make its curing reaction, and make adhering agent layer 12.
Or, it is possible to make it solidify in advance by being heated the coating layer 12 ' of the adhesion agent composition coated on base material 10 processing, after making adhering agent layer 12, be laminated to peeling base 22 with transfer printing.
Further, it is also preferred that do not use peeling base 22, it is heated the coating layer 12 ' being formed on base material 10 processing, thus makes it carry out curing reaction, and make adhering agent layer 12.
Additionally, the curing reaction in the coating layer 12 ' of adhesion agent composition is carried out by above-mentioned drying process and ageing treatment process.
Namely, condition as this ageing treatment process, the coating layer 12 ' of adhesion agent composition or base material 10 never cause the angle that the coating layer 12 ' damaging and making adhesion agent composition is uniform curing, and storage humidity is preferably 10～35 DEG C, more preferably 23～30 DEG C.
Additionally, as humidity when heating, it is preferred to 30～75%RH, more preferably 45～65%RH.
4. operation (4) (attaching operation)
The adhesive sheet 50 finally obtained is fitted in the operation of adherend 60.
Such as, as shown in Fig. 4 (c)～(d), after preferably first the stripping film 22 being layered on adhering agent layer 12 being peeled off, when making the surface of adhering agent layer 12 exposed with adherend 60 in relative direction, use stacking machine or press bonding roller etc., compress with authorized pressure, and fit equably.
In addition, the adhesive sheet 50 of the present invention owing to comprising the terminal silyl groups polymer of (A) composition in the adhesion agent composition constituting adhering agent layer 12, therefore it is characterized by the flexibility not only with regulation, affinity for adherend is excellent, air etc. will not be involved in, and can attach moisteningly.
Embodiment
Hereinafter, according to embodiment etc. and the present invention detailed further, when without special reason, the scope of the present invention is not subjected to these embodiments etc. and is limited.
[embodiment 1]
1. the preparation of adhesion agent composition
(1) preparation of silylating agent
N-amino-ethyl-gamma-amino hydroxypropyl methyl dimethoxysilane 206 weight portion, acrylic acid methyl ester. 172 weight portion is put in the reaction vessel with agitating device, it is stirred in a nitrogen environment, and it was heated reaction when 80 DEG C, 10 hours simultaneously, it is thus achieved that silylating agent.
(2) preparation of carbamate prepolymer
Polyoxypropylene diols (Asahi Glass (strain) system, PMLS4015, weight average molecular weight 15 is put in the reaction vessel with agitating device, 000) 1000 weight portions, isophorone diisocyanate 24.6 weight portion (NCO/OH ratio=1.7), dibutyl tin laurate 0.05 weight portion, it is stirred in a nitrogen environment, and it is heated reaction in the condition of 85 DEG C, 7 hours simultaneously, it is thus achieved that carbamate prepolymer (diisocyanate cpd).
(3) preparation of terminal silyl groups polymer
Silylating agent 42.1 weight portion of carbamate prepolymer 1000 weight portion of acquisition, acquisition is loaded in the reaction vessel with agitating device, it is stirred in a nitrogen environment and was heated when 80 DEG C, 1 hour simultaneously processing, and obtain terminal silyl groups polymer.
Now, use fourier-transform infrared spectrophotometer (FT-IR) to observe NCO and absorb (2265cm-1) vanishing state, thereby confirm that the carrying out of reaction.
Additionally, the terminal silyl groups polymer obtained is: have the two terminal silyl groups polymer that weight average molecular weight is 40,000 of end section represented by following formula (9) on two ends of the polyoxypropylene of main chain.
Additionally, by using N-amino-ethyl-gamma-amino hydroxypropyl methyl dimethoxysilane as the raw material of silylating agent, the terminal silyl groups polymer obtained imports the terminal silyl groups of 2 officials' energy.
[chemical formula 12]
(4) preparation of acrylate copolymer
On the other hand, after having carried out nitrogen flushing in the reaction vessel with agitating device, be respectively charged into the n-butyl acrylate (BA) of 90 weight portions as monomer component, 10 weight portions acrylic acid (AAc), as the polymerization initiator azodiisobutyronitrile of the ethyl acetate of solvent, 0.1 weight portion.
Secondly, heat, stir and carry out polymerisation in solution simultaneously, obtain the acrylate copolymer (in table 1, being called TYP1) that weight average molecular weight is 600,000.
Additionally, the acrylate copolymer obtained is dissolved in the ethyl acetate of solvent, its solid component concentration is 33.6 weight %.
(5) preparation of adhesion agent composition
Secondly, stirring container content enter using solid constituent conversion terminal silyl groups polymer 100 weight portion, acrylate copolymer (TYP1) 10 weight portion, as tackifying resin complete hydrogenated terpene phenol resin (pacify former chemistry (strain) system, YSPolystarNH, it is called " NH " to place an order) 100 weight portions, under the existence of the ethyl acetate of ormal weight, stirring, to uniformly, obtains the adhesion agent composition of solution state.
2. the making of adhesive sheet
Secondly, the adhesion agent composition of the solution state of acquisition is coated after on the one side of the mylar (east beautiful (strain) system, LumilarPET50) of thickness 50 μm by use scraper for coating method, it is heated when 100 DEG C, 1 point processing, makes the adhesive sheet of the adhering agent layer possessing thickness 21 μm.
3. the Ageing Treatment of adhesive sheet
Then, the adhesive sheet that the adhesion coating formed by the adhesion agent composition before solidifying and base material (mylar) are constituted, 23 DEG C, under the environment of 50%RH, place (Ageing Treatment) 14 days, adhesion agent composition is made fully to solidify, make the adhesive sheet of embodiment 1, and for various evaluations.
4. evaluate
(1) adhesion strength
According to JISZ0237:2000, measure the adhesion strength of adhesive sheet.That is, cut out the test film of wide 25mm, length 200mm from the adhesive sheet obtained, use the rubber rollers of 2kgf, after SUS304 plate (processs of #360 file) is fitted, 23 DEG C, placement 24 hours under the standard environment of 50%RH.
Then, use cupping machine (Orientec (strain) system, Tensilon), in the way of peeling rate 300mm/ minute, peel angle 180 °, test film is peeled off from SUS304 plate (process of #360 file), using adhesion strength (N/25mm) as adhesion agent composition of the peel load now measured.The result obtained is as shown in table 1.
(2) constant load
Evaluate the constant load of the adhesive sheet obtained.That is, cutting out the test film of wide 25mm, length 100mm from the adhesive sheet obtained, use the rubber rollers of 2kgf, from the end of the adhesive sheet being cut out, by 50mm, (area is 25mm × 50mm=1250mm2) sticker aspect conform to SUS#600 plate, after just laminating, be placed on 23 DEG C immediately, under the standard environment of 50%RH 24 hours.
Then, by the test film after placement to be pasted with configuring in the way of downside of two sides adhesive sheet, the end of adhesive sheet with vertical (under) direction is plus the load of 200g, maintain this state after 24 hours, measure two sides adhesive sheet by the distance (peel distance from SUS plate sur-face peeling, mm), according to following benchmark, evaluate constant load.The result obtained is as shown in table 1.
◎: peel distance is 0mm.
Zero: peel distance is for more than 0mm～5mm.
△: peel distance is for more than 5mm～10mm.
×: peel distance is more than 10mm, or adhesive sheet drops.
(3) gel fraction
The gel fraction of the adhering agent layer (adhesion agent composition after solidifying via ageing treatment process) in the adhesive sheet that mensuration obtains.
That is, 23 DEG C, under the environment of 50%RH, after only the adhering agent layer in adhesive sheet being impregnated in ethyl acetate 120 hours, with 100 DEG C dry 30 minutes, measure the weight before and after dipping, these weight substituted into following formula (10) and calculates gel fraction.The result obtained is as shown in table 1.
Gel fraction (%)=(weight before weight/dipping after dipping) × 100 (10)
[embodiment 2～3]
In embodiment 2～3, when preparing adhesion agent composition, except the addition of the acrylate copolymer (weight average molecular weight: 600,000) relative to terminal silyl groups polymer 100 weight portion is changed to 20 weight portions and 50 weight portions respectively from 10 weight portions, other and embodiment 1 prepare adhesive sheet identically, and are evaluated.The result obtained is as shown in table 1.
[embodiment 4]
In embodiment 4, except monomer weight ratio (BA/AAc) is changed to 95/5 weight % from 90/10 weight %, and obtain acrylate copolymer (in table 1, it is called TYP2), and the addition of the acrylate copolymer relative to terminal silyl groups polymer 100 weight portion is changed to beyond 20 weight portions from 10 weight portions respectively, other and embodiment 1 prepare adhesive sheet identically, and are evaluated.The result obtained is as shown in table 1.
Additionally, the acrylate copolymer used in embodiment 4, by gpc measurement, is confirming that its weight average molecular weight is 600,000.
[embodiment 5]
In embodiment 5, except monomer weight ratio (BA/AAc) is changed to 80/20 weight % from 90/10 weight %, and obtain acrylate copolymer (in table 1, being called TYP3), thereafter prepare adhesive sheet identically with embodiment 1, and be evaluated.The result obtained is as shown in table 1.
Additionally, the acrylate copolymer used in embodiment 5 is by gpc measurement, confirm that its weight average molecular weight is 700,000.
[embodiment 6～8]
In embodiment 6～8, research when preparing adhesion agent composition, the addition of tackifying resin and the impact on terminal silyl groups polymer of the addition of acrylate copolymer.
Namely, in embodiment 6, except the addition of the tackifying resin relative to terminal silyl groups polymer 100 weight portion being set to 90 weight portions and the addition of acrylate copolymer (weight average molecular weight: 600,000) is set to 20 weight portions, prepare adhesive sheet identically with embodiment 1, and be evaluated.
In addition, in embodiment 7, except the addition of the tackifying resin relative to terminal silyl groups polymer 100 weight portion is set to 80 weight portions, and the addition of acrylate copolymer (weight average molecular weight: 600,000) is set to beyond 20 weight portions, other and embodiment 1 prepare adhesive sheet identically, and are evaluated.
And, in embodiment 8, except the addition of the tackifying resin relative to terminal silyl groups polymer 100 weight portion is set to 70 weight portions, and the addition of acrylate copolymer (weight average molecular weight: 600,000) is set to beyond 50 weight portions, other and embodiment 1 prepare adhesive sheet identically, and are evaluated.
[comparative example 1]
In comparative example 1, the additive effect of the acrylate copolymer of research regulation.Namely, except being not added with the acrylate copolymer of regulation, and relative to terminal silyl groups polymer 100 weight portion, use boron trifluoride MEA 0.12 weight portion respectively, as beyond 3-TSL 8330 0.5 weight portion of crosslinking coagent, other and embodiment 1 prepare adhesive sheet identically, and are evaluated.The result obtained is as shown in table 1.
[comparative example 2]
In comparative example 2, when changing tackifying resin kind, study the additive effect of the acrylate copolymer of regulation identically with comparative example 1.
Namely, except being not added with the acrylate copolymer of regulation, and relative to terminal silyl groups polymer 100 weight portion, add YSPolystarG125 (An Yuan chemical company system, non-hydrogenated terpene phenol resin) 100 weight portions of tackifying resin, and, add as boron trifluoride MEA 0.12 weight portion of curing catalysts, as beyond 3-TSL 8330 0.5 weight portion of crosslinking coagent, other and embodiment 1 prepare adhesion agent composition identically, and prepare adhesive sheet further with it, and it is evaluated.The result obtained is as shown in table 1.
[comparative example 3]
In comparative example 3, do not use carboxylic monomer component (acrylic acid) to obtain the acrylate copolymer (being called TYP4 in table 1) through polymerisation in solution, and study its additive effect.
That is, use n-butyl acrylate (95 weight %) and 2-hydroxyethylmethacry,ate (5 weight %) as monomer component, and obtain acrylate copolymer and (table 1 is called TYP4；Weight average molecular weight: 500,000), prepare adhesive sheet thereafter identically with embodiment 2, and be evaluated.The result obtained is as shown in table 1.
[comparative example 4]
In comparative example 4, except being not added with acrylate copolymer and the tackifying resin of regulation, and being not added with beyond curing catalysts and crosslinking coagent, other and embodiment 1 prepare adhesion agent composition identically, and prepare adhesive sheet further with it, and are evaluated.
But, adhesion agent composition is not fully cured, and due to the fact that adhesive sheet cannot be prepared, therefore stop various evaluation.Therefore, stop each evaluation to represent in Table 1, be labeled as " _ ".
Table 1
* (A) composition: terminal silyl groups polymer
* (B) composition: (methyl) acrylate copolymer (TYP1～4)
* (C) composition: tackifying resin (NH and TH)
* (D) composition: curing catalysts (boron trifluoride MEA)
* (E) composition: crosslinking coagent (3-TSL 8330)
* the numeric representation strip length (mm) in () or with or without dropping in the hurdle of constant load.
Industrial applicibility
As set forth in more detail above, according to the adhesion agent composition of the present invention and employ the adhesive sheet of said composition, by terminal silyl groups polymer being added the acrylic copolymer and tackifying resin with the co-polymeric share from carboxylic vinyl monomer, even if therefore the addition of curing catalysts is a small amount of, even if or when being not added with curing catalysts, remain to when maintaining good adherence power, it is thus achieved that excellent constant load etc..
Therefore, the adhesion agent composition of the present invention and employ the adhesive sheet of said composition and be expected to be used in the various uses of an electrical article, automobile, OA equipment etc..
More specifically, it is expected to the laminating being used between the resin plate of the electronic equipment internal such as mobile phone or PC or the laminating etc. of optical recording media, Magnetooptic recording medium, liquid crystal display, contact panel parts.
Description of reference numerals
10 is base material；12,12a, 12b are adhering agent layer；12 ' is coating layer；18 is other adhering agent layers；22 is peeling base (stripping film)；50 is adhesive sheet (one side adhesive sheet)；50 ' is the adhesive sheet (one side adhesive sheet) with peeling base；52 is adhesive sheet (two sides adhesive sheet)；54 is adhesive sheet (the two sides adhesive sheet with adhering agent layer not of the same race)；60 is adherend.

Claims (9)

1. an adhesion agent composition, it is the adhesion agent composition of the tackifying resin including at least the terminal silyl groups polymer of (A) composition, (methyl) acrylate copolymer of (B) composition and (C) composition, it is characterized in that
The terminal silyl groups polymer of described (A) composition for have poly (oxyalkylene) based structures in main chain, and in a part or the side chain of main chain, there is amino-formate bond and urea key or any of which, and two ends in main chain have the hydrolyzable silyl group represented by following formula (1)
(methyl) acrylate copolymer of described (B) composition has the co-polymeric share from carboxylic vinyl monomer,
Further, relative to the total amount of described (A)～(C) composition, the addition of the curing catalysts of (D) composition is 0 or more than 0 and 0.1 weight % value below,
[chemical formula 1]
In formula (1), X1And X2Independently be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
2. adhesion agent composition according to claim 1, it is characterised in that relative to the total amount of described (A)～(C) composition, the addition of the curing catalysts of described (D) composition is 0 weight %.
3. adhesion agent composition according to claim 1, it is characterized in that, relative to terminal silyl groups polymer 100 weight portion of described (A) composition, the value in the scope that addition is 5～100 weight portions of (methyl) acrylate copolymer of (B) composition described in making.
4. adhesion agent composition according to claim 1, it is characterized in that, relative to terminal silyl groups polymer 100 weight portion of described (A) composition, the value in the scope that addition is 50～140 weight portions of the tackifying resin of (C) composition described in making.
5. adhesion agent composition according to claim 1, it is characterised in that the value in the scope that weight average molecular weight is 15,000～200,000 of the terminal silyl groups polymer of (A) composition described in making.
6. adhesion agent composition according to claim 1, it is characterized in that, the described carboxylic vinyl monomer that (methyl) acrylate copolymer of described (B) composition uses when carrying out copolymerization is (methyl) acrylic monomers.
7. adhesion agent composition according to claim 1, it is characterized in that, relative to whole monomer component 100 weight %, the value in the scope making consumption be 0.1～50 weight % of described carboxylic vinyl monomer when making (methyl) acrylate copolymer of described (B) composition carry out copolymerization.
8. adhesion agent composition according to claim 1, it is characterised in that the tackifying resin of described (C) composition is terpene phenolic resinoid.
9. a manufacture method for adhesive sheet, it for possessing the manufacture method of the adhesive sheet of the adhering agent layer being made up of adhesion agent composition on the two sides of base material or one side, it is characterised in that comprises following operation (1)～(3):
(1) operation of adhesion agent composition is prepared,
This adhesion agent composition is the terminal silyl groups polymer including at least (A) composition, (B) (methyl) acrylate copolymer of composition, and the adhesion agent composition of the tackifying resin of (C) composition, the terminal silyl groups polymer of described (A) composition for have poly (oxyalkylene) based structures in main chain, and in a part or the side chain of main chain, there is amino-formate bond and urea key, or any of which, and two ends in main chain have the hydrolyzable silyl group represented by following formula (1), (methyl) acrylate copolymer of described (B) composition has the co-polymeric share from carboxylic vinyl monomer, and, total amount relative to described (A)～(C) composition, (D) addition of the curing catalysts of composition is 0 or more than 0, and 0.1 weight % value below,
[chemical formula 2]
In formula (1), X1And X2Independently be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20；
(2) described adhesion agent composition is laminated on two sides or the one side of described base material, makes the operation of the adhesive sheet possessing the adhering agent layer being made up of uncured adhesion agent composition；
(3) heat described adhesion agent composition, make and possess by the operation of the adhesive sheet solidifying the adhering agent layer that adhesion agent composition is constituted.
CN201480063124.2A 2013-11-26 2014-11-11 Pressure-sensitive adhesive composition and process for manufacturing pressure-sensitive adhesive sheet Pending CN105745296A (en)

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