CN105331308A - Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing the same and reinforced flexible printed wiring board - Google Patents

Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing the same and reinforced flexible printed wiring board Download PDF

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Publication number
CN105331308A
CN105331308A CN201510763270.2A CN201510763270A CN105331308A CN 105331308 A CN105331308 A CN 105331308A CN 201510763270 A CN201510763270 A CN 201510763270A CN 105331308 A CN105331308 A CN 105331308A
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thermoset
epoxy resin
acrylic copolymer
thermoset adhesive
bonding composition
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CN105331308B (en
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名取稔城
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Dexerials Corp
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Dexerials Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4035—Hydrazines; Hydrazides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • 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
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0277—Bendability or stretchability details
    • H05K1/028—Bending or folding regions of flexible printed circuits
    • H05K1/0281—Reinforcement details thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • 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
    • C09J2301/304—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 the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • 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
    • C09J2463/00—Presence of epoxy resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00013—Fully indexed content

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

Disclosed is a thermosetting adhesive composition comprising (A) an acrylic copolymer, (B) an epoxy resin, and (C) an epoxy resin curing agent. The acrylic copolymer (A) is obtained by copolymerizing 65 to 75% by mass of (a) a (meth)acrylic ester monomer containing no epoxy group, 20 to 35% by mass of (b) an acrylonitrile monomer, and 1 to 10% by mass of (c) a (meth)acrylic ester monomer containing an epoxy group. The epoxy resin curing agent comprises particles of an organic acid dihydrazide having an average particle diameter of 0.5 to 15 [mu]m.

Description

Thermoset bonding composition, thermoset adhesive sheet, its manufacture method and enhancing flexible printing wiring board
The divisional application entering the PCT application of thenational phase that the application is application number is 201080045247.5 (international filing date is on July 26th, 2010), denomination of invention is " thermoset bonding composition, thermoset adhesive sheet, its manufacture method and enhancing flexible printing wiring board "
Technical field
The present invention relates to the thermoset bonding composition containing acrylic copolymer, epoxy resin and hardener for epoxy resin.
Background technology
Using polyimide film, glass epoxy board, sheet metal liner by comprising the portion of terminal of the flexible printing wiring board of polyimide film etc., improving its intensity.In this case, bonding between reinforcement plate and the polyimide of flexible printing wiring board normally makes the heat-curable adhesive layer clamped by them solidify to come bonding.As this heat-curable adhesive layer, in flexible printing wiring board field, widely use the epoxide resin adhesive (patent documentation 1) mainly comprising liquid-state epoxy resin, solid epoxy and their solidifying agent.
But this epoxide resin adhesive is many due to the compounding ratio of epoxy resin and solidifying agent, there is the problem being cured reaction in normal temperature is preserved lentamente, normal temperature preservation characteristics aspect has problems.Therefore, in order to improve normal temperature preservation characteristics, proposing the use level suppressing epoxy resin, correspondingly using acrylic acid polymer as the acrylic acid series thermoset bonding composition (patent documentation 2, particularly embodiment 2) of main component.
Patent documentation 1: Japanese Unexamined Patent Publication 04-370996 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2007-9058 publication.
Summary of the invention
But, when the acrylic acid series thermoset bonding composition of patent documentation 2, compared with the epoxide resin adhesive in the past of patent documentation 1, although normal temperature keeping quality improves, if but preservation reaches the time of several months at normal temperatures, then in the joint of flexible printed board and resin sheet, metal reinforcing plate or glass epoxy board, then cementability (stripping strength) and reflow soldering thermotolerance likely reduce, and require to improve it.
The object of the invention is to, solve above existing technical problem, be provided in the fields such as flexible printed board for bonding acrylic acid series thermoset bonding composition, it is can be bonding well with between polyimide film, metal reinforcing plate or glass epoxy substrate by resin substrates such as polyimide films, passes through the acrylic acid series thermoset bonding composition that the time reaching the several months also can show good normal temperature preservation characteristics.
As the conservatory hardener for epoxy resin of the normal temperature for improving epoxide resin adhesive, the present inventor is conceived to thus to react with epoxy resin for solid owing to not being readily dissolved in organic solvent, at normal temperatures, organic acid dihydrazide of initiation reaction by heating and epoxy resin melting mixing, to coordinating epoxy resin in acrylic copolymer, being studied as organic acid dihydrazide of hardener for epoxy resin.Usually used as the manufacture method of membranaceous adhesive sheet, adopt and above-mentioned title complex is dissolved, is dispersed in the organic solvents such as methylethylketone, carry out the method being coated with to manufacture, but although the solidifying agent particle that there is organic acid dihydrazide is not readily dissolved in organic solvent, but can slowly dissolve in organic solvent, the solidifying agent dissolved also dissolves in the epoxy, therefore carries out the problem of reacting.Based on this viewpoint, find by the median size of organic acid dihydrazide is controlled in specific particle size range, balance can realize suppressing when normal temperature is preserved carrying out fast of the dissolving in organic solvent of organic acid dihydrazide and thermofixation reaction well, and then as acrylic copolymer, by adopt specified range amount not containing (methyl) acrylate monomer of epoxy group(ing), acrylonitrile monemer and the multipolymer of (methyl) acrylate monomer containing epoxy group(ing), can above-mentioned purpose be reached, thus complete the present application.
That is, thermoset bonding composition provided by the invention, it is the thermoset bonding composition containing acrylic copolymer (A), epoxy resin (B) and hardener for epoxy resin (C), wherein
This acrylic copolymer (A) is not by containing epoxy group(ing) (methyl) acrylate monomer (a) 65 ~ 75 quality %, acrylonitrile monemer (b) 20 ~ 35 quality % and (methyl) acrylate monomer (c) 1 ~ 10 quality % copolymerization containing epoxy group(ing)
This hardener for epoxy resin is organic acid dihydrazide particle of median size 0.5 ~ 15 μm.Should illustrate, in this manual, " (methyl) vinylformic acid " this term refers to " methacrylic acid or vinylformic acid ".
In addition, the invention provides thermoset adhesive sheet, it is formed to comprise the thermoset adhesive linkage of this thermoset bonding composition on base material film.
Further, the invention provides manufacture method, it is the manufacture method of this thermoset adhesive sheet, and it comprises:
The thermoset bonding composition of the invention described above is put in organic solvent, hardener for epoxy resin (C) is disperseed in organic solvent, acrylic copolymer (A) and epoxy resin (B) is made to dissolve in organic solvent on the other hand, prepare the step of thermoset adhesive linkage formation coating thus, and
By thermoset adhesive linkage formation coatings on base material film, carry out drying, form the step of thermoset adhesive linkage thus.
Thermoset bonding composition of the present invention by between the metal sheets such as the resin substrates such as polyimide film and polyimide film, glass epoxy resin, stainless steel well bonding (preferred more than 15N/cm), and also show good film normal temperature preservation characteristics through reaching the time of several months.In addition, even if after the reflow soldering process more than 260 DEG C, the characteristic that can not produce expansion due to moisture absorption is also shown.
Embodiment
Thermoset bonding composition of the present invention contains acrylic copolymer (A), epoxy resin (B) and hardener for epoxy resin (C).
In the present invention, acrylic copolymer (A) is for providing film-forming properties, make cured article have flexibility, toughness when film is shaping, it is not by containing epoxy group(ing) (methyl) acrylate monomer (a), acrylonitrile monemer (b) and (methyl) acrylate monomer (c) copolymerization containing epoxy group(ing).
As (methyl) acrylate monomer (a) not containing epoxy group(ing), what can use from the acrylic acid series heat-curable adhesive being in the past applicable to field of electrical components does not use containing suitably selecting in (methyl) acrylate monomer of epoxy group(ing), such as methyl acrylate can be enumerated, ethyl propenoate, n-propyl, n-butyl acrylate, isobutyl acrylate, the just own ester of vinylformic acid, n-octyl, Isooctyl acrylate monomer, 2-EHA, vinylformic acid ester in the different ninth of the ten Heavenly Stems, stearyl acrylate ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the just own ester of methacrylic acid, n octyl methacrylate, Isooctyl methacrylate, 2-Ethylhexyl Methacrylate, methacrylic acid ester in the different ninth of the ten Heavenly Stems, methacrylic acid dodecyl ester, methacrylic acid Permethyl 99A. base ester, stearyl methacrylate etc.Wherein, butyl acrylate, ethyl propenoate is preferably used.
In the whole monomers used when preparing acrylic copolymer (A), not containing the consumption of (methyl) acrylate monomer (a) of epoxy group(ing), if cross fundamental characteristics at least to reduce, there is the trend that thermotolerance reduces if cross at most, be therefore preferably 65 ~ 75 quality %, be more preferably 65 ~ 70 quality %.
Acrylonitrile monemer (b) is for improving thermotolerance.
In the whole monomers used when preparing acrylic copolymer (A), the consumption of acrylonitrile monemer (b), reduces if cross thermotolerance at least, if cross the trend existing at most and be difficult to dissolve in a solvent, therefore be preferably 20 ~ 35 quality %, be more preferably 25 ~ 30 quality %.
Containing (methyl) acrylate monomer (c) of epoxy group(ing) for reacting with hardener for epoxy resin, in the cured article of thermoset bonding composition, form three-dimensional crosslinking structure.If formation three-dimensional crosslinking structure, then the wet fastness of cured article and thermotolerance improve, even if such as when to comprise the enhancing flexible printing wiring board being bonded and fixed to the enhancing resin sheet of flexible printing wiring board by the cured article of thermoset bonding composition carry out soldering process (the such as reflow soldering process) of more than 260 DEG C, also can prevent the swelling produced in its portion of being adhesively fixed because moisture absorption causes.As this (methyl) acrylate monomer (c) containing epoxy group(ing), suitably select in the monomer that can use from the acrylic acid series heat-curable adhesive being in the past applicable to field of electrical components to use, such as, can enumerate glycidyl acrylate (GA), glycidyl methacrylate (GMA) etc.Wherein, obtain easiness from the viewpoint of security, market, preferably use glycidyl methacrylate (GMA).
In the whole monomers used when preparing acrylic copolymer (A), containing the consumption of (methyl) acrylate monomer (c) of epoxy group(ing), if cross thermotolerance at least to reduce, the trend that stripping strength reduces is there is at most if cross, therefore be preferably 1 ~ 10 quality %, be more preferably 3 ~ 7 quality %.
Described above by not preparing acrylic copolymer containing (methyl) acrylate monomer (a) of epoxy group(ing), acrylonitrile monemer (b) and (methyl) acrylate monomer (c) containing epoxy group(ing), known copolymerization process can be suitable for carry out.
For the acrylic copolymer used in the present invention (A), if its weight-average molecular weight is too small, stripping strength and thermotolerance reduce, if excessive, there is the trend that soltion viscosity raises, coating is deteriorated, therefore preferably there is the weight-average molecular weight of 500000 ~ 700000, more preferably 550000 ~ 650000.
The epoxy resin (B) forming thermoset bonding composition of the present invention, for the formation of tridimensional network, makes thermotolerance, cementability good.
As epoxy resin (B), suitably select to use in the liquid state that can use from the epoxy resin heat-curable adhesive being in the past applicable to field of electrical components or the epoxy resin of solid state, such as, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type epoxy resin, bisphenol-A epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, polyalkylene polyol (neopentyl glycol etc.) poly epihydric alcohol base ether, four glycidyl group diaminodiphenyl-methane, triglycidyl group-p-aminophenol, triglycidyl group-Metha Amino Phenon, four glycidyl group-m-xylene diamine, phthalic acid 2-glycidyl ester, hexahydrobenzene dioctyl phthalate 2-glycidyl ester, four hydrogen phthalate 2-glycidyl esters, vinyl cyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxy-cyclohexane) carboxylicesters, two (3,4-epoxy group(ing)-6-methylcyclohexylmethyl) adipic acid ester etc.
The consumption of the epoxy resin (B) in thermoset bonding composition of the present invention, if cross thermotolerance at least to reduce, the trend that cementability reduces is there is at most if cross, therefore relative to acrylic copolymer (A) 100 mass parts, be preferably 5 ~ 30 mass parts, be more preferably 10 ~ 20 mass parts.
In thermoset bonding composition of the present invention, as the hardener for epoxy resin (C) of epoxy reaction with (methyl) acrylate monomer containing epoxy group(ing) used from epoxy resin (B) and when preparing acrylic copolymer (A), median size is used to be 0.5 ~ 15 μm, preferred organic acid dihydrazide particle of 1 ~ 5 μm.Use the reason of organic acid dihydrazide to be, because it is solid at normal temperatures, therefore can improve the normal temperature preservation characteristics of thermoset bonding composition.In addition, the median size of organic acid dihydrazide particle is made to be that the reason of 0.5 ~ 15 μm is, if be less than 0.5 μm, then in order to coated heat solidity bonding composition with an organic solvent time, the possibility that organic acid dihydrazide particle dissolves raises, and normal temperature preservation characteristics likely reduces, if be greater than 15 μm on the contrary, then the coating of thermoset bonding composition reduces, in addition because granularity is large, likely can not fully mixing with when acrylate copolymer, epoxy resin melting.
As this organic acid dihydrazide, can from be used as in the past epoxy resin solidifying agent organic acid dihydrazide suitably select to use, such as can enumerate careless acid dihydrazide, acid dihydrazide, amber acid dihydrazide, iminodiethanoic acid two hydrazides, adipic dihydrazide, pimelic acid two hydrazides, suberic acid two hydrazides, nonane diacid two hydrazides, sebacic dihydrazide, dodecanedicarboxylic acid two hydrazides, hexadecane dicarboxylic acid two hydrazides, Malaysia acid dihydrazide, fumaric acid two hydrazides, diglycolic acid two hydrazides, winestone acid dihydrazide, apple acid dihydrazide, isophthalic dihydrazide, terephthaldehyde's acid dihydrazide, 2,6-naphthoic acid two hydrazides, 4,4 '-bis-benzene two hydrazides, Isosorbide-5-Nitrae-naphthoic acid two hydrazides, two (Hydrazinocarbonyl ethyl)-5-sec.-propyl glycolylurea (ア ミ キ ュ ア VDH (trade(brand)name) of 1,3-, monosodium glutamate (strain)), 7,11-18 carbon diene-1,18-bis-carbohydrazide (ア ミ キ ュ ア UDH (trade(brand)name), monosodium glutamate (strain)), citric acid three hydrazides etc.Can be used alone the one in them or combine two or more use.Wherein, the balance of, solidified nature lower from the viewpoint of fusing point excellent, easily obtain, preferably use adipic dihydrazide or 7,11-18 carbon diene-1,18-bis-carbohydrazide.
The consumption of the hardener for epoxy resin (C) in thermoset bonding composition of the present invention, if cross the epoxy group(ing) of remained unreacted at least, crosslinked also insufficient, therefore thermotolerance, cementability reduce, if cross solidifying agent unreacted excessive at most and still remain, therefore there is the trend of thermotolerance, cementability reduction, so relative to total 100 mass parts of acrylic copolymer (A) and epoxy resin (B), be preferably 4 ~ 20 mass parts, be more preferably 6 ~ 15 mass parts.
In thermoset bonding composition of the present invention, except composition described above, in the scope not damaging effect of the present invention, the known additives such as the metal passivator of the dissolving that can not promote organic acid dihydrazide, defoamer, rust-preventive agent, dispersion agent can be coordinated as required.
Thermoset bonding composition of the present invention can be prepared by utilizing ordinary method acrylic copolymer (A), epoxy resin (B), hardener for epoxy resin (C) and other additive to be mixed equably.As its form, it is aqueous etc. to make paste, film, dispersion.Wherein, consider from viewpoints such as operability when keeping quality, use, preferably use to form with the thickness of 10 ~ 50 μm the mode comprising the thermoset adhesive sheet of the thermoset adhesive linkage of thermoset bonding composition of the present invention on the base material films (peeling base) such as polyethylene terephthalate film, polyimide film.Should illustrate, lift-off processing can also be implemented with organosilicon etc. to this base material film as required.
The manufacture method of this thermoset adhesive sheet contains following thermoset adhesive linkage formation coating preparation process and thermoset adhesive linkage forming step.
< thermoset adhesive linkage is formed with coating preparation process >
First, thermoset bonding composition of the present invention is put in the organic solvent such as methylethylketone, toluene to form the viscosity being suitable for coating method, hardener for epoxy resin (C) is disperseed in organic solvent, make acrylic copolymer (A) and epoxy resin (B) dissolve in organic solvent on the other hand, prepare thermoset adhesive linkage formation coating thus.Now, in order to improve the normal temperature keeping quality of thermoset adhesive sheet, preferably at room temperature 70 quality % of whole organic acid dihydrazide particle are dispersed in thermoset adhesive linkage formation coating with solid particulate form.
< thermoset adhesive linkage forming step >
Then, by bar coater, roller coating machine etc. by thermoset adhesive linkage formation coatings on base material film, to make dry thickness be 10 ~ 50 μm, carry out drying by ordinary method, form thermoset adhesive linkage thus.Thus thermoset adhesive sheet can be obtained.
Thermoset bonding composition described above and thermoset adhesive sheet can preferably be applicable in field of electrical components.Particularly above-mentioned thermoset adhesive sheet can preferably be applicable to portion of terminal of flexible printing wiring board etc. and the enhancing resin sheet for the formation of the polyethylene terephthalate of its lining, polyimide, glass epoxy resin, stainless steel, aluminium equal thickness being 50 μm ~ 2mm to be adhesively fixed, be suitable for by this, obtain the enhancing flexible printing wiring board that the portion of terminal of flexible printing wiring board and enhancing resin sheet are adhesively fixed by the thermosetting compound of the thermoset adhesive linkage after the base material film eliminating thermoset adhesive sheet of the present invention.
Embodiment
By the following examples more specific description is carried out to the present invention.
Embodiment 1 ~ 10, comparative example 1 ~ 8
(1) preparation of acrylic copolymer
Prepare the acrylic copolymer comprising the monomer shown in table 1 and table 2.The weight-average molecular weight of these acrylic copolymers as shown in Table 1 and Table 2.
(2) preparation of thermofixation adhesive linkage formation coating
Epoxy resin (B) and the organic acid dihydrazide as hardener for epoxy resin (C) is added using the compounding ratio of table 1 and table 2 in obtained acrylic copolymer solution, mix equably, prepare thermoset adhesive linkage formation coating thus as thermoset bonding composition.The viscosity of the coating obtained is measured by Brookfield viscometer, is shown in table 1 and table 2.
(3) manufacture of thermoset adhesive sheet
By obtained thermoset adhesive linkage formation coatings in the polyethylene terephthalate film implementing lift-off processing, dry in the drying oven of 50 ~ 130 DEG C, forms 35 μm of thick thermoset adhesive linkages, manufacture thermoset adhesive sheet thus.
(4) evaluation of the coating of thermoset adhesive linkage formation coating
When manufacturing above-mentioned thermoset adhesive sheet, evaluate according to the coating of following benchmark to thermoset adhesive linkage formation coating.The evaluation result obtained as shown in Table 1 and Table 2.
AA: the thickness of caking agent is homogeneous, do not form texture in coating, also do not observe the situation of solidifying agent particle in appearance
A: although do not form texture in coating, but situation film after the drying being observed solidifying agent particle
B: there is coating texture, thickness is inhomogenous situation also
C: solution forms gel, the situation that can not be coated with
(5) evaluation of stripping strength
The thermoset adhesive sheet just obtained is cut into the rectangle (5cm × 10cm) of prescribed level, by this thermoset adhesive linkage be set as the laminating machine of 80 DEG C temporarily paste 175 μm of thick polyimide films (175AH, (strain) カ ネ カ) upper after, removing base material film exposes thermoset adhesive linkage.For exposed thermoset adhesive linkage, from 50 μm of top coincidence formed objects thick polyimide films (200H, デ ュ ポン society), 170 DEG C, after the heating under pressure of 2.0MPa pressurizes 60 seconds, keep 60 minutes in the baking oven of 140 DEG C.
In addition, after the glass epoxy board of the thermoset adhesive linkage of the thermoset adhesive sheet being cut into rectangle (5cm × 10cm) being pressed the SUS304 plate or thickness 1mm that are pressed on 0.5mm is temporarily pasted, removing base material film exposes thermoset adhesive linkage.For exposed thermoset adhesive linkage, the polyimide film (5cm × 10cm) of the rectangular thickness 50 μm that overlaps from top, 170 DEG C, after the heating under pressure of 2.0MPa pressurizes 60 seconds, keep 60 minutes in the baking oven of 140 DEG C.
Then, for polyimide film, carry out 90 degree of stripping tests with peeling rate 50mm/min, measure the power needed for peeling off.The result obtained as shown in Table 1 and Table 2.Stripping strength is expected in practical for 10N/cm.In addition, expect that the difference that normal temperature preserves the stripping strength after 6 months and the stripping strength at initial stage is less than-30%.Therefore, situation difference being less than 2N/cm is denoted as normal temperature preservation characteristics well, if exceed, is denoted as bad.
In addition, normal temperature at 25 DEG C is preserved to the thermoset adhesive sheet of 6 months, carry out the evaluation of same stripping strength.The result obtained as shown in Table 1 and Table 2.
[table 1]
[table 2]
The investigation > of the result of < table 1 and table 2
In the thermoset adhesive sheet of embodiment 1 ~ 7, acrylic copolymer (A) is (methyl) acrylate monomer (c) 1 ~ 10 quality % copolymerization not containing epoxy group(ing) (methyl) acrylate monomer (a) 65 ~ 75 quality %, acrylonitrile monemer (b) 20 ~ 35 quality % and contain epoxy group(ing), hardener for epoxy resin is organic acid dihydrazide particle of median size 0.5 ~ 15 μm, and therefore coating, initial stage stripping strength and normal temperature preservation characteristics are all satisfactory.
Should illustrate, in the thermoset adhesive sheet of embodiment 8, the weight-average molecular weight of acrylic copolymer (A) is 300,000, lower than the thermoset adhesive sheet of embodiment 1 ~ 7, although therefore normal temperature preservation characteristics is good, but the stripping strength of entirety and thermotolerance reduce.
In the thermoset adhesive sheet of embodiment 9, the weight-average molecular weight of acrylic copolymer (A) is 900,000, higher than the thermoset adhesive sheet of embodiment 1 ~ 7, therefore on the surface of adhesive sheet, there is coating texture, thickness is heterogeneity also, but normal temperature preservation characteristics is good.
When the thermoset adhesive sheet of embodiment 10, the median size due to organic acid dihydrazide is greater than the thermoset adhesive sheet of embodiment 1 ~ 7, therefore coating reduce a little, in addition normal temperature have good keeping qualities, but the stripping strength of entirety reduces.In addition, because hydrazides particle is excessive, therefore reactive reduction, stripping strength, thermotolerance are insufficient.
On the other hand, in the thermoset adhesive sheet of comparative example 1, the composition (a) in acrylic copolymer is very few, composition (b) too much, therefore can not fully dissolve in organic solvent, produces gelation.
In the thermoset adhesive sheet of comparative example 2, the composition (a) in acrylic copolymer is too much, composition (b) is very few, although therefore normal temperature preservation characteristics is good, but initial stage stripping strength is be unsuitable for practical low-level.
In the thermoset adhesive sheet of comparative example 3, the composition (c) in acrylic copolymer is very few, although therefore normal temperature preservation characteristics is good, but initial stage stripping strength is be unsuitable for practical low-level.
In the thermoset adhesive sheet of comparative example 4, the composition (c) in acrylic copolymer is too much, although therefore normal temperature preservation characteristics is good, but initial stage stripping strength is be unsuitable for practical low-level.
In the thermoset adhesive sheet of comparative example 5, the median size of organic acid dihydrazide is excessive, and therefore initial stage stripping strength is be unsuitable for practical low-level.
In the thermoset adhesive sheet of comparative example 6 ~ 8, owing to there is hydroxyl or carboxyl in acrylic copolymer, therefore normal temperature preservation characteristics is bad.
Embodiment 11
Use the thermoset adhesive sheet of embodiment 1 ~ 10 and comparative example 2 ~ 8, as described below, manufacture and strengthen flexible printing wiring board.
< moisture absorption reflow soldering thermal test >
By the thermoset adhesive linkage being cut into the thermoset adhesive sheet of rectangle (2cm × 2cm) with after being set as that the laminating machine of 80 DEG C is temporarily pasted on 175 μm of thick polyimide films (ア ピ カ Le 175AH, (strain) カ ネ カ), removing peeling base exposes thermoset adhesive linkage.For exposed thermoset adhesive linkage, from 50 μm of top coincidence formed objects thick polyimide films (カ プ ト Application 200H, デ ュ ポン society), 170 DEG C, after the heating under pressure of 2.0MPa pressurizes 60 seconds, keep 60 minutes in the baking oven of 140 DEG C.Then, by the test film that is heating and curing 40 DEG C, place 96 hours in the damp and hot baking oven of 90%RH.
Make the test film after firm wet heat treatment by being set as the top temperature reflow soldering furnace of 260 DEG C × 30 seconds, visual observation pass through after test film with or without abnormal appearances such as expansion, strippings, outward appearance be there is no completely abnormal average evaluation for " A ", there is the still practical no problem average evaluation that expands to be " B " a little by observing test film, the average evaluation of the expansion that test film has foaming to cause will be observed for " C ".The result obtained as shown in Table 3 and Table 4.
[table 3]
[table 4]
But the result of moisture absorption reflow soldering thermal test is, what use the enhancing flexible printing wiring board of the thermoset adhesive sheet of embodiment 1 ~ 10 does not observe exception in appearance completely, or observes test film and have a little and to expand practical no problem.Particularly use the balance of the acrylic copolymer-epoxy resin-hydrazides crosslinking structure of the enhancing flexible printing wiring board of the thermoset adhesive sheet of embodiment 1 ~ 7 good, the raw material of remained unreacted, does not therefore observe abnormal appearance completely hardly.
On the other hand, when comparative example 2 ~ 8, except comparative example 4, after 25 DEG C/6 months, observe the expansion that test film has foaming to cause.Should illustrate, when comparative example 4, owing to being good crosslinking structure, moisture absorption reflow soldering thermotolerance is good, but as mentioned above, initial stage stripping strength is be unsuitable for practical low-level.
Industrial applicability
Thermoset bonding composition of the present invention and thermoset adhesive sheet can be bonding well with between polyimide film, stainless steel plate or glass epoxy substrate by resin substrates such as polyimide films, and also show good normal temperature preservation characteristics through reaching the time of several months.In addition, even if carry out 260 DEG C of reflow soldering process, also expansion can not be produced due to moisture absorption.Therefore, as often using the caking agent in the field of electrical components of polyimide material to be useful.

Claims (6)

1. thermoset bonding composition, it is the thermoset bonding composition containing acrylic copolymer (A), epoxy resin (B) and hardener for epoxy resin (C), wherein,
This acrylic copolymer (A) is not by containing epoxy group(ing) (methyl) acrylate monomer (a) 65 ~ 75 quality %, acrylonitrile monemer (b) 20 ~ 35 quality % and (methyl) acrylate monomer (c) 1 ~ 10 quality % copolymerization containing epoxy group(ing)
This hardener for epoxy resin is organic acid dihydrazide particle of median size 0.5 ~ 15 μm,
The weight-average molecular weight of described acrylic copolymer (A) is 400000 ~ 700000, described (methyl) acrylate monomer (a) not containing epoxy group(ing) does not contain hydroxyl and free carboxy, described (methyl) acrylate monomer (c) containing epoxy group(ing) is not containing hydroxyl and free carboxy
Relative to acrylic copolymer (A) 100 mass parts, containing epoxy resin (B) 5 ~ 30 mass parts, relative to total 100 mass parts of acrylic copolymer (A) and epoxy resin (B), containing hardener for epoxy resin 4 ~ 20 mass parts.
2. thermoset bonding composition as claimed in claim 1, wherein, organic acid dihydrazide is adipic dihydrazide or 7,11-18 carbon diene-1,18-bis-carbohydrazide.
3. thermoset bonding composition as claimed in claim 1 or 2, wherein, the weight-average molecular weight of acrylic copolymer (A) is 500000 ~ 700000.
4. thermoset adhesive sheet, it is that formation comprises the thermoset adhesive linkage of the thermoset bonding composition in claims 1 to 3 described in any one on base material film.
5. manufacture method, it is the manufacture method of thermoset adhesive sheet according to claim 4, and it comprises:
Thermoset bonding composition in claims 1 to 3 described in any one is put in organic solvent, hardener for epoxy resin (C) is disperseed in organic solvent, acrylic copolymer (A) and epoxy resin (B) is made to dissolve in organic solvent on the other hand, prepare the step of thermoset adhesive linkage formation coating thus, and
By thermoset adhesive linkage formation coatings on base material film, carry out drying, form the step of thermoset adhesive linkage thus.
6. strengthen flexible printing wiring board, it is the enhancing flexible printing wiring board of the portion of terminal enhancing resin sheet lining of flexible printing wiring board, and it is that the thermosetting compound of thermoset adhesive linkage after this portion of terminal and this enhancing resin sheet have been removed the base material film of thermoset adhesive sheet according to claim 4 is adhesively fixed.
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