CN103221449B - Heat-curing resin composition, heat-curing adhesive sheet, and method for producing heat-curing adhesive sheet - Google Patents
Heat-curing resin composition, heat-curing adhesive sheet, and method for producing heat-curing adhesive sheet Download PDFInfo
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- CN103221449B CN103221449B CN201180057389.8A CN201180057389A CN103221449B CN 103221449 B CN103221449 B CN 103221449B CN 201180057389 A CN201180057389 A CN 201180057389A CN 103221449 B CN103221449 B CN 103221449B
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
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- 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
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- 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
- C08G59/50—Amines
- C08G59/54—Amino amides>
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- 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
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Provided is a heat-curing resin composition capable of removing bubbles in a short time from between a circuit and the joining surface of an adhesive sheet during hot-pressing. The heat-curing resin composition is characterized by having a tensile modulus of 105-106Pa during hot-pressing at between 150 and 180 DEG C. In addition, the heat-curing resin composition contains: an acrylic copolymer containing a vinyl monomer that contains an epoxy group; an epoxy resin; a curing agent for the epoxy resin; and an organic acid dihydrazide as the curing agent.
Description
Technical field
The present invention relates to the thermosetting resin group of the firming agent containing acrylic copolymer, epoxy resin and epoxy resin
The manufacture method of compound, thermosetting adhesive sheet and thermosetting adhesive sheet.The application with Japan in November 29 in 2010
CLAIM OF PRIORITY based on Japanese patent application No. 2010-264790 that day files an application, is incorporated in by referring to by this application
In the application.
Background technology
In order to obtain good reflow thermostability, there are the acrylic acid seriess containing carboxyl and epoxy radicals in raw polymer
Polymer or in the acrylic acid series polymeric compounds containing carboxyl and the acrylic acid series polymeric compounds containing epoxy radicals contain cresol type
Phenolic resin and epoxy resin are as the resin combination of cure component.Propose using these acrylic acid series polymeric compounds,
Cresol type phenolic resin and epoxy resin, in low temperature and the short time cure under pressure（Solidification）Under can get good bonding force
Adhesive sheet（Referenced patent document 1 and patent documentation 2）.
But, used in the adhesive sheet of patent documentation 1 and patent documentation 2 record, adhesive composition is due to containing a large amount of
Carboxyl, epoxy radicals, cresol type phenolic resin etc. form the functional group of three-dimensional mesh structure, and therefore in room temperature preservation, solidification is anti-
Should slowly carry out, room temperature keeping quality is bad.
In addition, when actual pressurization presses, the bubble between circuit and adhesive sheet composition surface removes becomes speed control
Step processed, thus for the adhesive composition described in patent documentation 1 and patent documentation 2, in order to completely remove circuit with bonding
Bubble between sheet material composition surface, needs to be pressurizeed for a long time.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2007-9057 publication
Patent documentation 2：Japanese Unexamined Patent Publication 2007-9058 publication.
Content of the invention
Invention technical problem to be solved
The present invention is in view of above-mentioned conventional practical situation and the invention that proposes, its objective is to provide in heating pressurization,
Can the compositions of thermosetting resin of the bubble between removing circuit and adhesive sheet composition surface, thermosetting adhesive sheet at short notice
Material and the manufacture method of thermosetting adhesive sheet.
Method for solving technical problem
The tensile modulus of elasticity when carrying out heating pressurization for 150～180 DEG C for the compositions of thermosetting resin of the present invention is 105
～106Pa.
The thermosetting adhesive sheet of the present invention is formed with the thermosetting comprising described compositions of thermosetting resin on base material film
Property adhesive linkage.
The manufacture method of the thermosetting adhesive sheet of the present invention has following operation：
By making epoxy resin and the solidification containing this at least one epoxy resin in organic acid dihydrazide
Agent is dissolved in the organic solvent containing acrylic copolymer, to prepare the preparation section of thermosetting adhesive linkage formation coating,
Described acrylic copolymer is dissolved in the acrylic copolymer containing the monomer containing epoxy radicals of described organic solvent；With
By above-mentioned thermosetting adhesive linkage formation coatings and are dried on base material film, it is formed at 150～180 DEG C
Heating pressurization when tensile modulus of elasticity be 105～106The thermosetting adhesive linkage formation process of the thermosetting adhesive linkage of Pa.
Invention effect
For the compositions of thermosetting resin of the present invention, by making the stretching bullet when carrying out heating pressurization for 150～180 DEG C
Property modulus be 105～106Pa, heating pressurization when can be in the short time between removing circuit and adhesive sheet composition surface bubble.
Brief description
[Fig. 1] Figure 1A～Fig. 1 E is the process chart of the method for applied voltage test is described.
[Fig. 2] Fig. 2 be pattern represent the profile of sample used in applied voltage test.
Specific embodiment
Hereinafter, for compositions of thermosetting resin, thermosetting adhesive sheet and the thermosetting adhesive sheet being suitable for the present invention
The specific embodiment of manufacture method an example, illustrate in the following order referring to the drawings on one side.
1. compositions of thermosetting resin
1-1. acrylic copolymer
1-2. epoxy resin
1-3. firming agent
1-4. amine system firming agent
2. the manufacture method of compositions of thermosetting resin
3. thermosetting adhesive sheet
4. the manufacture method of thermosetting adhesive sheet
5. other embodiment
6. embodiment.
＜ 1. compositions of thermosetting resin ＞
When carrying out heating pressurization for 150～180 DEG C, tensile modulus of elasticity is the compositions of thermosetting resin of present embodiment
105～106Pa.Thus, heating pressurization when can be in the short time between removing circuit and adhesive sheet composition surface bubble.With
Under, " tensile modulus of elasticity " refers to using the JIS K7244-4 plastics " test method of dynamic mechanically characteristic（Stretching vibration）" survey
Surely the value obtaining.The tensile modulus of elasticity of compositions of thermosetting resin is less than 105During Pa, the viscosity of compositions of thermosetting resin becomes
Low, after heating pressurization, air easily enters between circuit and adhesive sheet composition surface, and therefore completely removing bubble then needs
For a long time.In addition, the tensile modulus of elasticity of compositions of thermosetting resin is more than 106During Pa, the viscosity of compositions of thermosetting resin
Uprise, completely removing the bubble existing between circuit and adhesive sheet composition surface then needs for a long time.
Compositions of thermosetting resin contains such as acrylic copolymer, epoxy resin and as hardener for epoxy resin
Organic acid dihydrazide, described acrylic copolymer contains the vinyl monomer containing epoxy radicals.
＜ 1-1. acrylic copolymer ＞
Acrylic copolymer has film property when film is formed, for giving pliability, obdurability to solidfied material.Acrylic acid
Copolymer is the copolymerization for example making vinyl monomer, acrylonitrile monemer and the monomer copolymerization without epoxy radicals containing epoxy radicals
Thing.
＜ contains the vinyl monomer ＞ of epoxy radicals
Vinyl monomer containing epoxy radicals is used for reacting with hardener for epoxy resin, with compositions of thermosetting resin
Solidfied material in formed three-dimensional crosslinking structure.When forming three-dimensional crosslinking structure, the moisture-proof of solidfied material and thermostability improve.Example
As even if to comprising to be bonded and fixed to the reinforced resin of flexible print wiring board by the solidfied material of compositions of thermosetting resin
The scolding tin that the enhancing flexible print wiring board of sheet material carries out more than 260 DEG C is processed（For example reflow is processed）When, prevented also from it
The swelling that the portion's generation that is adhesively fixed is led to because of moisture absorption.
As this vinyl monomer containing epoxy radicals, can be from the conventional acrylic acid seriess heat being applied to electronic parts sectors
Suitably select in material used in solidity bonding agent to be used.Such as glycidyl acrylate can be enumerated（GA）, first
Base glycidyl acrylate（Hereinafter referred to as " GMA "）, acrylic acid methylglycidyl esters, allyl glycidyl ether etc..
These contain in the vinyl monomer of epoxy radicals, from the viewpoint of being readily available, preferably use GMA from safety, market.Give
Illustrate, the monomer containing epoxy radicals can be used alone a kind, also and can use two or more.
The amount preparing the vinyl monomer containing epoxy resin in the whole monomers being used during acrylic copolymer is very few
When then thermostability reduce, then have the tendency of when excessive peel strength reduce, therefore preferably 1～10 mass %.
＜ acrylonitrile monemer ＞
Acrylonitrile monemer is used for improving thermostability.For example, as acrylonitrile monemer, acrylonitrile, metering system can be enumerated
Nitrile.Acrylonitrile monemer can be used alone a kind, also and can be used two or more.
Prepare acrylonitrile monemer in the whole monomers being used during acrylic copolymer amount very few when then thermostability fall
Low, then become when excessive to be difficult to be dissolved in solvent, therefore preferably 20～35 mass %, more preferably 25～30 mass %.
＜ does not contain epoxy radicals（Methyl）Acrylate monomer ＞
As without epoxy radicals（Methyl）Acrylate monomer, can be from the conventional propylene being applied to electronic parts sectors
Acid is suitably to select in material used in heat-curable adhesive to use.As without epoxy radicals（Methyl）Acrylate list
Body, for example, can enumerate acrylic acid methyl ester.（MA）, ethyl acrylate（EA）, n-propyl, n-butyl acrylate, acrylic acid different
Butyl ester, the just own ester of acrylic acid, n-octyl, Isooctyl acrylate monomer, 2-EHA, acrylic acid different nonyl ester, third
Olefin(e) acid stearyl, methyl methacrylate, ethyl methacrylate, n-BMA, isobutyl
Ester, the just own ester of methacrylic acid, n octyl methacrylate, 2-Propenoic acid, 2-methyl-, isooctyl ester, 2-Ethylhexyl Methacrylate, first
Base acrylic acid different nonyl ester, methacrylic acid n-dodecane base ester, methacrylic acid Fancol ID base ester, methacrylic acid octadecane
Base ester etc..These do not contain epoxy radicals（Methyl）In acrylate monomer, preferably use butyl acrylate, ethyl acrylate.This
Do not contain epoxy radicals a bit（Methyl）Acrylate monomer can be used alone a kind, also and can be used two or more.
Prepare the monomer without epoxy resin in the whole monomers being used during acrylic copolymer amount very few when then
Fundamental characteristics reduces, and then has the tendency of thermostability and reduce when excessive, therefore preferably 60～75 mass %.
＜ weight average molecular weight ＞
When the weight average molecular weight of acrylic copolymer is too small, then peel strength and thermostability reduce, when weight average molecular weight is excessive
Then there is solution viscosity raising, coating is deteriorated.Therefore, the weight average molecular weight of acrylic copolymer is preferably 500,000～70
Ten thousand.
＜ glass transition temperature ＞
Compositions of thermosetting resin can be by the glass transition temperature of acrylic copolymer（Tg）To adjust stretching bullet
Property modulus.The glass transition temperature of such as acrylic copolymer is preferably -4.5 DEG C～20 DEG C of scope.
＜ 1-2. epoxy resin ＞
The epoxy resin constituting compositions of thermosetting resin is used to form three-dimensional mesh structure, makes cementability become good
Good.
As epoxy resin, can be from institute be applied to the conventional epoxy resin heat-curable adhesive of electronic parts sectors
Suitably select in the liquid using or the epoxy resin of solid, shaped to use.For example, bisphenol A type epoxy resin, bisphenol-f type can be enumerated
Epoxy resin, bisphenol-A D-ring oxygen tree fat, bisphenol-A epoxy resin, phenol novolak type epoxy resin, cresol novolac
Type epoxy resin, polyalkylene polyol（Neopentyl glycol etc.）Polyglycidyl ether, four glycidyl group diaminourea hexichol
Methylmethane, triglycidyl group para-aminophenol, triglycidyl meta-aminophenol, four glycidyl group m-xylene diamine,
O-phthalic acid diglycidyl ester, hexahydrophthalic acid 2-glycidyl ester, tetrahydrophthalic acid 2-glycidyl ester,
VCH diepoxide, 3,4- epoxycyclohexylmethyl（3,4- epoxy-cyclohexane）Formic acid esters, double（3,4- rings
Epoxide -6- methylhexyl methyl）Adipate ester etc..These epoxy resin can be used alone a kind, also and can be used two or more.
When the usage amount of epoxy resin is very few, then thermostability reduces, and then has the tendency of cementability and reduce when excessive, therefore phase
For acrylic copolymer 100 mass parts, preferably 5～30 mass parts, more preferably 10～20 mass parts.
＜ 1-3. firming agent ＞
Compositions of thermosetting resin contains organic acid dihydrazide as the firming agent of epoxy resin.By using organic acid two
Hydrazides, as firming agent, can improve under room temperature the room temperature keeping quality of the compositions of thermosetting resin being solid.
The preferred mean diameter of organic acid dihydrazide is 0.5～15 μm and is uniformly dispersed.Organic acid dihydrazide average
When particle diameter is less than 0.5 μm, when using the organic solvent for being coated with compositions of thermosetting resin, organic acid dihydrazide particle is molten
The probability of solution improves, and room temperature keeping quality is likely to decrease.When the mean diameter of organic acid dihydrazide is more than 15 μm, thermosetting tree
The coating of oil/fat composition reduces and granularity is big, thus is possible to fill when with acrylate copolymer or epoxy resin melting
Divide ground mixing.
As organic acid dihydrazide, suitably can select from the organic acid dihydrazide as the firming agent of epoxy resin in the past
Select.For example, careless acid dihydrazide, acid dihydrazide, succinum acid dihydrazide, iminodiacetic acid two hydrazides, adipic acid can be enumerated
Two hydrazides, 1,5-pentanedicarboxylic acid. two hydrazides, suberic acid two hydrazides, Azelaic Acid two hydrazides, sebacic dihydrazide, dodecanedioic acid two hydrazides,
Hexadecandioic acid (hexadecane diacid) two hydrazides, Malaysia acid dihydrazide, fumaric acid two hydrazides, diethylene glycol acid dihydrazide, winestone acid dihydrazide, malic acid
Two hydrazides, isophthalic dihydrazide, terephthaldehyde's acid dihydrazide, 2,6- naphthoic acid two hydrazides, 4,4 '-RH-5992, Isosorbide-5-Nitrae-
Naphthoic acid two hydrazides, ア ミ キ ュ ア VDH, ア ミ キ ュ ア UDH（Trade name, aginomoto（Strain）System）, citric acid three hydrazides, 7,
11- 18 carbon diene -1,18- diformylhydrazine etc..Organic acid dihydrazide can be used alone a kind, also and can be used two or more.These
In organic acid dihydrazide, from relatively low, curable the balancing good of fusing point, obtain from the viewpoint of easily, preferably use adipic acid
Two hydrazides or 7,11- 18 carbon diene -1,18- diformylhydrazine.
When the usage amount of firming agent is very few, then unreacted epoxy radicals residual, crosslinked insufficient, therefore thermostability, bonding
Property can reduce.In addition, when the usage amount of firming agent is excessive, then because excessive firming agent is remained with unreacted state, therefore
There is thermostability, cementability reduces.Thus, the usage amount of firming agent is total with respect to acrylic copolymer and epoxy resin
Count 100 mass parts and be preferably 2～15 mass parts.
＜ 1-4. amine system firming agent ＞
For compositions of thermosetting resin, the epoxy base section of acrylic copolymer is partly handed over by amine system firming agent
Connection.So, by the epoxy radicals of the acrylic copolymer in compositions of thermosetting resin are crosslinked with amine system curing agent part ground,
Tensile modulus of elasticity can be adjusted as described above to 105～106Pa.Amine system firming agent is from solidifying at normal temperatures with epoxy resin
From the point of view of, preferably liquid.
As amine system firming agent, polyamines or the polyamide-amide of liquid can be enumerated, specifically, can enumerate as aliphatic
The chain fatty race polyamines of polyamines, annular aliphatic polyamines etc..As chain fatty race polyamines, for example, can enumerate diethylidene three
Amine, triethylene polyamines, tetren, trien, dipropylenediamine, diethyl amino propyl amine.As
Annular aliphatic polyamines, for example, can enumerate menthene diamidogen, isophorone diamine.
In the case that in acrylic copolymer, crosslinked epoxy base section is few, tensile modulus of elasticity becomes bad.In addition,
In the case that in acrylic copolymer, crosslinked epoxy base section is many, tensile modulus of elasticity has no problem, but room temperature preserves
Property is bad.For the crosslinked ratio of epoxy radicals, for example can be by using DSC (Differential Scanning
Calorimetry, differential scanning calorimetry) measure and observe exothermal peak to confirm.
As described above, the compositions of thermosetting resin of present embodiment passes through to make to carry out adding at 150～180 DEG C
Tensile modulus of elasticity during heat pressurization is 105～106Pa, can removing circuit and adhesive sheet in the short time in heating pressurization
Bubble between composition surface.Activity time thus can be shortened, improve productivity ratio.
In addition, the compositions of thermosetting resin of present embodiment due to containing organic acid dihydrazide as firming agent, therefore
Room temperature excellent storage stability, do not need the equipment such as refrigerator, the operation such as carrying, preservation can be made to become very easy.
And then, the compositions of thermosetting resin of present embodiment due to having excellent adhesive strength, therefore with respect to example
As polyimide film, metallic plate also can maintain high adhesiveness.
In addition, the compositions of thermosetting resin of present embodiment is due to moisture absorption scolding tin excellent heat resistance, so even for example
Resistance to unleaded reflow when also can make actual load under the high humility of summer etc. becomes good.
Manufacture method ＞ of ＜ 2. compositions of thermosetting resin
The compositions of thermosetting resin of present embodiment can equably mix acrylic acid copolymer by using conventional method
Thing, epoxy resin, firming agent and amine system firming agent are being prepared.For example by be dissolved in organic solvent acrylic copolymer,
After carrying out while mixing with blender with amine system firming agent reacting, mixing, put into the asphalt mixtures modified by epoxy resin of ormal weight in organic solvent
Fat and firming agent, can make the adhesive solution forming compositions of thermosetting resin.Shape as compositions of thermosetting resin
State, for example, can enumerate paste, film, dispersion liquid.
＜ 3. thermosetting adhesive sheet ＞
Thermosetting adhesive sheet is, for example, in base material film（Peeling base）Upper formation comprises above-mentioned compositions of thermosetting resin
Thermosetting adhesive linkage sheet material.As base material film, polyethylene terephthalate film, polyimide film can be enumerated
Deng.Thermosetting adhesive sheet from keeping quality or use when the viewpoint such as treatability, preferably to poly terephthalic acid second two
Alcohol ester film, polyimide film etc. have been carried out on the base material film of lift-off processing with organosilicon etc. with 10～50 μm of thickness as needed
It is formed with the thermosetting adhesive linkage comprising compositions of thermosetting resin.
Manufacture method ＞ of ＜ 4. thermosetting adhesive sheet
Thermosetting adhesive sheet for example can be by following method manufacture.The manufacture method of thermosetting adhesive sheet include with
Lower operation：Prepare the preparation section of thermosetting adhesive linkage formation coating；With the thermosetting adhesive linkage forming thermosetting adhesive linkage
Formation process.
In preparation section, put into compositions of thermosetting resin in the way of reaching viscosity corresponding with organic solvent, make
Firming agent disperses in organic solvent, to make acrylic copolymer and epoxy resin dissolve in organic solvent, thus prepare thermosetting
Property adhesive linkage formation coating.As organic solvent, for example, can use butanone, toluene etc..
In preparation section, preferably all 70 mass % of organic acid dihydrazide particle are divided as solids at room temperature
It is dispersed in thermosetting adhesive linkage formation coating.Thus, it is possible to improve the room temperature keeping quality of thermosetting adhesive sheet.
In thermosetting adhesive linkage formation process, with bar coater, roll coater in the way of dry thickness reaches 10～50 μm
, done by conventional method on base material film Deng by the thermosetting prepared in preparation section adhesive linkage formation coatings
Dry, form thermosetting adhesive linkage.Thus, thermosetting bonding layer of sheet material can be obtained.
Above-mentioned compositions of thermosetting resin and thermosetting adhesive sheet are for example preferably applied to electronic parts sectors.Especially
It is that thermosetting adhesive sheet is preferably applied to portion of terminal to flexible print wiring board etc. and gathering to benzene two for its lining
Formic acid glycol ester, polyimides, expoxy glass, rustless steel, the enhancing of 50 μm～2mm of aluminum equal thickness are glued with resin sheet
Connect fixation.Thus, portion of terminal and the solidification by present embodiment for the enhancing resin sheet of flexible print wiring board can be obtained
Property bonding layer of sheet material the thermosetting compound of the thermosetting adhesive linkage eliminating base material film to carry out the enhancing that is adhesively fixed flexible
Printed circuit board (PCB).
＜ 5. other embodiment ＞
In the above description, by a part of epoxy radicals in acrylic copolymer are passed through the crosslinking of amine system firming agent,
The tensile modulus of elasticity when carrying out heating pressurization for 150～180 DEG C is made to be 105～106Pa, but it is not limited to this example.For example also may be used
Not use amine system firming agent, and adjust the Weight-average molecular of the glass transition temperature of acrylic copolymer, acrylic copolymer
Amount, obtaining the tensile modulus of elasticity when carrying out heating pressurization for 150～180 DEG C is 105～106The compositions of thermosetting resin of Pa.
Embodiment
Hereinafter the specific embodiment of the present invention is illustrated.It is explained, following embodiments do not limit the present invention's
Scope.
（Material）
Acrylic copolymer
Butyl acrylate（BA）, ethyl acrylate（EA）, acrylonitrile（AN）, GMA, acrylic acid（AA）, methacrylic acid -2-
Hydroxy methacrylate（HEMA）
Epoxy resin
JER806、JER1031S（It is all Mitsubishi chemical Co., Ltd's system）
Firming agent
7,11- ten eight carbon diene -1,18- diformylhydrazine（UDH）
Precrosslink amine system firming agent
Trien and its mixture of modifier.
（The preparation of heat cure adhesive linkage formation coating）
In embodiment 1～4, embodiment 6 and comparative example 4, weighed in the way of reaching table 1 composition and be dissolved in organic solvent
Acrylic copolymer and the trien as amine system firming agent and its modifier mixture, use blender
（Asada Iron Works Co., Ltd. デ ィ ゾ Le バ）Mix 2 hours while making it react.After mixing, put into the epoxy of ormal weight
Resin, firming agent, make the adhesive solution of table 1 composition（Compositions of thermosetting resin）.It is explained, in Table 1, each chemical combination
The unit of the addition of thing is mass parts.
In embodiment 5 and comparative example 3, except trien and its modifier as amine system firming agent is not used
Mixture beyond, in the same manner as embodiment 1～4, embodiment 6 and comparative example 4, make table 1 composition adhesive solution.
In comparative example 1, except not being used GMA acrylic acid to be used as acrylic copolymer as acrylic acid copolymer
Beyond thing, in the same manner as embodiment 5 and comparative example 3, make the adhesive solution of table 1 composition.
In comparative example 2, except being used methacrylic acid -2- hydroxy methacrylate to replace the acrylic acid as acrylic copolymer
In addition, in the same manner as comparative example 5 and comparative example 3, make the adhesive solution of table 1 composition.
（The making of thermosetting adhesive sheet）
By the thermosetting adhesive linkage formation coatings of gained in the poly terephthalic acid second two implementing lift-off processing
Alcohol ester film, is dried in 50～130 DEG C of drying oven, forms the thermosetting adhesive linkage of 35 μ m-thick, thus makes embodiment 1
The thermosetting adhesive sheet of～embodiment 5 and comparative example 1～comparative example 4.
Table 1
.
（For tensile modulus of elasticity）
For each thermosetting cementability sheet material, the tensile modulus of elasticity at measuring 170 DEG C.Result is shown in table 1.
（Applied voltage test）
In applied voltage test, as vacuum pressed, employ Vacuum Star (ミ カ De テ Network ノ ス society system）.Pressurization
Condition is pressed temperature：170 DEG C, moulding pressure：1.8MPa, pressing time：Vacuum retention time 10s.
As shown in Figure 1A, with the condition lamination of 100 DEG C, 1m/min, 5kg/cm on as the polyimide film 1 strengthening plate
As the composition of table 1, the thermosetting adhesive linkage 2 of cooperation, obtains laminated sample 3.Then, as illustrated in figures ib and 1 c, by lamination
Sample 3 is punched to and evaluation FPC（Flexible Printed Circuits, flexible printed circuit）Enhancing position identical
Pattern, make evaluation film（Strengthen plate/thermosetting adhesive sheet sample）4.
As shown in figure ip, the evaluation film 4 of punching is pasted onto as on the one side FPC5 of evaluation FPC.One side FPC5
As shown in Fig. 1 D and Fig. 2, comprise the one side CCL that thickness is 56 μm（Copper clad laminate, coper-coated laminate）8 and
The thickness being arranged in the one side of one side CCL8 is 45 μm of coating（Overlay film）7.One side CCL8 is the Copper Foil making thickness be 18 μm
6 and polyimide film 9 that thickness is 25 μm be 13 μm across thickness the material that is laminated of layer of adhesive material 11.
As referring to figure 1e, confirm the enhancing plate bonding site after pressurization under these conditions using optical microscope 10,
Confirm there is bubble-free.Shortest time till bubble is wholly absent will be started from pressurization as the " pressing time in table 1
（Bubble removes）”.In Table 1, pressing time represents, for "○", the situation that pressing time is less than 45 seconds, and pressing time is "×"
Represent the situation more than 45 seconds for the pressing time.
（The evaluation of peel strength）
The evaluation of peel strength is carried out as follows.The firm thermosetting cementability sheet material obtaining is cut into the rectangular of prescribed level
Shape（5cm×10cm）, using the thermosetting being set as that 80 DEG C of laminator will be cut in rectangular thermosetting cementability sheet material
Property adhesive linkage is temporarily pasted onto 175 μm of polyimide film（175AH、カネカ（Strain）System）After upper, base material film removed, makes heat
Solidity adhesive linkage exposes.With respect to the thermosetting adhesive linkage exposing, from upper overlap and thermosetting cementability sheet material formed objects
The polyimide film of 50 μ m-thick（200H, デ ュ ポン society system）, pressurizeed 60 seconds with the pressure heating of 2. 0MPa at 170 DEG C
Afterwards, keep 60 minutes in 140 DEG C of baking oven.
In addition, rectangle will be cut into（5cm×10cm）The thermosetting adhesive linkage of thermosetting adhesive sheet be pressed against
After temporarily pasting on the expoxy glass plate of the SUS304 plate of 0.5mm or thickness 1mm, base material film is removed, makes thermosetting adhesive linkage
Expose.With respect to the thermosetting adhesive linkage exposing, from 50 μm of polyimide film of upper overlapping OBL thickness（5cm×
10cm）, after being pressurizeed 60 seconds with the pressure heating of 2.0MPa at 170 DEG C, keep 60 minutes in 140 DEG C of baking oven.
] and then, with respect to polyimide film, 90 degree of disbonded tests are carried out with peeling rate 50mm/min, measure the institute that tears
The power needing.The obtained results are shown in table 1.Peel strength is expected for 10N/cm in practical.
（Moisture absorption reflow heat-resistance test）
Moisture absorption reflow heat-resistance test proceeds as described below.Rectangle will be cut into using the laminator being set as 80 DEG C
（2cm×2cm）The thermosetting adhesive linkage of thermosetting cementability sheet material be temporarily pasted onto the polyimide film of 175 μ m-thick（アピ
カル175AH、カネカ（Strain）System）After upper, peeling base removed, so that thermosetting adhesive linkage is exposed.With respect to the heat exposed
Solidity adhesive linkage, from the polyimide film of 50 μm of the thickness of upper overlap formed objects（カ プ ト Application 200H, デ ュ ポン society system）,
After being pressurizeed 60 seconds with the pressure heating of 2.0MPa at 170 DEG C, keep 60 minutes in 140 DEG C of baking oven.Then, will carry out
The test film being heating and curing is placed 96 hours in 40 DEG C, the damp and hot baking oven of 90RH.
Make just to have carried out the test film of humid heat treatment by being set as the maximum temperature reflow oven of 260 DEG C × 30 seconds, to logical
Later test film is visually observed and is had or not the abnormal appearances such as expansion, stripping.Observed result is shown in table 1.In table 1, moisture absorption reflow
Thermostability refers to, for " 260 DEG C of Pass ", the situation that outward appearance has no problem completely.Moisture absorption reflow thermostability refers to try for " 260 DEG C of NG "
Test and observe in piece by the situation of led to expansion of foaming.
（With regard to room temperature keeping quality）
Room temperature keeping quality proceeds as described below evaluation.I.e., in Table 1, room temperature keeping quality represents for "○" makes each thermosetting
The peel strength at adhesive sheet initial stage, compared with this thermosetting adhesive sheet is preserved the peel strength after 3 months at normal temperatures
Relatively, the situation that the reduction rate of peel strength is less than 30%.Should illustrate, even if the reduction rate for above-mentioned peel strength is less than
30%, but the moisture absorption reflow Evaluation of Heat Tolerance at initial stage is good（Above-mentioned " 260 DEG C of Pass "）, and after preserving 3 months at normal temperatures
Moisture absorption reflow Evaluation of Heat Tolerance be bad（Above-mentioned " 260 DEG C of NG "）Thermosetting adhesive sheet, can specify its pass through room temperature
Place and produce characteristic variations, be therefore evaluated as " △ ".
The thermosetting adhesive sheet obtaining in embodiment 1～embodiment 6 meets the stretching when carrying out heating pressurization for 170 DEG C
Elastic modelling quantity is 1.1 × 105～3.5 × 105Pa, the tensile modulus of elasticity when carrying out heating pressurization for 150～180 DEG C are 105~
106The condition of Pa.Accordingly, for the thermosetting adhesive sheet obtaining in embodiment 1～embodiment 5, adding in heating pressurization
The pressure time is 20～40 seconds, bubble that can at short notice between the composition surface of removing circuit and thermosetting adhesive sheet.In addition,
The thermosetting adhesive sheet obtaining in embodiment 1～embodiment 5 is heat-resisting in the room temperature keeping quality of film, peel strength, moisture absorption reflow
Property test evaluation aspect all good.
The tensile modulus of elasticity when carrying out heating pressurization for 170 DEG C for the thermosetting adhesive sheet obtaining in comparative example 1 is 7.0
×104Pa, therefore heating pressurization when can not be in the short time between the composition surface of removing circuit and thermosetting adhesive sheet gas
Bubble.In addition, the thermosetting adhesive sheet obtaining in comparative example 1 does not contain GMA, therefore room temperature keeping quality is bad.
The tensile modulus of elasticity when carrying out heating pressurization for 170 DEG C for the thermosetting adhesive sheet obtaining in comparative example 2 is 6.5
×104Pa, therefore heating pressurization when can not be in the short time between the composition surface of removing circuit and thermosetting adhesive sheet gas
Bubble.In addition, the thermosetting adhesive sheet obtaining in comparative example 2 does not contain GMA, therefore room temperature keeping quality is bad.
The tensile modulus of elasticity when carrying out heating pressurization for 170 DEG C for the thermosetting adhesive sheet obtaining in comparative example 3 is 7.0
×104Pa, therefore heating pressurization when can not be in the short time between the composition surface of removing circuit and thermosetting adhesive sheet gas
Bubble.
The tensile modulus of elasticity when carrying out heating pressurization for 170 DEG C for the thermosetting adhesive sheet obtaining in comparative example 4 is 6.0
×104Pa, therefore heating pressurization when can not be in the short time between the composition surface of removing circuit and thermosetting adhesive sheet gas
Bubble.
Claims (7)
1. compositions of thermosetting resin, it comprises acrylic copolymer, epoxy resin and this hardener for epoxy resin, its
150～180 DEG C of tensiles modulus of elasticity carrying out heating during pressurization are 105～106Pa, described acrylic copolymer makes containing epoxy radicals
Vinyl monomer, acrylonitrile monemer and forming without the monomer copolymerization of epoxy radicals,
Wherein, with respect to acrylic copolymer 100 mass parts, containing acrylate monomer 60～75 mass without epoxy radicals
Part, acrylonitrile monemer 20～35 mass parts and vinyl monomer 1～10 mass parts containing epoxy radicals,
A part of epoxy radicals in aforesaid propylene acid copolymer are crosslinked by amine system firming agent.
2. compositions of thermosetting resin according to claim 1, wherein, this hardener for epoxy resin contains organic acid two
Hydrazides.
3. compositions of thermosetting resin according to claim 2, wherein, with respect to aforesaid propylene acid copolymer 100 mass
Part, it is combined with above-mentioned epoxy resin 10～20 mass parts.
4. the compositions of thermosetting resin according to Claims 2 or 3, wherein, with respect to aforesaid propylene acid copolymer 100 matter
Amount part, is combined with above-mentioned organic acid dihydrazide 10～20 mass parts.
5. the compositions of thermosetting resin according to Claims 2 or 3, wherein, the mean diameter of above-mentioned organic acid dihydrazide
For 0.5～15 μm, and it is uniformly dispersed.
6. thermosetting adhesive sheet, wherein, is formed with the thermosetting comprising any one of Claims 1 to 5 on base material film
The thermosetting adhesive linkage of property resin combination.
7. the manufacture method of thermosetting adhesive sheet, it has following operations：
By making epoxy resin and the firming agent containing this at least one epoxy resin in organic acid dihydrazide molten
Solution, in the organic solvent containing acrylic copolymer and amine system firming agent, to prepare the system of thermosetting adhesive linkage formation coating
Standby operation, described acrylic copolymer is dissolved in the vinyl monomer making containing epoxy radicals of described organic solvent, acrylonitrile list
Body and the monomer copolymerization without epoxy radicals form acrylic copolymer, and a part of epoxy radicals in described acrylic copolymer are led to
Cross described amine system firming agent crosslinked；With
By by above-mentioned thermosetting adhesive linkage formation coatings on base material film and be dried, be formed at 150～180 DEG C plus
During heat pressurization, tensile modulus of elasticity is 105～106The thermosetting adhesive linkage formation process of the thermosetting adhesive linkage of Pa.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-264790 | 2010-11-29 | ||
| JP2010264790A JP5820108B2 (en) | 2010-11-29 | 2010-11-29 | Thermosetting adhesive sheet and method for producing thermosetting adhesive sheet |
| PCT/JP2011/075936 WO2012073672A1 (en) | 2010-11-29 | 2011-11-10 | Heat-curing resin composition, heat-curing adhesive sheet, and method for producing heat-curing adhesive sheet |
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| JP (1) | JP5820108B2 (en) |
| KR (1) | KR101871532B1 (en) |
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| DK3026076T3 (en) * | 2014-11-27 | 2019-01-28 | Polynt Composites France | Vinyl ester prepreg Powder |
| KR101949632B1 (en) | 2015-03-26 | 2019-02-18 | 데쿠세리아루즈 가부시키가이샤 | Method for manufacturing flexible mounting module body |
| JP6721325B2 (en) * | 2015-12-14 | 2020-07-15 | デクセリアルズ株式会社 | Thermosetting adhesive sheet and method for manufacturing semiconductor device |
| CN108905632B (en) * | 2018-07-16 | 2020-12-08 | 安徽智泓净化科技股份有限公司 | Rapid curing method for membrane element sealant with reverse osmosis function |
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| TWI257415B (en) * | 1999-06-18 | 2006-07-01 | Hitachi Chemical Co Ltd | Adhesive, adhesive member, interconnecting substrate for semiconductor mounting having adhesive member, and semiconductor device containing the same |
| CN101522751A (en) * | 2006-10-06 | 2009-09-02 | 日立化成工业株式会社 | Liquid resin composition for electronic part sealing and electronic part apparatus utilizing the same |
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| JPH01113476A (en) * | 1987-10-28 | 1989-05-02 | Nissan Motor Co Ltd | Epoxy adhesive composition |
| JPH02202973A (en) * | 1989-02-02 | 1990-08-13 | Sumitomo Electric Ind Ltd | Adhesive composition for flexible printed circuit board |
| JPH0433915A (en) * | 1990-05-29 | 1992-02-05 | Ajinomoto Co Inc | One pack-type epoxy resin composition |
| JPH093021A (en) * | 1995-06-16 | 1997-01-07 | Otsuka Chem Co Ltd | Fine powdery hydrazine compound |
| JP3617417B2 (en) * | 1999-06-18 | 2005-02-02 | 日立化成工業株式会社 | Adhesive, adhesive member, wiring board for semiconductor mounting provided with adhesive member, and semiconductor device using the same |
| JP2004075914A (en) * | 2002-08-21 | 2004-03-11 | Toray Ind Inc | Epoxy resin composition and prepreg |
| JP2005330300A (en) * | 2004-05-18 | 2005-12-02 | Mitsui Chemicals Inc | Thermosetting resin composition, film-like adhesive and semiconductor package |
| JP5228426B2 (en) * | 2006-10-06 | 2013-07-03 | 日立化成株式会社 | Liquid resin composition for electronic component sealing and electronic component device using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI257415B (en) * | 1999-06-18 | 2006-07-01 | Hitachi Chemical Co Ltd | Adhesive, adhesive member, interconnecting substrate for semiconductor mounting having adhesive member, and semiconductor device containing the same |
| CN101522751A (en) * | 2006-10-06 | 2009-09-02 | 日立化成工业株式会社 | Liquid resin composition for electronic part sealing and electronic part apparatus utilizing the same |
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| CN103221449A (en) | 2013-07-24 |
| TW201235430A (en) | 2012-09-01 |
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| KR101871532B1 (en) | 2018-06-26 |
| KR20140018205A (en) | 2014-02-12 |
| TWI550047B (en) | 2016-09-21 |
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| WO2012073672A1 (en) | 2012-06-07 |
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