WO2012073703A1 - 熱硬化性樹脂組成物、熱硬化性接着シート及び熱硬化性接着シートの製造方法 - Google Patents
熱硬化性樹脂組成物、熱硬化性接着シート及び熱硬化性接着シートの製造方法 Download PDFInfo
- Publication number
- WO2012073703A1 WO2012073703A1 PCT/JP2011/076454 JP2011076454W WO2012073703A1 WO 2012073703 A1 WO2012073703 A1 WO 2012073703A1 JP 2011076454 W JP2011076454 W JP 2011076454W WO 2012073703 A1 WO2012073703 A1 WO 2012073703A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- thermosetting
- acrylic copolymer
- amino group
- epoxy
- Prior art date
Links
Images
Classifications
-
- 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
- C08G59/20—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
- C08G59/3209—Epoxy compounds containing three or more epoxy groups obtained by polymerisation of unsaturated mono-epoxy compounds
-
- 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
- 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
-
- 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
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
-
- 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
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K5/17—Amines; Quaternary ammonium compounds
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2813—Heat or solvent activated or sealable
- Y10T428/2817—Heat sealable
- Y10T428/2826—Synthetic resin or polymer
Definitions
- the present invention relates to a thermosetting resin composition containing an acrylic copolymer, an epoxy resin, and a curing agent for epoxy resin, a thermosetting adhesive sheet, and a method for producing a thermosetting adhesive sheet.
- Adhesives used for flexible printed circuit boards use a mixture of epoxy resin and epoxy resin curing agent as a curing component to improve peel strength and flexibility
- FPC Flexible Printed Circuits
- NBR acrylonitrile butadiene rubber
- NBR acrylonitrile butadiene Rubber
- a resin-based composition containing an epoxy resin and a crosslinkable carboxyl group is widely used in order to obtain good solder heat resistance (see Patent Document 1).
- the adhesive composition used for FPC contains a large amount of epoxy resin, a large amount of unreacted epoxy resin oozes out at the time of heat and pressure molding, resulting in holes provided in coverlays, reinforcing plates, etc. There was a problem of blocking the opening.
- the present invention has been proposed in view of such a conventional situation, and does not irradiate with ultraviolet rays or the like, and has a good exudation property such as an unreacted epoxy resin at the time of heat and pressure molding. It aims at providing the manufacturing method of curable resin composition, a thermosetting adhesive sheet, and a thermosetting adhesive sheet.
- thermosetting resin composition includes an acrylic copolymer containing an epoxy group-containing (meth) acrylic acid ester monomer, an epoxy resin, and a curing agent for the epoxy resin.
- the epoxy group portion of the acrylic copolymer is partially crosslinked by a liquid polyamine or polyamidoamine having at least one of a primary amino group and a secondary amino group.
- the method for producing a thermosetting adhesive sheet according to the present invention includes an acrylic copolymer containing an epoxy group-containing (meth) acrylic acid ester monomer dissolved in an organic solvent, and at least one of a primary amino group and a secondary amino group.
- a thermosetting adhesive layer that forms a thermosetting adhesive layer by applying a coating for forming an adhesive layer on a base film and drying it. And a step.
- the epoxy group portion of the acrylic copolymer is partially crosslinked by a liquid polyamine or polyamidoamine having at least one of a primary amino group and a secondary amino group, The exudation property of an unreacted epoxy resin or the like can be improved.
- thermosetting resin composition 1-1.
- Curing agent 1-4. Liquid polyamine or polyamidoamine having at least one of a primary amino group and a secondary amino group 2.
- Method for producing thermosetting resin composition 3.
- Thermosetting adhesive sheet 4. Manufacturing method of thermosetting adhesive sheet Other Embodiments 6 Example
- thermosetting resin composition contains an acrylic copolymer containing an epoxy group-containing (meth) acrylic acid ester monomer, an epoxy resin, and a curing agent for the epoxy resin.
- the acrylic copolymer has a film-forming property at the time of film forming, and imparts flexibility and toughness to the cured product.
- the acrylic copolymer is, for example, a copolymer of an epoxy group-containing (meth) acrylic acid ester monomer, an acrylonitrile monomer, and an epoxy group-free (meth) acrylic acid ester monomer.
- Epoxy group-containing (meth) acrylic acid ester monomer is used for reacting with a curing agent for epoxy resin to form a three-dimensional cross-linked structure in the cured product of the thermosetting resin composition.
- the moisture resistance and heat resistance of the cured product are improved.
- soldering treatment eg, solder reflow processing
- Such an epoxy group-containing (meth) acrylic acid ester monomer can be appropriately selected from those used in conventional acrylic thermosetting adhesives applied in the field of electronic components.
- examples of the epoxy group-containing (meth) acrylic acid ester monomer include glycidyl acrylate (GA) and glycidyl methacrylate (hereinafter referred to as “GMA”).
- GMA is preferably used from the viewpoint of safety and easy availability on the market.
- an epoxy group containing (meth) acrylic acid ester monomer may be used individually by 1 type, and may use 2 or more types together.
- the content is preferably 3 to 15% by mass.
- the amount of the acrylonitrile monomer in the total monomers used for preparing the acrylic copolymer is too low, the heat resistance is reduced, and if it is too high, it is difficult to dissolve in the solvent.
- the content is 25 to 30% by mass.
- Epoxy group-free (meth) acrylic acid ester monomer can be appropriately selected from those used in conventional acrylic thermosetting adhesives applied in the field of electronic components.
- Epoxy group-free (meth) acrylic acid ester monomers include, for example, methyl acrylate (MA), ethyl acrylate (EA), n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, n- Octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, i-nonyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate,
- epoxy group-free (meth) acrylic acid ester monomers it is preferable to use butyl acrylate or ethyl acrylate. These epoxy group-free (meth) acrylic acid ester monomers may be used alone or in combination of two or more.
- the amount of the epoxy resin-free monomer in the total monomer used for preparing the acrylic copolymer is too small, the basic characteristics are lowered, and when it is too much, the heat resistance tends to be lowered. More preferably, it is 65 to 70% by mass.
- the weight average molecular weight of the acrylic copolymer is preferably 500,000 to 700,000, more preferably 550,000 to 650,000.
- Epoxy resin which comprises a thermosetting resin composition forms a three-dimensional network structure, and is used in order to make adhesiveness favorable.
- the epoxy resin can be appropriately selected from liquid or solid epoxy resins used in conventional epoxy resin thermosetting adhesives applied in the field of electronic components.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyalkylene polyol (neopontyl glycol, etc.)
- Polyglycidyl ether, tetraglycidyl diaminodiphenylmethane triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, tetraglycidyl-m-xylenediamine, diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, vinyl Cyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxy
- the amount of the epoxy resin used is too small, the heat resistance is lowered, and when it is too large, the adhesiveness tends to be lowered. More preferably, it is 5 to 20 parts by mass.
- An organic acid dihydrazide may be used individually by 1 type, and may use 2 or more types together.
- adipic acid dihydrazide or 7,11-octadecadien-1,18-dicarbohydrazide is used from the viewpoint of relatively low melting point, excellent curability balance, and availability. It is preferable to use it.
- the amount of the curing agent used is preferably 2 to 15 parts by mass with respect to 100 parts by mass in total of the acrylic copolymer and the epoxy resin.
- thermosetting resin composition the epoxy group portion of the acrylic copolymer is partially crosslinked by a liquid polyamine or polyamidoamine having at least one of a primary amino group and a secondary amino group.
- the exudation property of the thermosetting resin composition is adjusted, and unreacted at the time of heat and pressure molding
- the exuding property of epoxy resin or the like can be improved.
- good exudation means that, for example, the amount of unreacted epoxy resin that exudes during heat and pressure molding is small.
- the polyamine or polyamidoamine having at least one of a primary amino group and a secondary amino group is preferably in a liquid form from the viewpoint of curing with an epoxy resin at room temperature.
- the thermosetting resin composition according to the present embodiment is preferably 1% or more of the epoxy group portion of the acrylic copolymer, more preferably 3 to 12% of the epoxy group portion of the acrylic copolymer is 1%. It is crosslinked by a liquid polyamine or polyamidoamine having at least one of a primary amino group and a secondary amino group.
- the cross-linked epoxy group portion in the acrylic copolymer is less than 1%, the exuding property of unreacted epoxy resin or the like at the time of heat and pressure molding is not sufficiently good.
- the curing reaction proceeds too much and the room temperature storage property becomes poor. It should be noted that it is difficult to strictly measure the ratio of the epoxy group crosslinked, but for example, the approximate ratio can be calculated by observing the calorific value of DSC (Differential-Scanning-Calorimetry) measurement.
- thermosetting resin composition according to the present embodiment is a polyamine or polyamide in which 3 to 12% of the epoxy group portion of the acrylic copolymer has at least one of a primary amino group and a secondary amino group. It is particularly preferred that it is crosslinked with an amine. This adjusts the amount of adhesive to bleed out, improves the oozing property of unreacted epoxy resin, etc. at the time of heat and pressure molding, and shows good film storage stability for a long period of time. it can.
- thermosetting resin composition according to the present embodiment includes an organic acid dihydrazide as a curing agent, so that it is excellent in storage stability at room temperature, no equipment such as a refrigerator is necessary, and handling such as transportation and storage is very easy. Can be easily.
- thermosetting adhesive sheet can be manufactured by the following method, for example.
- the method for producing a thermosetting adhesive sheet includes a crosslinking step in which 1 to 15% of an epoxy group portion of an acrylic copolymer is crosslinked with a liquid polyamine or polyamidoamine, and a coating for forming a thermosetting adhesive layer.
- thermosetting resin composition is introduced so as to have a viscosity corresponding to the organic solvent, the curing agent is dispersed in the organic solvent, and the acrylic copolymer and the epoxy resin are dissolved in the organic solvent.
- a coating for forming a thermosetting adhesive layer is prepared.
- the organic solvent for example, methyl ethyl ketone, toluene or the like can be used.
- thermosetting adhesive layer forming step the thermosetting adhesive layer forming coating material prepared in the preparation step is applied onto the base film with a bar coater, roll coater, etc. so that the dry thickness is 10 to 50 ⁇ m. Dry by the method to form a thermosetting adhesive layer. Thereby, a thermosetting adhesive layer sheet can be obtained.
- thermosetting resin composition and thermosetting adhesive sheet can be preferably applied to the electronic component field, for example.
- the thermosetting adhesive sheet bonds the terminal portion of a flexible printed wiring board to a reinforcing resin sheet having a thickness of 50 ⁇ m to 2 mm, such as polyethylene terephthalate, polyimide, glass epoxy, stainless steel, aluminum, etc. It can be preferably applied to fix.
- the terminal part of the flexible printed wiring board and the reinforcing resin sheet are bonded and fixed with the thermosetting material of the thermosetting adhesive layer excluding the base film of the curable adhesive layer sheet according to the present embodiment.
- a reinforced flexible printed wiring board can be obtained.
- thermosetting resin composition according to the present embodiment is a metal deactivator and antifoaming agent that does not promote the dissolution of the organic acid dihydrazide as necessary, as long as the effects of the present invention are not impaired.
- Known additives such as additives, rust inhibitors and dispersants may be blended.
- Curing agent 4 4,4′-diaminodiphenyl sulfone (DDS), 7,11-octadecadien-1,18-dicarbohydrazide (UDH)
- thermosetting adhesive layer An acrylic copolymer composed of the monomers shown in Table 1 was prepared. An acrylic copolymer dissolved in an organic solvent and a mixture of triethylenetetramine and its modified product are weighed so as to have the composition shown in Table 1, and reacted for 2 hours while mixing with a stirrer. The base part was partially crosslinked with a mixture of triethylenetetramine and its modification. After mixing, predetermined amounts of an epoxy resin and a curing agent were added to prepare a thermosetting adhesive layer forming coating composition (adhesive solution) having the composition shown in Table 1. In Comparative Example 1, a mixture of triethylenetetramine and a modified product thereof was not mixed.
- thermosetting adhesive sheet (Preparation of thermosetting adhesive sheet)
- the obtained thermosetting adhesive layer-forming coating material is applied to a polyethylene terephthalate film that has been subjected to a release treatment, and dried in a drying oven at 50 to 130 ° C. to form a thermosetting adhesive layer having a thickness of 35 ⁇ m.
- a thermosetting adhesive sheet was produced.
- BA is butyl acrylate
- EA is ethyl acrylate
- AN is acrylonitrile
- GMA is glycidyl methacrylate
- DDS is 4,4′-diaminodiphenylsulfone
- UH refers to 7,11-octadecadien-1,18-dicarbohydrazide.
- curing agent, a primary or secondary liquid amine, and carboxyl group-containing NBR is a mass part, respectively.
- “Actual blending amount of primary or secondary liquid amine” indicates the amount (part by mass) of triethylenetetramine and a modified product thereof actually added.
- epoxy group cross-linking ratio in acrylic rubber refers to the ratio (%) in which the epoxy group portion of the acrylic copolymer is cross-linked by a mixture of triethylenetetramine and a modified product thereof.
- the exudation property was evaluated as follows. As shown in FIG. 1A, on the surface of the thermosetting adhesive layer 1 filmed to 35 ⁇ m, a light release type release film (hereinafter referred to as “light side film”) 2 and a heavy release type release film (hereinafter referred to as “light release side film”).
- the light side film 2 of the adhesive sheet 4 was peeled off and laminated on a 175 ⁇ m polyimide film 5 as shown in FIG.
- the test piece 10 has a short side of 50 mm and a long side of 100 mm, and has a diameter of 10 mm, a diameter of 5 mm, and a diameter of 3 mm in the short direction (thickness direction) of the test piece 10. Holes for measuring exudation properties are formed.
- the test piece 10 was pressed under conditions of 170 ° C., 2 MPa, and 1 minute, and the amount of the thermosetting adhesive layer 1 that exudes from the punched section after pressing was measured with an optical microscope.
- Table 1 shows the results of measuring exudation properties.
- “O” indicates that the extruding width of the thermosetting adhesive layer 1 exuding from the hole provided in the test piece 10 is 50 to 100 ⁇ m.
- the protrusion property “ ⁇ ” indicates that the protrusion width of the thermosetting adhesive layer 1 oozing out from the hole provided in the test piece 10 is 100 to 200 ⁇ m.
- the oozing property “x” indicates that the oozing-out width of the oozing thermosetting adhesive layer 1 is 200 ⁇ m or more.
- thermosetting adhesive sheet immediately after being obtained is cut into a strip (5 cm ⁇ 10 cm) of a predetermined size, and the thermosetting adhesive layer is applied to a 175 ⁇ m polyimide film (175AH, Kaneka Corp.). After temporarily sticking with a laminator set at ° C., the base film was removed to expose the thermosetting adhesive layer. On the exposed thermosetting adhesive layer, a 50 ⁇ m-thick polyimide film (200H, manufactured by DuPont) of the same size is superimposed from above and heated and pressurized at 170 ° C. and a pressure of 2.0 MPa for 60 seconds, and then 140 Hold in oven at 60 ° C. for 60 minutes.
- thermosetting adhesive layer of the thermosetting adhesive sheet cut into a strip (5 cm ⁇ 10 cm) to a 0.5 mm SUS304 plate or a glass epoxy plate having a thickness of 1 mm, and temporarily attaching the substrate film, Removed to expose the thermosetting adhesive layer.
- a strip-shaped polyimide film (5 cm ⁇ 10 cm) having a thickness of 50 ⁇ m is superimposed on the exposed thermosetting adhesive layer, heated and pressurized at 170 ° C. and a pressure of 2.0 MPa for 60 seconds, and then heated at 140 ° C. Hold in oven for 60 minutes.
- thermosetting adhesive layer of the thermosetting adhesive sheet cut into a strip (2 cm ⁇ 2 cm) was temporarily attached to a 175 ⁇ m-thick polyimide film (Apical 175AH, Kaneka Corporation) with a laminator set at 80 ° C.
- the release substrate was removed from the thermosetting adhesive sheet to expose the thermosetting adhesive layer.
- a polyimide film Kerpton 200H, manufactured by DuPont
- Kapton 200H manufactured by DuPont
- the test piece immediately after the wet heat treatment was passed through a reflow oven set at a top temperature of 260 ° C. for 30 seconds, and the test piece after passing was visually observed for any abnormal appearance such as swelling and peeling.
- Table 1 “A” for moisture absorption reflow soldering heat resistance indicates a case where there was no problem in appearance.
- the moisture absorption reflow solder heat resistance of “C” indicates a case where swelling due to foaming is observed on the test piece.
- the room temperature storage was evaluated as follows. In Table 1, the room temperature storage property “ ⁇ ” indicates that the peel strength value is less than 30% compared to the initial value, and the moisture-absorbing solder reflow property is not changed. Moreover, the room temperature storage property “x” indicates that the peel strength value is 30% or more lower than the initial value, or the moisture-absorbing solder reflow property is changed.
- thermosetting adhesive sheets obtained in Examples 1 to 5 0.5 to 18% of the epoxy group portion of the acrylic copolymer is crosslinked with a mixture of triethylenetetramine and a modified product thereof. For this reason, the thermosetting adhesive sheets obtained in Examples 1 to 5 had good exuding properties of unreacted epoxy resin and the like at the time of heat and pressure molding.
- thermosetting adhesive sheets obtained in Examples 3 to 5 contain an organic acid dihydrazide in the thermosetting adhesive layer, and 3 to 12% of the epoxy group portion of the acrylic copolymer contains triethylenetetramine and Cross-linked by a mixture of the modified products.
- the thermosetting adhesive sheets obtained in Examples 3 to 5 have the ability to exude unreacted epoxy resin and the like during heat and pressure molding, room temperature storage property, peel strength, moisture absorption reflow soldering heat resistance All the evaluations of the property tests were good.
- thermosetting adhesive sheet obtained in Comparative Example 1 does not contain an organic acid dihydrazide in the thermosetting adhesive layer, and the epoxy group portion of the acrylic copolymer is at least one of a primary amino group and a secondary amino group. It is not crosslinked by a liquid polyamine or polyamidoamine having Therefore, the thermosetting adhesive sheet obtained in Comparative Example 1 was evaluated for exudation properties of unreacted epoxy resin, etc. during heat-pressure molding, room temperature storage property, peel strength, moisture absorption reflow solder heat resistance test. All were not good.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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
Description
1.熱硬化性樹脂組成物
1-1.アクリル共重合体
1-2.エポキシ樹脂
1-3.硬化剤
1-4.1級アミノ基及び2級アミノ基の少なくとも一方を有する液状のポリアミン又はポリアミドアミン
2.熱硬化性樹脂組成物の製造方法
3.熱硬化性接着シート
4.熱硬化性接着シートの製造方法
5.他の実施の形態
6.実施例
本実施の形態に係る熱硬化性樹脂組成物は、エポキシ基含有(メタ)アクリル酸エステルモノマーを含むアクリル共重合体と、エポキシ樹脂と、エポキシ樹脂用の硬化剤とを含有する。
アクリル共重合体は、フィルム成形時に成膜性をもたせ、硬化物に可撓性、強靭性を付与するためのものである。アクリル共重合体は、例えば、エポキシ基含有(メタ)アクリル酸エステルモノマーと、アクリロニトリルモノマーと、エポキシ基非含有(メタ)アクリル酸エステルモノマーとを共重合させたものである。
エポキシ基含有(メタ)アクリル酸エステルモノマーは、エポキシ樹脂用硬化剤と反応し、熱硬化性樹脂組成物の硬化物に3次元架橋構造を形成するために用いられる。3次元架橋構造が形成されると、硬化物の耐湿性及び耐熱性が向上する。例えば、熱硬化性樹脂組成物の硬化物でフレキシブルプリント配線板に接着固定された補強樹脂シートからなる補強フレキシブルプリント配線板を260℃以上でのはんだ処理(例えば、はんだリフロー処理)を行った場合でも、その接着固定部に吸湿を原因とする膨れ現象が発生することを防止することができる。
アクリロニトリルモノマーは、耐熱性を向上させるために用いられる。例えば、アクリルニトリルモノマーとしては、アクリロニトリル、メタクリロニトリルが挙げられる。アクリロニトリルモノマーは、1種単独で使用してもよいし、2種以上を併用してもよい。
エポキシ基非含有(メタ)アクリル酸エステルモノマーとしては、電子部品分野に適用されている従来のアクリル系熱硬化性接着剤で使用されているものから適宜選択して使用することができる。エポキシ基非含有(メタ)アクリル酸エステルモノマーとしては、例えば、メチルアクリレート(MA)、エチルアクリレート(EA)、n-プロピルアクリレート、n-ブチルアクリレート、i-ブチルアクリレート、n-ヘキシルアクリレート、n-オクチルアクリレート、i-オクチルアクリレート、2-エチルヘキシルアクリレート、i-ノニルアクリレート、ステアリルアクリレート、メチルメタクリレート、エチルメタクリレート、n-ブチルメタクリレート、i-ブチルメタクリレート、n-ヘキシルメタクリレート、n-オクチルメタクリレート、i-オクチルメタクリレート、2-エチルヘキシルメタクリレート、i-ノニルメタクリレート、n-ドデシルメタクリレート、i-ドデシルメタクリレート、ステアリルメタクリレート等が挙げられる。これらのエポキシ基非含有(メタ)アクリル酸エステルモノマーの中では、ブチルアクリレート、エチルアクリレートを用いるのが好ましい。これらエポキシ基非含有(メタ)アクリル酸エステルモノマーは、1種単独で使用してもよいし、2種以上を併用してもよい。
アクリル共重合体は、重量平均分子量が小さすぎると、剥離強度及び耐熱性が低下し、重量平均分子量が大きすぎると、溶液粘度が上がり塗布性が悪化する傾向がある。そこで、アクリル共重合体の重量平均分子量は、50万~70万、より好ましくは、55万~65万とするのが好ましい。
熱硬化性樹脂組成物を構成するエポキシ樹脂は、3次元網目構造を形成し、接着性を良好にするために用いられる。
熱硬化性樹脂組成物は、エポキシ樹脂の硬化剤として、有機酸ジヒドラジドを含んでいる。硬化剤として有機酸ジヒドラジドを用いることにより、常温で固体である熱硬化性樹脂組成物の常温保管性を向上させることができる。
熱硬化性樹脂組成物は、1級アミノ基及び2級アミノ基の少なくとも一方を有する液状のポリアミン又はポリアミドアミンによって、アクリル共重合体のエポキシ基部分が、部分的に架橋されている。このように、熱硬化性樹脂組成物におけるアクリル共重合体のエポキシ基を部分的に架橋することにより、熱硬化性樹脂組成物のしみ出し性を調整して、加熱加圧成形時における未反応のエポキシ樹脂等のしみ出し性を良好にすることができる。ここで、しみ出し性が良好とは、例えば、加熱加圧成形時における未反応のエポキシ樹脂のしみ出し量が少ないことをいう。1級アミノ基及び2級アミノ基の少なくとも一方を有するポリアミン又はポリアミドアミンは、エポキシ樹脂と常温で硬化する観点から、液状のものが好ましい。
本実施の形態に係る熱硬化性樹脂組成物は、アクリル共重合体と、エポキシ樹脂と、硬化剤と、1級アミノ基及び2級アミノ基の少なくとも一方を有する液状のポリアミン又はポリアミドアミンとを、常法により均一に混合することにより調整することができる。熱硬化性樹脂組成物の形態としては、例えば、ペースト、フィルム、分散液状が挙げられる。
熱硬化性接着シートは、例えば、基材フィルム(剥離基材)上に上述した熱硬化性樹脂組成物からなる熱硬化性接着層が形成されてなるものである。基材フィルムとしては、ポリエチレンテレフタレートフィルム、ポリイミドフィルム等が挙げられる。熱硬化性接着シートは、保管性や使用時のハンドリング性等の観点から、ポリエチレンテレフタレートフィルム、ポリイミドフィルム等に必要に応じてシリコーン等で剥離処理した基材フィルムに、熱硬化性樹脂組成物からなる熱硬化性接着層が10~50μmの厚さで成形されていることが好ましい。
熱硬化性接着シートは、例えば次の方法により製造することができる。熱硬化性接着シートの製造方法は、アクリル共重合体のエポキシ基部分の1~15%を、液状のポリアミン又はポリアミドアミンによって架橋させる架橋工程と、熱硬化性接着層形成用の塗料を調製する調製工程と、熱硬化性接着層を形成する熱硬化性接着層形成工程とを含む。
本実施の形態に係る熱硬化性樹脂組成物は、上述した成分以外にも、本発明の効果を損なわない範囲で、必要に応じて有機酸ジヒドラジドの溶解を促進させない金属不活性剤、消泡剤、防錆剤、分散剤等の公知の添加材が配合されていてもよい。
・アクリル共重合体
ブチルアクリレート(BA)、エチルアクリレート(EA」、アクリロニトリル(AN)、グリシジルメタクリレート(GMA)
JER828、JER1001
4,4’-ジアミノジフェニルスルホン(DDS)、7,11-オクタデカジエン-1,18-ジカルボヒドラジド(UDH)
トリエチレンテトラミン及びその変性物の混合物
ニポール1072J
表1に示すモノマーからなるアクリル共重合体を用意した。有機溶剤に溶解したアクリル共重合体と、トリエチレンテトラミン及びその変性物の混合物とを、表1の組成になるように計りとり、攪拌機で混合しながら2時間反応させ、アクリル共重合体のエポキシ基部分をトリエチレンテトラミン及びその変性物の混合物によって部分的に架橋させた。混合後、エポキシ樹脂、硬化剤を所定量投入し、表1の組成となる熱硬化性接着層形成用塗料(接着剤溶液)を作製した。なお、比較例1では、トリエチレンテトラミン及びその変性物の混合物を混合しなかった。
得られた熱硬化性接着層形成用塗料を、剥離処理が施されたポリエチレンテレフタレートフィルムに塗布し、50~130℃の乾燥炉中で乾燥し、35μm厚の熱硬化性接着層を形成することにより、熱硬化性接着シートを作製した。
しみ出し性の評価は、次のようにして行った。図1Aに示すように、35μmにフィルム化した熱硬化性接着層1の表面に、軽剥離タイプの剥離フィルム(以下、「軽面側フィルム」という)2と、重剥離タイプの剥離フィルム(以下、「重面側フィルム」という)3とが設けられたダブルセパレート(両面剥離)タイプに加工した接着シート4を準備した。図1Bに示すように、接着シート4の軽面側フィルム2を剥し、図1Cに示すように175μmのポリイミドフィルム5に、100℃、1m/min、5kg/cmの条件でラミネートした。図1D及び図1Eに示すように、ポリイミドフィルム5にラミネートした接着シート4を、図2に示すビク型6を用いて、接着シート4をポリイミドフィルム5側から打抜いた。図1Fに示すように、ポリイミドフィルム5側から打抜いた接着シート4のサンプルの重面側フィルム3を剥がし、銅7とポリイミドフィルム8とからなるCCL(copper clad laminate)9をラミネートした。これにより、試験片10を作製した。試験片10は、図1G及び図3に示すように、短辺が50mm、長辺が100mmであり、試験片10の短手方向(厚さ方向)に、直径10mm、直径5mm及び直径3mmのしみ出し性の測定用の穴が形成されている。
剥離強度の評価は、次のようにして行った。得られた直後の熱硬化性接着性シートを所定の大きさの短冊(5cm×10cm)にカットし、その熱硬化性接着層を、175μmのポリイミドフィルム(175AH、カネカ(株)製)に80℃に設定したラミネータで仮貼りした後、基材フィルムを取り除いて熱硬化性接着層を露出させた。露出した熱硬化性接着層に対し、同じ大きさの50μm厚のポリイミドフィルム(200H、デュポン社製)を上から重ね合わせ、170℃で2.0MPaの圧力で60秒間加熱加圧した後、140℃のオーブン中に60分間保持した。
吸湿リフロー半田耐熱性試験は、次のようにして行った。短冊(2cm×2cm)にカットした熱硬化性接着性シートの熱硬化性接着層を、175μm厚のポリイミドフィルム(アピカル175AH、カネカ(株)製)に80℃に設定したラミネータで仮貼りした。熱硬化性接着性シートから剥離基材を取り除いて熱硬化性接着層を露出させた。露出した熱硬化性接着層に対し、同じ大きさの厚さ50μm厚のポリイミドフィルム(カプトン200H、デュポン社製)を上から重ね合わせ、170℃で2.0MPaの圧力で60秒間加熱加圧した後、140℃のオーブン中で60分間保持した。加熱硬化した試験片を40℃、90RHの湿熱オーブンで96時間放置した。
常温保管性は、次のようにして評価した。表1において、常温保管性が「○」とは、剥離強度の値が初期と比較して低下率が30%以内、且つ、吸湿半田リフロー性の変化がないことを示す。また、常温保管性が「×」とは、剥離強度の値が初期と比較して低下率が30%以上、又は、吸湿半田リフロー性が変化した場合を示す。
Claims (8)
- エポキシ基含有(メタ)アクリル酸エステルモノマーを含むアクリル共重合体と、エポキシ樹脂と、該エポキシ樹脂用の硬化剤とを含有する熱硬化性樹脂組成物であって、
1級アミノ基及び2級アミノ基の少なくとも一方を有する液状のポリアミン又はポリアミドアミンにより、前記アクリル共重合体のエポキシ基部分が、部分的に架橋されている熱硬化性樹脂組成物。 - 前記アクリル共重合体のエポキシ基部分の1%以上が、前記1級アミノ基及び2級アミノ基の少なくとも一方を有する液状のポリアミン又はポリアミドアミンによって架橋されている請求項1記載の熱硬化性樹脂組成物。
- 前記アクリル共重合体のエポキシ基部分の3~12%が、前記1級アミノ基及び2級アミノ基の少なくとも一方を有する液状のポリアミン又はポリアミドアミンによって架橋されている請求項2記載の熱硬化性樹脂組成物。
- 前記硬化剤は、有機酸ジヒドラジドを含む請求項3記載の熱硬化性樹脂組成物。
- 前記エポキシ基含有(メタ)アクリル酸エステルモノマーの配合比率は、前記アクリル共重合体の3~15質量%である請求項4記載の熱硬化性樹脂組成物。
- 前記有機酸ジヒドラジドは、平均粒径が0.5~15μmであり、均一に分散されている請求項4又は5記載の熱硬化性樹脂組成物。
- 基材フィルム上に、請求項1乃至6のうちいずれか1項記載の熱硬化性樹脂組成物からなる熱硬化性接着層が形成されている熱硬化性接着シート。
- 有機溶媒に溶解したエポキシ基含有(メタ)アクリル酸エステルモノマーを含むアクリル共重合体と、1級アミノ基及び2級アミノ基の少なくとも一方を有する液状のポリアミン又はポリアミドアミンとを混合し、該アクリル共重合体のエポキシ基部分を、該液状のポリアミン又はポリアミドアミンによって部分的に架橋させる架橋工程と、
前記エポキシ基部分が架橋されたアクリル共重合体を含む有機溶媒に、エポキシ樹脂と、有機酸ジヒドラジドを含む該エポキシ樹脂用の硬化剤とを溶解させることにより、熱硬化性接着層形成用塗料を調製する調製工程と、
前記熱硬化性接着層形成用塗料を基材フィルム上に塗布し、乾燥することにより、熱硬化性接着層を形成する熱硬化性接着層形成工程と
を有する熱硬化性接着シートの製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/824,616 US9365754B2 (en) | 2010-12-01 | 2011-11-06 | Heat-curing resin composition, heat-curing adhesive sheet, and method for producing heat-curing adhesive sheet |
CN201180052892.4A CN103180359B (zh) | 2010-12-01 | 2011-11-16 | 热固性树脂组合物、热固性粘接片材及热固性粘接片材的制造方法 |
KR1020137010950A KR101890444B1 (ko) | 2010-12-01 | 2011-11-16 | 열경화성 수지 조성물, 열경화성 접착 시트 및 열경화성 접착 시트의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-268081 | 2010-12-01 | ||
JP2010268081A JP5770995B2 (ja) | 2010-12-01 | 2010-12-01 | 熱硬化性樹脂組成物、熱硬化性接着シート及び熱硬化性接着シートの製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012073703A1 true WO2012073703A1 (ja) | 2012-06-07 |
Family
ID=46171649
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/076454 WO2012073703A1 (ja) | 2010-12-01 | 2011-11-16 | 熱硬化性樹脂組成物、熱硬化性接着シート及び熱硬化性接着シートの製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9365754B2 (ja) |
JP (1) | JP5770995B2 (ja) |
KR (1) | KR101890444B1 (ja) |
CN (1) | CN103180359B (ja) |
TW (1) | TWI519586B (ja) |
WO (1) | WO2012073703A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016076356A1 (ja) * | 2014-11-12 | 2016-05-19 | デクセリアルズ株式会社 | 熱硬化性接着組成物、及び熱硬化性接着シート |
JP2019056031A (ja) * | 2017-09-20 | 2019-04-11 | シンフォニアテクノロジー株式会社 | 樹脂組成物 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5842736B2 (ja) * | 2012-06-06 | 2016-01-13 | デクセリアルズ株式会社 | 熱硬化性樹脂組成物、熱硬化性接着シート及び熱硬化性接着シートの製造方法 |
ES2688532T3 (es) | 2013-01-18 | 2018-11-05 | Basf Se | Composiciones de recubrimiento a base de dispersión acrílica |
US9680143B2 (en) * | 2013-10-18 | 2017-06-13 | Miltec Uv International Llc | Polymer-bound ceramic particle battery separator coating |
JP6073263B2 (ja) * | 2014-03-31 | 2017-02-01 | 日東電工株式会社 | ダイシングシート付きダイボンドフィルム、及び、半導体装置の製造方法 |
JP6517032B2 (ja) * | 2015-02-06 | 2019-05-22 | デクセリアルズ株式会社 | 熱硬化性接着組成物、及び熱硬化性接着シート |
JP6721325B2 (ja) * | 2015-12-14 | 2020-07-15 | デクセリアルズ株式会社 | 熱硬化性接着シート、及び半導体装置の製造方法 |
CN107417889A (zh) * | 2017-06-27 | 2017-12-01 | 山东诚汇双达药业有限公司 | 邻苯二甲酰肼在制备自流平地坪漆中的应用 |
US11193016B2 (en) * | 2018-05-09 | 2021-12-07 | 3M Innovative Properties Company | Curable and cured compositions |
JP7298342B2 (ja) * | 2019-07-01 | 2023-06-27 | 東レ株式会社 | 電子機器用接着剤組成物 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6154653A (ja) * | 1984-08-25 | 1986-03-18 | Kyocera Corp | 電子部品用封止体およびその製造方法 |
JPH01113476A (ja) * | 1987-10-28 | 1989-05-02 | Nissan Motor Co Ltd | エポキシ系接着剤組成物 |
JPH02202973A (ja) * | 1989-02-02 | 1990-08-13 | Sumitomo Electric Ind Ltd | フレキシブル印刷配線板用接着剤組成物 |
JPH04332722A (ja) * | 1991-05-07 | 1992-11-19 | Toagosei Chem Ind Co Ltd | エポキシ樹脂組成物 |
JPH11181398A (ja) * | 1997-12-25 | 1999-07-06 | Hitachi Chem Co Ltd | 接着剤組成物、この接着剤組成物を用いてなる多層プリント配線板及び多層プリント配線板の製造方法 |
JP2000159860A (ja) * | 1998-11-27 | 2000-06-13 | Hitachi Chem Co Ltd | 耐熱性樹脂組成物 |
JP2001220565A (ja) * | 1999-06-18 | 2001-08-14 | Hitachi Chem Co Ltd | 接着剤、接着部材、接着部材を備えた半導体搭載用配線基板及びこれを用いた半導体装置 |
JP2008111106A (ja) * | 2006-10-06 | 2008-05-15 | Hitachi Chem Co Ltd | 電子部品封止用液状樹脂組成物及びこれを用いた電子部品装置 |
JP2010126642A (ja) * | 2008-11-27 | 2010-06-10 | Shin-Etsu Chemical Co Ltd | 常温保存可能な接着剤組成物、ならびにそれを用いた接着シートおよびカバーレイフィルム |
JP2011079959A (ja) * | 2009-10-07 | 2011-04-21 | Sony Chemical & Information Device Corp | 熱硬化性接着組成物、熱硬化性接着シート、その製造方法及び補強フレキシブルプリント配線板 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6285941A (ja) | 1985-10-11 | 1987-04-20 | ニツカン工業株式会社 | カバ−レイフイルム |
JPS6385941A (ja) | 1986-09-30 | 1988-04-16 | Toshiba Corp | 故障診断回路 |
JPH0793497B2 (ja) | 1991-06-19 | 1995-10-09 | 信越化学工業株式会社 | ボンディングシート |
JPH093021A (ja) * | 1995-06-16 | 1997-01-07 | Otsuka Chem Co Ltd | 微粉状ヒドラジド化合物 |
US5952446A (en) * | 1998-02-09 | 1999-09-14 | Molex Incorporated | Elastomeric epoxy composition |
US6673441B1 (en) | 1999-06-18 | 2004-01-06 | Hitachi Chemical Company, Ltd. | Adhesive, adhesive member, interconnecting substrate for semiconductor mounting having adhesive member, and semiconductor device containing the same |
US6448301B1 (en) * | 2000-09-08 | 2002-09-10 | 3M Innovative Properties Company | Crosslinkable polymeric compositions and use thereof |
MY143209A (en) * | 2006-10-06 | 2011-03-31 | Hitachi Chemical Co Ltd | Liquid resin composition for electronic part sealing, and electronic part apparatus utilizing the same |
-
2010
- 2010-12-01 JP JP2010268081A patent/JP5770995B2/ja active Active
-
2011
- 2011-11-06 US US13/824,616 patent/US9365754B2/en active Active
- 2011-11-16 KR KR1020137010950A patent/KR101890444B1/ko active IP Right Grant
- 2011-11-16 CN CN201180052892.4A patent/CN103180359B/zh active Active
- 2011-11-16 WO PCT/JP2011/076454 patent/WO2012073703A1/ja active Application Filing
- 2011-11-23 TW TW100142819A patent/TWI519586B/zh active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6154653A (ja) * | 1984-08-25 | 1986-03-18 | Kyocera Corp | 電子部品用封止体およびその製造方法 |
JPH01113476A (ja) * | 1987-10-28 | 1989-05-02 | Nissan Motor Co Ltd | エポキシ系接着剤組成物 |
JPH02202973A (ja) * | 1989-02-02 | 1990-08-13 | Sumitomo Electric Ind Ltd | フレキシブル印刷配線板用接着剤組成物 |
JPH04332722A (ja) * | 1991-05-07 | 1992-11-19 | Toagosei Chem Ind Co Ltd | エポキシ樹脂組成物 |
JPH11181398A (ja) * | 1997-12-25 | 1999-07-06 | Hitachi Chem Co Ltd | 接着剤組成物、この接着剤組成物を用いてなる多層プリント配線板及び多層プリント配線板の製造方法 |
JP2000159860A (ja) * | 1998-11-27 | 2000-06-13 | Hitachi Chem Co Ltd | 耐熱性樹脂組成物 |
JP2001220565A (ja) * | 1999-06-18 | 2001-08-14 | Hitachi Chem Co Ltd | 接着剤、接着部材、接着部材を備えた半導体搭載用配線基板及びこれを用いた半導体装置 |
JP2008111106A (ja) * | 2006-10-06 | 2008-05-15 | Hitachi Chem Co Ltd | 電子部品封止用液状樹脂組成物及びこれを用いた電子部品装置 |
JP2010126642A (ja) * | 2008-11-27 | 2010-06-10 | Shin-Etsu Chemical Co Ltd | 常温保存可能な接着剤組成物、ならびにそれを用いた接着シートおよびカバーレイフィルム |
JP2011079959A (ja) * | 2009-10-07 | 2011-04-21 | Sony Chemical & Information Device Corp | 熱硬化性接着組成物、熱硬化性接着シート、その製造方法及び補強フレキシブルプリント配線板 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016076356A1 (ja) * | 2014-11-12 | 2016-05-19 | デクセリアルズ株式会社 | 熱硬化性接着組成物、及び熱硬化性接着シート |
JP2016094511A (ja) * | 2014-11-12 | 2016-05-26 | デクセリアルズ株式会社 | 熱硬化性接着組成物、及び熱硬化性接着シート |
US10011745B2 (en) | 2014-11-12 | 2018-07-03 | Dexerials Corporation | Thermosetting adhesive composition and thermosetting adhesive sheet |
JP2019056031A (ja) * | 2017-09-20 | 2019-04-11 | シンフォニアテクノロジー株式会社 | 樹脂組成物 |
JP7004899B2 (ja) | 2017-09-20 | 2022-01-21 | シンフォニアテクノロジー株式会社 | 樹脂組成物 |
Also Published As
Publication number | Publication date |
---|---|
TWI519586B (zh) | 2016-02-01 |
CN103180359B (zh) | 2016-08-31 |
KR20140003414A (ko) | 2014-01-09 |
CN103180359A (zh) | 2013-06-26 |
JP2012116957A (ja) | 2012-06-21 |
KR101890444B1 (ko) | 2018-08-21 |
US20130183520A1 (en) | 2013-07-18 |
JP5770995B2 (ja) | 2015-08-26 |
US9365754B2 (en) | 2016-06-14 |
TW201237090A (en) | 2012-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5770995B2 (ja) | 熱硬化性樹脂組成物、熱硬化性接着シート及び熱硬化性接着シートの製造方法 | |
JP5842736B2 (ja) | 熱硬化性樹脂組成物、熱硬化性接着シート及び熱硬化性接着シートの製造方法 | |
KR101702694B1 (ko) | 열경화성 접착 조성물, 열경화성 접착 시트, 그 제조 방법 및 보강 플렉시블 인쇄 배선판 | |
JP6542526B2 (ja) | 熱硬化性接着組成物、及び熱硬化性接着シート | |
WO2016076096A1 (ja) | 熱硬化性接着組成物 | |
JP5820108B2 (ja) | 熱硬化性接着シート及び熱硬化性接着シートの製造方法 | |
JP2012219154A (ja) | 熱硬化性接着組成物、熱硬化性接着シート、その製造方法及び補強フレキシブルプリント配線板 | |
TWI417357B (zh) | 粘接片用樹脂組成物及利用此組成物之撓性印刷電路板用之粘接片 | |
JP2016145287A (ja) | 熱硬化性接着組成物、及び熱硬化性接着シート | |
JP5978782B2 (ja) | 熱硬化性接着組成物、熱硬化性接着シート及び補強フレキシブルプリント配線板 | |
JP6553427B2 (ja) | 補強フレキシブルプリント配線板の製造方法、熱硬化性樹脂組成物及び熱硬化性接着シート | |
JP2017179064A (ja) | 電子部品用接着剤 | |
KR20100084031A (ko) | 플렉시블 프린트 배선판용 열경화성 접착제 조성물 | |
JP2003013031A (ja) | 熱反応性接着剤組成物および熱反応性接着フィルム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11844802 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13824616 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20137010950 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11844802 Country of ref document: EP Kind code of ref document: A1 |