WO1990002768A1 - Preparation a base de silicone-resine epoxyde et adhesif conducteur obtenu a partir de cette preparation - Google Patents

Preparation a base de silicone-resine epoxyde et adhesif conducteur obtenu a partir de cette preparation Download PDF

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Publication number
WO1990002768A1
WO1990002768A1 PCT/JP1989/000905 JP8900905W WO9002768A1 WO 1990002768 A1 WO1990002768 A1 WO 1990002768A1 JP 8900905 W JP8900905 W JP 8900905W WO 9002768 A1 WO9002768 A1 WO 9002768A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
silicone
silicone epoxy
resin composition
conductive adhesive
Prior art date
Application number
PCT/JP1989/000905
Other languages
English (en)
Japanese (ja)
Inventor
Akio Ohura
Masakazu Hirose
Tetsuya Watanabe
Original Assignee
Toray Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP30652288A external-priority patent/JPH02151624A/ja
Application filed by Toray Industries, Inc. filed Critical Toray Industries, Inc.
Publication of WO1990002768A1 publication Critical patent/WO1990002768A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances

Definitions

  • the present invention has excellent mutual solubility with an epoxy resin and a curing agent, has a faster curing property, and has a good balance of flexibility, moisture resistance and heat resistance when cured.
  • the present invention is directed to a silicone epoxy resin composition that can satisfy the requirements.
  • the present invention relates to a low-stress conductive adhesive using such a silicone epoxy resin composition.
  • epoxy resins are widely used because of their excellent electrical, mechanical and adhesive properties.
  • An object of the present invention is to increase the ratio of the silicone ethoxy resin in the resin to an extremely high level without impairing the mutual solubility with the epoxy resin or the curing agent and the rapid curing property.
  • An object of the present invention is to provide a silicone eboxy resin composition capable of simultaneously satisfying all of the flexibility, moisture resistance, and heat resistance as a compound.
  • Another object of the present invention is to provide a low-stress conductive adhesive using the silicone resin composition.
  • a silicone epoxy resin composition comprising a silicone epoxy resin represented by the following general formula (I) and a curing agent.
  • (I) (Wherein, H 1, R 2, R 3 are an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a phenyl group having 1 to 4 carbon atoms, and R 5 and R 6 are a hydrogen atom or a methoxy group.
  • R 6 may be the same as or different from each other. / N represents 1 to L 0. )
  • n represents a number of 1 to 100, but when n is large, it becomes a polymer compound and is usually obtained as a mixture. In that case, n is the average value Is done. In the present invention, n is preferably 1 to 10.
  • R 1, R 2, R 3, and R 4 include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, a phenyl group, and a phenyl group.
  • silicone epoxy resin used in the present invention include those represented by the following formula.
  • the method for producing the silicone epoxy resin used in the present invention is not particularly limited.
  • aryl glycidyl ether in the presence of chloroplatinic acid or an olefin complex of chloroplatinic acid as a catalyst, aryl glycidyl ether
  • it can be obtained by a method of hydrosilylating a siloxane compound having hydrogen bonded to eugenol glycidyl ether and silicon.
  • a hydroxyl group is glycidylated after a hydrosilylation reaction of an arylphenol or eugenol with a siloxane compound.
  • the curing agent used in the present invention is not particularly limited as long as it is a usual epoxy resin curing agent.
  • curing agent of the present invention among the conventionally known curing accelerators, those having an action as a curing agent are also included as the curing agent of the present invention.
  • Specific examples thereof include, for example, 2—methylimidazole, 2-ethyl-4-methylimidazole, 2—phenyl-4-methylinomidazole, and 2—phenyl-14-methyl.
  • '1 5 Or an acid addition salt thereof such as hydroxybenzoic acid or dihydroxybenzoic acid;
  • N, N ' Dimethyl piperazine, 2, 4, 6 — Tris (dimethylaminometyl) phenol, 1, 8 — diazabicyclo (5, 4, 0) pentacene 7, 4 — Dimethyla
  • amide compounds such as minopyridine and acid addition salts thereof such as hydroxybenzoic acid and di-t-hydroxybenzoic acid.
  • the curing agent added to the silicone epoxy resin composition of the present invention is usually 0.1 to 200 parts by weight based on 100 parts by weight of the silicone epoxy resin.
  • the silicone epoxy resin composition of the present invention may optionally contain other generally used curing accelerators.
  • curing accelerators include triphenylphosphine, tricyclohexylphosphine, and bis (diphenyl), in addition to the compounds that can be included as the curing agent described above.
  • Metals such as phosphine compounds such as phenyl phosphino) methane and tris (2,6-dimethoxyphenyl) phosphine, aluminum acetyl acetate, and cobalt acetyl acetate Acetyl acetate toners.
  • the above curing accelerator is added to the silicone epoxy resin composition of the present invention, it is usually added in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the silicone epoxy resin. .
  • silicone epoxy resins used in the present invention are Since it has excellent mutual solubility with other epoxy resins, it can be used by mixing with other epoxy resins as needed.
  • the other epoxy resin is not particularly limited as long as it is a compound having one or more epoxy groups per molecule.
  • bisphenol A diglycidyl ether bisphenol F diglycidyl Sidyl ether, bisphenol C diglycidyl ether, 3,3'-diarylbisphenol A diglycidyl ether, phenol novolak polyglycidyl ether, cresol novolak polyglycidyl ether, phloroglucinol Triglycidyl ether, resorcinol diglycidyl ether, tetraglycidyl diaminominodiphenyl methane, triglycidyl methaminophenol, 1,5-naphthalene diol diglycidyl ether, 1, 6-naphtha diol diol diglycidyl ether, 3, 3 ', 5, 5'Tetramethyl-4,4'-biphenol diglycidyl ether, 4,4'-biphenol digly
  • the conductive filler added to the silicone epoxy resin composition is silver, gold, copper, or nickel.
  • Conductive metals such as Kel, inorganic insulators such as alumina and glass, or organic polymer compounds such as polyethylene and polystyrene coated with a conductive material, carbon, graphite And the like.
  • the shape of these conductive fillers is arbitrary, and may be selected, for example, from powder, sphere, flake, fiber, etc. as necessary.
  • the conductive filler to be added to the conductive adhesive is used in an amount of 50 to 1,500 parts by weight based on 100 parts by weight of the silicone epoxy resin of the present invention. I like it.
  • a filler, a rubber component, a diluent, a colorant, a pigment, a flame retardant, and the like are added to the silicone epoxy resin composition of the present invention as needed.
  • filler examples include, in addition to the conductive filler added when used as the conductive adhesive, aluminum oxide, magnesium oxide, aluminum hydroxide, and carbonate. Calcium, magnesium carbonate, silica, quartz, porolin, myriki, asbestos, antimony trioxide, etc. No.
  • rubber components include, but are not limited to, silicone rubber, carboxyl group-containing butadiene nitrile rubber, styrene-butadiene block copolymer, and styrene-isoprene block copolymer. Coalescence, natural rubber, and the like.
  • diluent examples include, in addition to the above-mentioned low-viscosity reactive compound having one epoxy group in one molecule, ethyl cellulose, sorbitol, sorbitol acetate, sorbitol acetate, ethyl carbitol, butyl carbitol, ethyl carbitol Examples include bitol acetate, acetyl lactone, 4-butanol lactone, propylene carbonate, xylene, toluene, ethyl acetate, methylethyl ketone, and methyl isobutyl ketone.
  • colorants, pigments and flame retardants include titanium dioxide, graphite carbon black, iron black, molybdenum red, navy blue, cadmium yellow, triphenyl phosphate and decabromo.
  • examples include diphenyl ether and hexabromobenzene.
  • a method for mixing the silicone epoxy resin composition of the present invention a method of melting at a high temperature if necessary, or a Banbury mixer, a kneader at a temperature of about room temperature to about 150 ° C. A mixing method using a roll, a single-screw or twin-screw extruder is applied. Further, a conductive adhesive containing the silicone epoxy resin composition of the present invention is prepared. In this case, a predetermined amount of the silicone epoxy resin, curing agent, curing accelerator, diluent and other additives are weighed and then mixed. A method of kneading with a kneader or a kneader is used.
  • Silicone epoxy resin A j Silicone epoxy resins B, C, and D were each synthesized using the raw materials shown in Table 1 in accordance with the above operation. Table 1 shows the raw materials used and the corresponding reaction products. 5 one
  • the silicone epoxy resins A to C synthesized in Reference Example 1 were cured with 4,4'-diaminodiphenylsulfonic acid (DDS) and 4,4'-diaminodiphenylmethane (DDS).
  • DDM 4,4'-diaminodiphenylsulfonic acid
  • DDS 4,4'-diaminodiphenylmethane
  • DDM phenolic novolak resin
  • Me-HHPA 4-methylcyclohexane 1,2-dibonic anhydride
  • SA Salicylic acid
  • silicone epoxy resin composition was obtained by blending at the ratio shown in Table 2. However, in Examples 4 and 5, triphenylphosphine (TPP) was used in combination as a curing accelerator.
  • TPP triphenylphosphine
  • Mutual solubility Shows the mutual solubility between the silicone epoxy resin and other epoxy resins or curing agents when each composition in Table 2 is dissolved at 100 to 150 ° C. Judgment was made by visual observation. ⁇ indicates that no separation occurred during dissolution, and X indicates that separation occurred in two layers.
  • Shore hardness The hardness of the cured product (short D or short A) was measured according to ASTM D224. 8 Aging mass
  • the wet area of the adhesive, the adhesive strength, the volume resistance value, the warpage of the chip, and the mechanical properties (tensile properties) of the cured product were measured by the following methods. Table 3 shows the results. The curing was performed using a strong wind circulation oven and the curing conditions were set at 150 and 1 hour. Glue area of adhesive: Lead frame made of silver-plated copper
  • Conductive adhesive 2 is precisely weighed on the top, and silicon chip (10 oval angle, 0.5 female thickness) And pressed for 2 seconds under a load of 100 g (operated at room temperature).
  • the chip was peeled off and the spread area of the adhesive on the lead frame was measured.
  • the area was the area where the silver powder was present.
  • Bonding strength Lead frame made of silver-plated copper
  • the resistance of a 1 X 0.1 nun (thickness) conductor was measured, and the volume resistance was determined.
  • Chip warpage 10 ram square silicon chip (thickness 0.5
  • a No. 2 test piece was prepared, and its elastic modulus, breaking elongation, and breaking strength were measured at a tensile speed of 1 mm / min and room temperature.
  • the curing properties 20 of the silicone epoxy resin A obtained in Reference Example 1 were examined by gel time measurement, and for comparison, bis (3-glycidoxypropyl) tetramethyldisiloxae was used.
  • Table 4 shows the measurement results of the composition and the gel time using the compound (B2405, the same compound as in Comparative Example 4). The gel time was measured according to the hot plate method (JIS 599).
  • the silicone epoxy resin composition of the present invention has mutual solubility with other epoxy resins and curing agents, fast curability, and flexibility when formed into a cured product, moisture resistance, and heat resistance. Both can be used for adhesives and sealants in the electric and electronic fields where both are required. In particular, it is effective in places where bonding of different kinds of objects having different coefficients of thermal expansion and absorption of vibration are required, and more specifically, conductive adhesive containing the silicone epoxy resin composition of the present invention.
  • the agent can be used for applications such as bonding large ICs and LSIs to lead frames and assembling crystal units.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La préparation ci-décrite comprend une résine silicone-résine époxyde selon la formule générale (I) et un agent de polymérisation. Cette préparation présente une excellente compatibilité avec une résine époxyde ou un agent de polymérisation ainsi qu'une grande vitesse de polymérisation; une fois polymérisée, elle présente des caractéristiques équilibrées de flexibilité, de résistance à l'humidité et à la chaleur. On peut l'utiliser efficacement pour souder et sceller des composants électriques ou électroniques nécessitant de faibles contraintes. Par exemple, un adhésif conducteur obtenu par l'adjonction d'une charge conductrice à cette préparation présente d'excellentes caractéristiques, indiquées pour la fixation de circuits intégrés ou de circuits à forte intégration de grandes dimensions, ou pour l'assemblage d'oscillateurs à quartz.
PCT/JP1989/000905 1988-09-02 1989-09-01 Preparation a base de silicone-resine epoxyde et adhesif conducteur obtenu a partir de cette preparation WO1990002768A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP22155588 1988-09-02
JP63/221555 1988-09-02
JP30652288A JPH02151624A (ja) 1988-12-02 1988-12-02 新規なシリコーンエポキシ化合物
JP63/306522 1988-12-02

Publications (1)

Publication Number Publication Date
WO1990002768A1 true WO1990002768A1 (fr) 1990-03-22

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Application Number Title Priority Date Filing Date
PCT/JP1989/000905 WO1990002768A1 (fr) 1988-09-02 1989-09-01 Preparation a base de silicone-resine epoxyde et adhesif conducteur obtenu a partir de cette preparation

Country Status (2)

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EP (1) EP0388473A4 (fr)
WO (1) WO1990002768A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6465550B1 (en) 2000-08-08 2002-10-15 Dow Corning Corporation Silicone composition and electrically conductive, cured silicone product
CN102286261A (zh) * 2011-07-14 2011-12-21 上海景涵实业有限公司 Led用氨基固化体系环氧功能化有机硅导电胶粘剂
US20130059081A1 (en) * 2011-09-01 2013-03-07 Industrial Technology Research Institute Method of fabricating flexible substrate structure
CN109400638A (zh) * 2018-09-30 2019-03-01 浙江大学 一种丁香酚基环氧树脂及其制备工艺和应用
CN109456463A (zh) * 2018-09-30 2019-03-12 江苏和和新材料股份有限公司 一种酚羟基环氧化工艺
CN109467677A (zh) * 2018-09-30 2019-03-15 江苏和和新材料股份有限公司 一种生物基环氧树脂组合物及其在制备环氧树脂胶膜中的应用
CN109503644A (zh) * 2018-09-30 2019-03-22 江苏和和新材料股份有限公司 一种生物基环氧树脂的制备工艺、产品及应用
CN113046020A (zh) * 2021-03-29 2021-06-29 浙江元通线缆制造有限公司 一种防水胶及其制备方法与在水密电缆上的应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5227093A (en) * 1991-11-29 1993-07-13 Dow Corning Corporation Curable organosiloxane compositions yielding electrically conductive materials
US5700581A (en) * 1996-06-26 1997-12-23 International Business Machines Corporation Solvent-free epoxy based adhesives for semiconductor chip attachment and process
US7312261B2 (en) * 2004-05-11 2007-12-25 International Business Machines Corporation Thermal interface adhesive and rework

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JPS59172571A (ja) * 1983-03-18 1984-09-29 Hitachi Chem Co Ltd 導電性接着剤

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DE1251034B (de) * 1967-09-28 Deutsche Akademie der Wissenschaften zu Berlin Berlin Adlershof Verfah ren zur Herstelung von siliciumhaltigen Epoxydverbmdungen
DE1793228A1 (de) * 1967-08-23 1972-02-03 Koslikow Wadim Lwowitsch Verfahren zur Herstellung von 1,3-bis-hydroxyalkyl(aryl)-tetraorganodisiloxanen
JPS59212250A (ja) * 1983-05-17 1984-12-01 三菱電機株式会社 サ−マルインシユレ−タの製造方法
US4954580A (en) * 1987-12-01 1990-09-04 Ciba-Geigy Corporation Epoxysiloxanes

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JPS59172571A (ja) * 1983-03-18 1984-09-29 Hitachi Chem Co Ltd 導電性接着剤

Non-Patent Citations (1)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6465550B1 (en) 2000-08-08 2002-10-15 Dow Corning Corporation Silicone composition and electrically conductive, cured silicone product
CN102286261A (zh) * 2011-07-14 2011-12-21 上海景涵实业有限公司 Led用氨基固化体系环氧功能化有机硅导电胶粘剂
US20130059081A1 (en) * 2011-09-01 2013-03-07 Industrial Technology Research Institute Method of fabricating flexible substrate structure
CN109400638A (zh) * 2018-09-30 2019-03-01 浙江大学 一种丁香酚基环氧树脂及其制备工艺和应用
CN109456463A (zh) * 2018-09-30 2019-03-12 江苏和和新材料股份有限公司 一种酚羟基环氧化工艺
CN109467677A (zh) * 2018-09-30 2019-03-15 江苏和和新材料股份有限公司 一种生物基环氧树脂组合物及其在制备环氧树脂胶膜中的应用
CN109503644A (zh) * 2018-09-30 2019-03-22 江苏和和新材料股份有限公司 一种生物基环氧树脂的制备工艺、产品及应用
CN113046020A (zh) * 2021-03-29 2021-06-29 浙江元通线缆制造有限公司 一种防水胶及其制备方法与在水密电缆上的应用
CN113046020B (zh) * 2021-03-29 2022-12-09 浙江元通线缆制造有限公司 一种防水胶及其制备方法与在水密电缆上的应用

Also Published As

Publication number Publication date
EP0388473A4 (en) 1992-03-04
EP0388473A1 (fr) 1990-09-26

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