WO2013157551A1 - Composition durcissable contenant du silicium et produit durci de celle-ci - Google Patents

Composition durcissable contenant du silicium et produit durci de celle-ci Download PDF

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WO2013157551A1
WO2013157551A1 PCT/JP2013/061313 JP2013061313W WO2013157551A1 WO 2013157551 A1 WO2013157551 A1 WO 2013157551A1 JP 2013061313 W JP2013061313 W JP 2013061313W WO 2013157551 A1 WO2013157551 A1 WO 2013157551A1
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group
carbon atoms
silicon
curable composition
containing curable
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PCT/JP2013/061313
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English (en)
Japanese (ja)
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雅子 斎藤
憲司 原
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株式会社Adeka
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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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • 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
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen

Definitions

  • the present invention relates to a silicon-containing curable composition and a cured product obtained by curing the same.
  • the silicon-containing curable composition and the cured product thereof are useful for electrical / electronic component materials such as sealants, interlayer insulating films, passivation films, protective films, adhesives, and the like.
  • an object of the present invention is to provide a silicon-containing curable composition that is excellent in crack resistance, hardness, and outgas resistance and is useful for electrical / electronic materials and the like.
  • the present inventor has focused on the structure and prepolymer of a specific silicon-containing compound, and has completed the present invention.
  • the present invention is obtained by hydrosilylation reaction of one or more cyclic siloxane compounds ( ⁇ ) represented by the following formula (1) and one or more compounds ( ⁇ ) selected from the following ⁇ Group G>.
  • a silicon-containing curable composition comprising a prepolymer (A) containing two or more Si—H groups in one molecule and a linear siloxane (B) represented by the following formula (2): It provides things.
  • R 1 , R 2 and R 3 each independently represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms.
  • a number of R 1 s may be the same or different, and b number of R 2 s and b number of R 3 s may be the same or different.
  • b represents a number from 0 to 8.
  • R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an epoxy group having 2 to 10 carbon atoms) Or a phenyl group substituted with an alkenyl group having 2 to 10 carbon atoms, an acrylic group having 3 to 10 carbon atoms, or an epoxy group having 2 to 10 carbon atoms, and R 4 , Any two of R 5 and R 6 are substituents having a carbon-carbon double bond, and m and n are each independently 1 or 2.
  • R 13 and R 32 are each independently a group having an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an epoxy group having 2 to 10 carbon atoms. Or a trimethylsilyl group, wherein R 14 , R 15 , R 16 , R 17 , R 21 , R 25 , R 29 , R 30 and R 31 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 18 , R 19 and R 20 each independently represent a phenyl group
  • R 22 , R 23 and R 24 each independently represents an alkenyl group having 2 to 6 carbon atoms
  • R 26 , R 27 and R 28 each independently represents a group having an epoxy group having 2 to 10 carbon atoms, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 and Z 8.
  • R 16 and R 17 may be the same or different, q R 18 and R 19 , r R 20 and R 21 , v R 22 and R 23 , w R 24 and R 25 , x R 26 and R 27 , y R 28 and R 29 may be the same or different, and p, q, r, v, w, x and y are each independently 0 to Represents the number of 3000, p + q + r + v + w + x + y ⁇
  • the cured product of the present invention is obtained by curing the silicon-containing curable composition.
  • the cured product is excellent in crack resistance, hardness and outgas resistance, and is an insulating film of electrical / electronic materials, a passivation film, a sealing material, a low dielectric constant material, an adhesive material, a heat resistant material, a transparent material, etc.
  • a silicon-containing curable composition useful for the above can be provided.
  • the silicon-containing curable composition of the present invention comprises one or more cyclic siloxane compounds ( ⁇ ) represented by the formula (1) (hereinafter also referred to as ( ⁇ ) component) and a compound ( ⁇ ) selected from ⁇ Group G>.
  • Prepolymer (A) (hereinafter referred to as component (A)) obtained by hydrosilylation reaction of one or more of (hereinafter also referred to as ( ⁇ ) component) containing two or more Si—H groups in one molecule
  • a linear siloxane represented by the formula (2) hereinafter also referred to as the component (B)).
  • the prepolymer as the component (A) is obtained by hydrosilylation reaction of one or more selected from the following ( ⁇ ) component and ( ⁇ ) component, and two or more Si—H in one molecule thereof. It has a group.
  • the component ( ⁇ ) is a cyclic siloxane compound represented by the above formula (1) and containing two or more Si—H groups in one molecule.
  • R 1 is preferably a methyl group from the viewpoint of industrial availability
  • R 2 and R 3 are preferably a methyl group or a phenyl group.
  • a is preferably 4 to 6 from the viewpoint of ease of production
  • b is preferably 0 to 1 from the viewpoint of the crosslinking density of the curing reaction.
  • the ratio of the methyl group to the phenyl group is preferably 4: 1 to 1: 4 in the entire substituents of R 1 to R 3 .
  • component ( ⁇ ) examples include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9, Examples include 11-hexamethylcyclohexasiloxane, and 1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of industrial availability and an appropriate number of Si-H functional groups.
  • the component ( ⁇ ) may be used alone or in combination of two or more.
  • the component ( ⁇ ) is a compound containing two or more carbon-carbon double bonds having reactivity with the Si—H group in one molecule, and is selected from the above ⁇ Group G>.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R 4 , R 5 and R 6 in the formula in ⁇ Group G> include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, Examples include tributyl, isobutyl, amyl, isoamyl, tertiary amyl, cyclopentyl, hexyl, 2-methylpentyl, 3-methylpentyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl and the like.
  • the alkyl group substituted by the halogen atom, the cyano group, etc. may be sufficient, and chloromethyl, trifluoromethyl, cyanomethyl, dichloroethyl etc. are mentioned as such an alkyl group.
  • alkenyl group having 2 to 10 carbon atoms examples include vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3- Examples include pentenyl, 4-hexenyl, cyclohexenyl, heptenyl, octenyl, decenyl and the like.
  • alkenyloxy group having 2 to 10 carbon atoms examples include groups in which the alkenyl group is interrupted by an oxygen atom, such as vinyloxy, propenyloxy, and 3-butenyloxy.
  • acrylic group having 3 to 10 carbon atoms examples include acryloyloxymethyl, methacryloylmethyl, acryloyloxyethyl, methacryloylethyl, acryloyloxypropyl, methacryloylpropyl, acryloyloxybutyl, methacryloylbutyl, acryloyloxyhexyl and methacryloyl Examples include hexyl and (meth) acryloyloxy.
  • Examples of the group having an epoxy group having 2 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an alkyl group interrupted with an oxygen atom, a tetrahydrobenzyl group, and a dicyclopentadienyl group, which are substituted with an epoxy group. , Norbornyl group, norborneneyl group and the like.
  • Specific examples include epoxy, epoxy methyl, epoxy ethyl, epoxy propyl, epoxy cyclohexyl, glycidyl, cyclohexane epoxy methyl, norbornane epoxy methyl, epoxy cyclohexene, epoxy tetrahydrobenzyl, epoxy methyl tetrahydrobenzyl, epoxy dicyclopentadienyl, and the like. It is done.
  • the compound selected from the above ⁇ Group G> which is the component ( ⁇ ) is a compound represented by G-1, when n is 1, o-divinylbenzene, m-divinylbenzene, p-divinyl.
  • Benzene when n is 2, 1,2,3-trivinylbenzene, 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene and the like can be mentioned.
  • the compound represented by G-2 is divinylcyclohexane when m is 1, and may be any of 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, and 1,4-divinylcyclohexane.
  • the compound selected from the above ⁇ Group G> may be one in which a functional group other than a vinyl group (for example, an alkyl group such as a methyl group) is bonded to a ring, or a mixture thereof.
  • a functional group other than a vinyl group for example, an alkyl group such as a methyl group
  • the component ( ⁇ ) one type of compound may be used alone, or two or more types of compounds may be used in combination.
  • the number of carbon-carbon double bonds having reactivity with the Si—H group is the crosslinking density. From the viewpoint, it is preferably 2 to 3 per molecule. Preferably, it is selected from the group consisting of G-1, G-2, G-3 and G-7 out of the ⁇ G group>.
  • R 4 , R 5 and R 6 are alkenyl groups having 2 to 10 carbon atoms.
  • the prepolymer of the component (A) can be obtained by hydrosilylation reaction of the components ( ⁇ ) and ( ⁇ ).
  • the reaction ratio of the component ( ⁇ ) and the component ( ⁇ ) is not particularly limited as long as two or more Si—H groups are contained in one molecule of the prepolymer of the component (A).
  • the concentration of the Si—H group contained in the prepolymer of the component (A) is preferably 0.0001 mmol / g to 100 mmol / g, more preferably 0.01 mmol / g to 20 mmol, from the viewpoint of curability and storage stability. / G is preferred.
  • the weight average molecular weight of the prepolymer (A) is preferably 500 to 500,000, more preferably 1,000 to 300,000 from the viewpoint of heat resistance and handling properties.
  • the weight average molecular weight of the prepolymer may be measured using GPC, and may be determined by polystyrene conversion.
  • the hydrosilylation reaction between the ( ⁇ ) component and the ( ⁇ ) component can be performed using a platinum-based catalyst.
  • a platinum-based catalyst a known catalyst containing one or more metals of platinum, palladium and rhodium that promote the hydrosilylation reaction can be used.
  • Platinum-based catalysts used as catalysts for these hydrosilylation reactions include platinum-carbonyl vinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum-cyclovinylmethylsiloxane complexes, platinum-octylaldehyde complexes, etc.
  • compounds containing platinum-based metals such as palladium and rhodium can be used instead of platinum.
  • platinum-divinyltetramethyldisiloxane complex Karsttedt catalyst
  • platinum-carbonylvinylmethyl complex Ossko catalyst
  • Wilkinson catalyst containing the above platinum-based metal such as chlorotristriphenylphosphine rhodium (I) is also included in the platinum-based catalyst in the present invention.
  • the amount of the platinum-based catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass of the total amount of the components ( ⁇ ) and ( ⁇ ) from the viewpoint of reactivity.
  • the hydrosilylation reaction conditions for the ( ⁇ ) component and the ( ⁇ ) component are not particularly limited, and may be carried out under the conventionally known conditions using the above-mentioned catalyst.
  • a conventionally known solvent such as toluene, hexane, MIBK (methyl isobutyl ketone), cyclopentanone, PGMEA (propylene glycol monomethyl ether acetate) or the like may be used during the reaction.
  • the prepolymer of the component (A) is a compound containing a carbon-carbon double bond having reactivity with the component ( ⁇ ), which is a cyclic siloxane compound having a Si—H group, and a Si—H group ( ( ⁇ ) component is a prepolymer obtained by hydrosilylation reaction.
  • component ( ⁇ ) component constituting component (A) is cyclic, and ( ⁇ ) component is converted to ( ⁇ ) component.
  • the component ( ⁇ ) constituting the component (A) since the component ( ⁇ ) constituting the component (A) has a cyclic structure, the curing shrinkage is small, and therefore a cured product having excellent adhesion can be obtained. Furthermore, since the silicon content can be increased while the viscosity is low, a curable composition having excellent heat resistance can be obtained.
  • the component (B) is a linear siloxane compound represented by the formula (2).
  • R 13 and R 32 are each independently an alkenyl group having 2 to 6 carbon atoms or an epoxy group having 2 to 10 carbon atoms.
  • the general formula (2) is (Wherein R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 30 , R 31 and R 32 , Z 1 , Z 2 and Z 3 , and p and q are The same).
  • R 13 and R 32 are preferably a vinyl group, a group having an epoxy group having 2 to 10 carbon atoms, or a methyl group from the viewpoint of reactivity.
  • R 13 14 , R 15 , R 16 , R 17 , R 21 , R 25 , R 29 , R 30 and R 31 are preferably a methyl group or an ethyl group
  • R 22 , R 23 and R 24 are a vinyl group or a 2-propenyl group. Is preferred.
  • Specific examples of the preferred component (B) include linear siloxane compounds represented by the following formulas (3) to (12).
  • those represented by the formulas (4), (6), and (8) prevent yellowing of the cured product, impart toughness to the cured product, and provide resin strength. Can be adjusted, which is preferable.
  • the component (B) is a linear siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si—H groups in one molecule.
  • the component (B) is a linear siloxane compound.
  • the silicon-containing curable composition of the present invention preferably contains 0.05 to 30 parts by mass of the linear siloxane copolymer of the component (B) with respect to 100 parts by mass of the component (A). From the viewpoint of the effect of improving the adhesion, the content is more preferably 0.1 to 25 parts by mass, and further preferably 3 to 20 parts by mass.
  • the component (A) is preferably 5 to 90% by mass
  • the component (B) is preferably 0.05 to 50% by mass, and more preferably 5 to 40% by mass.
  • the content of the component (A) and the component (B) may be appropriately determined in consideration of the ratio of Si—H groups and carbon-carbon double bonds reactive with the Si—H groups.
  • the equivalent ratio (the former / the latter) of the Si—H group contained in the component and the carbon-carbon double bond having reactivity with the Si—H group contained in the component (B) is preferably from 0.1 to 10, 1.0 to 5.0 is particularly preferable. If the equivalent ratio is less than 0.1, the silicon-containing curable composition is not cured, and if it is greater than 10, the silicon-containing curable composition may be colored.
  • a cyclic siloxane compound represented by the following formula (13) can be further added to improve close adhesion.
  • R 41 , R 42 and R 43 each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and c R 41 s may be the same or different. , D R 42 and d R 43 may be the same or different from each other, c represents a number of 2 to 10, and d represents a number of 0 to 8.
  • R 41 , R 42 and R 43 are preferably a methyl group or a phenyl group from the viewpoint of industrial availability.
  • c is preferably 2 to 4 from the viewpoint of crosslinking density, and d is preferably 1 to 3 from the viewpoint of viscosity.
  • cyclic siloxane compounds represented by the following formulas (14) to (16) are preferable from the viewpoints of heat resistance and adhesion.
  • a compound having a cyanuric acid structure can be further added to improve close adhesion.
  • the compound having a cyanuric acid structure include isocyanuric acid, triallyl cyanuric acid, 1,3,5-triglycidyl isocyanuric acid, triallyl isocyanuric acid, 1-allyl-3,5-diglycidyl isocyanuric acid, 1 , 3-diallyl-5-glycidyl isocyanuric acid, tris (2-hydroxyethyl) isocyanuric acid, tris (2,3-dihydroxypropyl) isocyanuric acid, tris (2,3-epoxypropyl) isocyanuric acid, the following compound no.
  • the silicon-containing curable composition of the present invention can also contain a filler as an optional component.
  • a filler include colloidal silica, silica gel, minerals such as mica and montmorillonite; metal oxides such as titanium oxide, iron oxide, aluminum oxide, magnesium oxide, zinc oxide, and beryllium oxide; Ceramics such as silicon nitride, aluminum nitride, boron nitride, silicon carbide or the like modified by organic modification treatment; metal hydroxide such as aluminum hydroxide or magnesium hydroxide or organic modification treatment of these Metal carbonates such as calcium carbonate, magnesium carbonate, barium carbonate or the like modified by organic modification treatment, etc .; Pigments such as metal borate and carbon black; Carbon fiber, graphite, whisker , Kaolin, talc, glass fiber , Glass beads, the layered clay mineral, clay, potassium titanate, silicon carbide,
  • the particle size of these fillers is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less from the viewpoint of heat resistance.
  • the content of the filler in the silicon-containing curable composition of the present invention is preferably 90% by mass or less and more preferably 50% by mass or less from the viewpoint of heat resistance and handling.
  • the content of the filler in the silicon-containing curable composition of the present invention is preferably 5% by mass or more in order to sufficiently exhibit the effect of addition.
  • the silicon-containing curable composition of the present invention may further contain a free radical scavenger as an optional component.
  • the free radical scavenger in this case may be any antioxidant substance such as an antioxidant or a stabilizer, such as triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl). ) Propionate], dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-paracresol (DBPC) and the like.
  • the content of the free radical scavenger in the silicon-containing curable composition of the present invention is preferably 0.1 to 50% by mass from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling. 1 to 30% by mass is more preferable.
  • the silicon-containing curable composition of the present invention has good fluidity at room temperature (25 ° C.) and excellent handling properties.
  • the viscosity measured with an E-type viscometer at room temperature (25 ° C.) is preferably 1 Pa ⁇ S or less, and more preferably 0.1 Pa ⁇ S or less.
  • the silicon-containing curable composition of the present invention includes other known components as optional components other than the above-described cyclic siloxane compound, filler and compound having a cyanuric acid structure, as long as the target performance of the present invention is not impaired.
  • Various resins, additives and the like can also be blended.
  • the amount of the optional component other than the filler and the compound having a cyanuric acid structure is not particularly limited, but in order not to impair the effects of the present invention, in the silicon-containing curable composition of the present invention. It is preferable to set it as the range of 5 mass% or less.
  • various organic functional groups can be bonded to any one or more of the component (A) and the component (B) to further impart functions.
  • a highly functional composite material in which the silicon-containing curable composition of the present invention or a cured product thereof is used as a matrix and other useful compounds are dispersed therein can also be produced.
  • various resins that can be arbitrarily blended include polyimide resins, polyether resins such as polyethylene glycol and polypropylene glycol, polyurethane resins, epoxy resins, phenol resins, polyester resins, melamine resins, polyamide resins, polyphenylene sulfide resins, and the like.
  • additives that can be optionally added include ultraviolet absorbers, antistatic agents, and antioxidants.
  • the silicon-containing curable composition of the present invention can be cured by heating and can be a cured product.
  • This curing reaction may be performed by any method, such as a method of mixing the compounding components of the silicon-containing curable composition of the present invention immediately before use, a method of mixing all in advance and curing by heating or the like when performing the curing reaction. You may go.
  • the heating temperature for curing is preferably 35 to 350 ° C, more preferably 50 to 250 ° C.
  • the curing time is preferably 0.01 to 10 hours, more preferably 0.05 to 6 hours.
  • the cured product obtained from the silicon-containing curable composition of the present invention is particularly excellent in heat resistance and adhesion.
  • a cured product having a temperature causing a weight loss of 5% by mass of the cured product is preferably 400 ° C. or higher, more preferably 500 ° C. or higher.
  • cured material with few crack generation is suitably obtained from the silicon-containing curable composition of this invention.
  • the silicon-containing curable composition of the present invention has an Si—H group as the component (A) and Si— as the component (B) due to the effect of the platinum-based catalyst that is a catalyst for the hydrosilylation reaction contained in the component (A).
  • the curing reaction by the reaction of a carbon-carbon double bond (for example, Si—CH ⁇ CH 2 group) having reactivity with the H group proceeds rapidly.
  • the silicon-containing curable composition of the present invention can be photocured by adding a photoreactive catalyst.
  • a photoreactive monomer or resin may be further blended, and any one or more of each component in the silicon-containing curable composition may have a photoreactive group.
  • silicon-containing curable composition of the present invention weather resistance, hardness, stain resistance, flame resistance, moisture resistance, gas barrier properties, flexibility, elongation and strength, electrical insulation, low dielectric constant properties
  • a material having excellent mechanical properties such as mechanical properties, optical properties, electrical properties, and the like can be obtained.
  • the silicon-containing curable composition of the present invention can be used as a curable composition in which the cured product has excellent physical properties such as heat resistance, light resistance, adhesion, transparency, and colorability.
  • the silicon-containing curable composition and cured product of the present invention are used for sealing materials such as display materials, optical materials, recording materials, semiconductors, and solar cells in the electric and electronic materials field; high-voltage insulating materials; -It can be used as various materials for moisture prevention purposes.
  • film forming methods such as spin casting, potting, dipping, etc. can be appropriately applied.
  • Applications include prototype molds for plastic parts, coating materials, interlayer insulating films, passivation films, prepregs, insulating packings, heat-shrinkable rubber tubes, O-rings, sealants and protective materials for display devices, optical waveguides, Optical fiber protective materials, optical lenses, adhesives for optical equipment, high heat resistant adhesives, elastic adhesives, adhesives, die bonding agents, high heat dissipation materials, high heat resistant sealing materials, solar cell / fuel cell components, batteries It can also be applied to solid electrolytes, insulation coating materials, photosensitive drums for copying machines, and gas separation membranes. It can also be applied to concrete protective materials, linings, soil injecting agents, sealing agents, regenerator materials, glass coatings, foams, paints, etc.
  • sealing materials in the civil engineering and building materials fields, and in the medical materials field, tubes, It can be applied to sealing materials, coating materials, sealing materials for sterilization equipment, contact lenses, oxygen-enriched membranes, etc. It can be applied to other films, gaskets, casting materials, various molding materials, sealants for rust prevention and waterproofing of glass with a mesh, automobile parts, various machine parts, and the like.
  • Component (A) Synthesis of Prepolymer A-1 1,3,5,7-tetramethylcyclotetrasiloxane 100 parts, trivinylcyclohexane 100 parts, toluene 60 parts and a platinum-carbonylvinylmethyl complex ( Ossko catalyst) 0.0005 part was added and refluxed for 5 hours with stirring. The solvent was distilled off from the reaction solution at 70 ° C. under reduced pressure to obtain a prepolymer A-1 as component (A).
  • the solvent was distilled off under reduced pressure at 70 ° C., and the linear siloxane compound B as component (B) represented by the above formula (4) -3 was obtained.
  • the epoxy equivalent (molecular weight per number of epoxy groups) determined by potentiometric titration based on JIS standard K7236 is 3000 g / mmol. Met.
  • Examples 1 to 15 and Comparative Examples 1 to 4 Preparation and evaluation of silicon-containing curable compositions
  • A Prepolymers and (B) linear siloxane compounds having the compositions shown in [Table 1] to [Table 2], A cyclic siloxane compound as an optional component was blended to obtain a silicon-containing curable composition.
  • the resulting silicon-containing curable composition was tested for crack resistance, hardness, and outgas by the following methods.
  • the silicon-containing curable composition was added to a container having an inner diameter of 20 mm up to a height of 1 mm, and the effect was performed by heating at 200 ° C. for 1 hour.
  • a cured product of the silicon-containing curable composition was taken out of the container and used as a test piece.
  • ⁇ Crack resistance> A test piece cured in a cylindrical shape having a diameter of 20 mm and a height of 1 mm was tested in a 200 ° C. forced air constant temperature bath. ⁇ : Cracks did not occur at 200 ° C. for 100 hours. ⁇ : Cracks occurred at 200 ° C. for 100 hours. ⁇ : Crack resistance was evaluated as cracks occurred at 200 ° C. for 40 hours. ⁇ Hardness> The measurement was performed according to JIS K6253 or ASTM D2240. In any evaluation, since it exceeded 90 with the Shore A durometer, the measurement was performed with the Shore D durometer, and the scale value of the Shore D durometer was used as the hardness evaluation.

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Abstract

L'invention concerne une composition durcissable contenant du silicium qui a une bonne résistance à la fissuration, une dureté élevée et d'excellentes propriétés de libération de gaz et est utile comme matières électriques et électroniques et ainsi de suite. La composition durcissable contenant du silicium est caractérisée en ce qu'elle comprend : un prépolymère (A) ayant au moins deux groupes Si-H par molécule, ledit prépolymère (A) étant obtenu par hydrosilylation d'au moins une sorte d'un composé siloxane cyclique (α) représenté par la formule (1) et d'au moins une sorte d'un composé (β) choisi dans le <groupe G> ; et un composé siloxane linéaire (B) représenté par la formule (2).
PCT/JP2013/061313 2012-04-18 2013-04-16 Composition durcissable contenant du silicium et produit durci de celle-ci WO2013157551A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015012141A1 (fr) * 2013-07-24 2015-01-29 株式会社Adeka Composition de résine durcissable
CN110760067A (zh) * 2019-10-22 2020-02-07 广东万木新材料科技有限公司 一种有机硅低聚物及其合成方法与应用

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014205823A (ja) * 2013-03-21 2014-10-30 株式会社Adeka ケイ素含有硬化性組成物
JP6265468B2 (ja) * 2013-10-24 2018-01-24 株式会社Adeka プレポリマー及び硬化性樹脂組成物
JP6060876B2 (ja) * 2013-11-11 2017-01-18 信越化学工業株式会社 低温硬化性コーティング剤組成物及びその硬化物品
KR101728308B1 (ko) * 2015-09-14 2017-04-19 기초과학연구원 비전이금속 촉매법 수소규소화 반응을 이용한 규소 고분자 제조방법
JP6599240B2 (ja) * 2016-01-06 2019-10-30 住友精化株式会社 シルフェニレン化合物、その製造方法、該シルフェニレン化合物を含有するエポキシ樹脂組成物、及び該組成物の用途

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089733A (ja) * 2003-08-14 2005-04-07 Shin Etsu Chem Co Ltd 硬化性シリコーン樹脂組成物
JP2006232970A (ja) * 2005-02-24 2006-09-07 Adeka Corp ケイ素含有硬化性組成物及びその硬化物
JP2010018719A (ja) * 2008-07-11 2010-01-28 Adeka Corp ケイ素含有硬化性組成物
JP2010100758A (ja) * 2008-10-24 2010-05-06 Adeka Corp ケイ素含有硬化性組成物
JP2011088982A (ja) * 2009-10-21 2011-05-06 Adeka Corp ケイ素含有硬化性組成物及びその硬化物
WO2013021717A1 (fr) * 2011-08-10 2013-02-14 株式会社Adeka Composition durcissable contenant du silicium et produit durci à base de celle-ci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089733A (ja) * 2003-08-14 2005-04-07 Shin Etsu Chem Co Ltd 硬化性シリコーン樹脂組成物
JP2006232970A (ja) * 2005-02-24 2006-09-07 Adeka Corp ケイ素含有硬化性組成物及びその硬化物
JP2010018719A (ja) * 2008-07-11 2010-01-28 Adeka Corp ケイ素含有硬化性組成物
JP2010100758A (ja) * 2008-10-24 2010-05-06 Adeka Corp ケイ素含有硬化性組成物
JP2011088982A (ja) * 2009-10-21 2011-05-06 Adeka Corp ケイ素含有硬化性組成物及びその硬化物
WO2013021717A1 (fr) * 2011-08-10 2013-02-14 株式会社Adeka Composition durcissable contenant du silicium et produit durci à base de celle-ci

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015012141A1 (fr) * 2013-07-24 2015-01-29 株式会社Adeka Composition de résine durcissable
CN110760067A (zh) * 2019-10-22 2020-02-07 广东万木新材料科技有限公司 一种有机硅低聚物及其合成方法与应用
CN110760067B (zh) * 2019-10-22 2021-09-24 广东万木新材料科技有限公司 一种有机硅低聚物及其合成方法与应用

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