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WO2025126719A1 - Composition de silicone durcissable contenant un composé organopolysiloxane amino-modifié contenant un diyne - Google Patents

Composition de silicone durcissable contenant un composé organopolysiloxane amino-modifié contenant un diyne Download PDF

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Publication number
WO2025126719A1
WO2025126719A1 PCT/JP2024/039182 JP2024039182W WO2025126719A1 WO 2025126719 A1 WO2025126719 A1 WO 2025126719A1 JP 2024039182 W JP2024039182 W JP 2024039182W WO 2025126719 A1 WO2025126719 A1 WO 2025126719A1
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Prior art keywords
curable silicone
silicone composition
group
hydrocarbon group
substituted
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Japanese (ja)
Inventor
勇志 多畑
啓太 北沢
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from 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
    • C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen

Definitions

  • the present invention relates to a curable silicone composition containing an amino-modified organopolysiloxane compound that has a diyne in the molecule and is curable, a cured product thereof, and a method for producing the composition.
  • Silicone elastomers are elastic materials based on silicone resin, and because silicone itself has excellent heat and chemical resistance, they are widely used as coating agents, sealants, and encapsulants for semiconductor elements.
  • Curable silicone compositions are liquid silicone compositions when used, and can be cured into silicone elastomers when triggered by heat, light, or moisture in the air.
  • Specific curing forms include addition reactions using radicals, addition reactions by hydrosilylation, and condensation reactions.
  • Addition reactions by radicals generally use peroxides, and often require high temperatures to generate initiating species. In addition, they can have poor surface curing properties because they are inhibited by oxygen.
  • Addition reactions by hydrosilylation can be cured at room temperature or by heating, depending on the catalyst and reaction control agent used. However, inadequate curing can occur if curing inhibitors such as sulfur, phosphorus, nitrogen compounds, water, or organic metal salts are mixed in or come into contact with the material. Condensation reactions can be cured at room temperature using moisture in the air, but they generate gas during curing, causing volumetric shrinkage, and they have poor deep curing properties.
  • curable silicone compositions are used in the vicinity of electrical and electronic components and semiconductor elements, but an increasing number of electrical and electronic components are heat-sensitive and cannot be exposed to high temperatures during mounting, so there is a demand for curable silicone compositions that can be cured under mild conditions of 100°C or less.
  • the [2+2+2] cycloaddition reaction is a reaction that forms an aromatic ring from three triple bonds, and is a very useful reaction that does not produce any by-product gas during the reaction, but there have been few reports of its application to organopolysiloxane compounds or their cured products.
  • this reaction has a high activation barrier, and when a catalyst that is stable at room temperature is used, a high temperature of 100°C or higher is required to proceed with the reaction.
  • Non-Patent Documents 1-3 to proceed with the reaction under mild conditions below 100°C, a highly active catalyst must be used, but such catalysts require preparation in advance or are deactivated under normal humidity conditions, making it difficult to use as a composition or store at room temperature or humidity for long periods of time.
  • the present invention aims to provide a curable silicone composition capable of undergoing a [2+2+2] cycloaddition reaction under particularly mild conditions, as well as a silicone cured product produced from the composition.
  • the present invention provides a curable silicone composition, comprising: (A) an organopolysiloxane compound having a substituent represented by the following general formula (1) in the molecule: 100 parts by mass, (wherein R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, R 2 is independently a substituted or unsubstituted divalent hydrocarbon group, and R 3 is a divalent linking group); and (B) an effective amount of a metal compound capable of catalyzing a [2+2+2] cycloaddition reaction,
  • the present invention provides a curable silicone composition comprising:
  • the curable silicone composition of the present invention allows the [2+2+2] cycloaddition reaction to proceed under mild conditions, and the composition can be cured to obtain a silicone cured product.
  • R2 in the general formula (1) above is preferably a methylene group, and R1 in the general formula (1) above is also preferably a hydrogen atom.
  • the organopolysiloxane compound (A) is easy to synthesize.
  • the component (A) is preferably an organopolysiloxane compound having, on average, two or more substituents represented by the general formula (1) per molecule.
  • Such component (A) has an average of four or more ethynylene groups per molecule that contribute to the [2+2+2] cycloaddition and are linked to each other by nitrogen atoms, allowing the [2+2+2] cycloaddition reaction to proceed more smoothly.
  • component (A) it is preferable to further contain (C) at least one inorganic or organic filler in an amount of 0.1 to 5,000 parts by mass per 100 parts by mass of component (A).
  • Such component (C) can impart various properties to the curable silicone composition of the present invention, such as thermal conductivity, heat resistance, reinforcing properties, electrical conductivity, and design properties, and can also provide a homogeneous composition that is not too viscous and therefore easy to handle.
  • the component (C) is a filler made of one or more materials selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, carbon allotropes, resins, dyes, and pigments.
  • the present invention also provides a silicone cured product obtained by curing the above-mentioned curable silicone composition.
  • the silicone cured product of the present invention is an elastic material, and since the silicone itself has excellent heat resistance and chemical resistance, it is useful as a silicone elastomer used as a coating agent, a sealant, or an encapsulant for semiconductor elements.
  • the present invention also provides a method for producing a curable silicone composition, comprising the steps of: (A) an organopolysiloxane compound having a substituent represented by the following general formula (1) in the molecule: 100 parts by mass, (wherein R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, R 2 is independently a substituted or unsubstituted divalent hydrocarbon group, and R 3 is a divalent linking group); and (B) an effective amount of a metal compound capable of catalyzing a [2+2+2] cycloaddition reaction,
  • the present invention provides a method for producing a curable silicone composition, comprising mixing:
  • the method for producing the curable silicone composition of the present invention allows the silicone composition to be produced easily and efficiently.
  • an organopolysiloxane compound by introducing a specific structure into an organopolysiloxane compound, it is possible to provide an organopolysiloxane compound and a silane compound that are useful for [2+2+2] cycloaddition reactions.
  • a silicone composition that can be cured under mild conditions of 100°C or less. By having such curing performance, it is possible to cure even when using parts that are sensitive to heat and cannot be exposed to high temperatures during mounting, and it is highly useful as a material used in the periphery of electric and electronic parts and semiconductor elements.
  • the silicone cured product obtained by curing the composition is an elastic material, and since the silicone itself has excellent heat resistance and chemical resistance, it is useful as a silicone elastomer used as a coating agent, a sealant, a sealant for semiconductor elements, etc. Furthermore, according to the method for producing a curable silicone composition of the present invention, the above composition can be produced easily and efficiently.
  • the present invention provides a curable silicone composition
  • the curable silicone composition is characterized by comprising:
  • the present invention relates to an amino-modified organopolysiloxane compound that has a diyne in the molecule and is curable under mild conditions, for example at 100°C or less, via a [2+2+2] cycloaddition reaction, a curable silicone composition that contains a metal catalyst that can catalyze the [2+2+2] cycloaddition reaction, a silicone cured product, and a method for producing such a composition.
  • the organopolysiloxane compound that is component (A) of the present invention is an organopolysiloxane compound having a substituent in the molecule represented by the following general formula (1):
  • Component (A) is a compound that contains a diyne having two carbon-carbon triple bonds, and this diyne contributes to [2+2+2] cycloaddition.
  • R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom
  • R 2 is independently a substituted or unsubstituted divalent hydrocarbon group
  • R 3 is a divalent linking group.
  • R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom.
  • the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, octyl, and dodecyl; aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, and tolyl; aralkyl groups such as benzyl and 2-phenylethyl; and chloromethyl and 3,3,3-trifluoropropyl groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, and bromine. From the viewpoint of ease of synthesis, etc., a methyl group, an ethyl group, a
  • R2 is independently a substituted or unsubstituted divalent hydrocarbon group.
  • R2 may be the substituent represented by general formula (1) itself (in this case, a dendritic structure is formed via a tertiary nitrogen atom).
  • Specific examples of the divalent hydrocarbon group include alkylene groups such as methylene, ethylene, ethylidene, propylene, trimethylene, propylidene, and isopropylidene, but from the viewpoint of ease of synthesis, methylene and ethylene groups are preferred, and methylene is particularly preferred.
  • R 3 is a divalent linking group.
  • the divalent linking group is not particularly limited, and examples thereof include linear, branched, or ring-containing aliphatic hydrocarbon groups or aromatic hydrocarbon groups.
  • the number of carbon atoms in the aliphatic/aromatic hydrocarbon group can be, for example, 1 to 20.
  • the aliphatic hydrocarbon group or aromatic hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
  • a part of the carbon atoms or hydrogen atoms constituting the hydrocarbon group may be substituted with a bond such as an ether bond, an ester bond, a carbonyl bond, a carbonate bond, a carbamate bond, an amino bond, a urethane bond, or a urea bond.
  • a linear aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group having an amino bond is preferred, and a linear aliphatic hydrocarbon group is particularly preferred.
  • the number of carbon atoms in the linear aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 3.
  • substituents include: In the above structural formula, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
  • the (A) component preferably contains one or more of the substituents shown in the above formula (1) in one molecule, and more preferably contains two or more.
  • Such (A) component has at least two, and more preferably four or more, ethynylene groups that contribute to the [2+2+2] cycloaddition reaction, which are linked to each other by nitrogen atoms, making the synthesis easy and allowing the [2+2+2] cycloaddition reaction to proceed smoothly.
  • the component (A) is preferably an organopolysiloxane compound having, on average, two or more substituents represented by the general formula (1) in each molecule.
  • "having two or more on average in each molecule” means that if the compound of component (A) is one type, it has two or more of the above-mentioned substituents in the molecule, and if it is two or more types, the sum of the number of the above-mentioned substituents in each molecule and the molar fraction of each molecule is two or more.
  • the component (A) is a compound containing the substituent shown in formula (1)
  • its molecular structure is not particularly limited, and examples include a linear structure, a branched structure, a partially branched structure, and a linear structure having a cyclic structure.
  • the main chain is composed of repeated diorganosiloxane units and has a linear structure in which both ends of the molecular chain are blocked with triorganosiloxy groups.
  • the organopolysiloxane having the linear structure may have a partially branched structure or a cyclic structure.
  • the substituent shown in formula (1) may be possessed by the triorganosiloxy group at the molecular chain end, or may be possessed by the partially branched or cyclic structure.
  • the (A) component preferably has an average molecular weight of 150 to 500,000 g/mol, and particularly preferably 250 to 150,000 g/mol.
  • the average molecular weight here means the sum of the products of the molecular weights and the molar fractions of each compound, that is, the number average molecular weight.
  • the average molecular weight can be measured by GPC (gel permeation chromatography) using tetrahydrofuran as an eluent and polystyrene as a standard substance.
  • the kinetic viscosity of the component (A) at 25°C is preferably in the range of 1 to 500,000 mm2 /s, and more preferably 5 to 300,000 mm2 /s.
  • the kinetic viscosity is 10 to 100,000 mm2 /s, the cured product obtained from the composition has superior strength, fluidity, and workability.
  • the kinetic viscosity is a value measured with an Ostwald viscometer at 25°C.
  • the component (A) preferably has an amine value of 0.1 to 2000 mg KOH/g.
  • the amine value is the number of milligrams of potassium hydroxide (KOH: 56.11) equivalent to the acid required to neutralize 1 g of sample.
  • the organopolysiloxane compound of the present invention that satisfies the above requirements is, for example, an organopolysiloxane compound represented by the following general formula (2):
  • R 4 's are each independently an unsubstituted or substituted monovalent hydrocarbon group, with the proviso that at least one R 4 is a substituent represented by the above formula (1), and a+b+c+d is a number of 0 or more.
  • a 2
  • b is preferably 2 or more and 800 or less
  • a or b is a number of 0 or more, b is preferably 2 or more and 800 or less, and c or d is 1 or more.
  • the organopolysiloxane compound include those represented by the following formula:
  • at least one R 4 in the terminal M unit (R 4 3 SiO 1/2 ) or D unit (R 4 2 SiO 2/2 ) in the general formula (2) is preferably a substituent represented by the formula (1).
  • e or f or g is a number of 0 or more, and e or f is more preferably a number of 2 or more and 800 or less. g is more preferably a number of 0 or more and 800 or less. h or i is 0 or more, and h+i is preferably a number of 20 or more and 800 or less.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • Metal-catalyzed [2+2+2] cycloaddition reactions are a direct and atom-efficient method for the synthesis of fused polycyclic aromatic compounds.
  • the component (A) of the present invention is a metal compound capable of catalyzing a [2+2+2] cycloaddition reaction, in which the [2+2+2] cycloaddition reaction proceeds.
  • the component (A) of the present invention has the advantage that the reaction proceeds under relatively mild conditions, particularly at 100°C or below.
  • the above-mentioned (A) component can be used alone or in combination of two or more types.
  • Component (B) is a metal compound capable of catalyzing a [2+2+2] cycloaddition reaction, and is blended as a catalyst for curing the curable silicone composition of the present invention.
  • “capable of catalyzing a [2+2+2] cycloaddition reaction” means having catalytic activity for a [2+2+2] cycloaddition reaction.
  • the metal compound is also simply referred to as a "catalyst" or "metal catalyst”.
  • the metal compound of the component (B) can be composed of a central metal atom, a ligand, and a counter ion.
  • central metal atoms include those in Groups 4 to 12. Specifically, examples include those in Group 4 (titanium (Ti), zirconium (Zr), hafnium (Hf)), Group 5 (vanadium (V), niobium (Nb), tantalum (Ta)), Group 6 (chromium (Cr), molybdenum (Mo), tungsten (W)), Group 7 (manganese (Mn), rhenium (Re)), Group 8 (iron (Fe), ruthenium (Ru), osmium (Os)), Group 9 (cobalt (Co), rhodium (Rh), iridium (Ir)), Group 10 (nickel (Ni), palladium (Pd), platinum (Pt)), and Group 12 (zinc (Zn)).
  • the central metal atom may be one type or two or more types, and when there are two or more types, they may all be the same metal or a combination of different metals.
  • the ligand is not particularly limited, and examples thereof include carbonyl (CO), ammonia, water, halide ions such as F ⁇ , Cl ⁇ , Br ⁇ , and I ⁇ , anions such as cyanide ion (CN ⁇ ), PF 6 ⁇ , BF 4 ⁇ , NO 3 ⁇ , BPh 4 ⁇ , and ClO 4 ⁇ , onium cations such as ammonium, sulfonium, and phosphonium, organic phosphorus compounds such as triphenylphosphine and 1,2-bis(diphenylphosphino)ethane, cyclopentadienyl (Cp) group, pentamethylcyclopentadienyl (Cp *) group, and the like.
  • CO carbonyl
  • halide ions such as F ⁇ , Cl ⁇ , Br ⁇ , and I ⁇
  • anions such as cyanide ion (CN ⁇ ), PF
  • the ligand may be a monodentate ligand or a bidentate or higher polydentate ligand.
  • the counter ion is not particularly limited, and examples thereof include halide ions, cyanide ions, and carbonates which can also serve as ligands, anions such as PF 6 ⁇ , BF 4 ⁇ , NO 3 ⁇ , BPh 4 ⁇ , and ClO 4 ⁇ , and onium cations such as ammonium, sulfonium, and phosphonium.
  • Cl ⁇ is more preferable.
  • Preferred metal compounds capable of catalyzing the [2+2+2] cycloaddition reaction are cyclopentadienylcobalt(I) dicarbonyl, tetrakis(triphenylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), and tris(triphenylphosphine)rhodium(I) chloride.
  • the metal compound may be used after dilution, such as by dissolving or dispersing it in a solvent, as necessary.
  • a solvent any known solvent may be used, and examples of such a solvent include alcohols such as methanol, ketones such as acetone, hydrocarbon solvents such as hexane, toluene, and xylene, halogenated hydrocarbon solvents such as methylene chloride, chloroform, and 1,2-dichloroethane, esters such as ethyl acetate, and polysiloxanes such as dimethylpolysiloxane, both ends of which are capped with trimethylsilyl groups and have a kinetic viscosity of 50,000 mm 2 /s at 25° C.
  • the concentration of the metal compound in the solvent can be set as needed, for example, to 0.01 to 10% by mass, preferably 0.1 to 5% by mass, calculated as the mass of the central metal.
  • the desired composition can be prepared by adding the dilution to the mixture in an amount that is capable of catalyzing the [2+2+2] cycloaddition reaction described below.
  • the amount of the metal compound capable of catalyzing the [2+2+2] cycloaddition reaction should be an effective amount as a catalyst, that is, an effective amount required to accelerate the curing reaction and cure the curable silicone composition of the present invention.
  • the amount is preferably 0.1 to 10,000 ppm, more preferably 1 to 5,000 ppm, and even more preferably 10 to 3,000 ppm by mass converted into the central metal atom relative to the entire composition. If the amount of catalyst is equal to or greater than the lower limit, the catalytic effect is obtained, and if it is equal to or less than the upper limit, the catalytic effect is sufficient and economical.
  • the curable silicone composition of the present invention may contain an inorganic or organic filler as component (C) as necessary.
  • Component (C) can impart various properties such as thermal conductivity, heat resistance, reinforcing properties, electrical conductivity, and design properties to the curable silicone composition of the present invention, and is preferably a filler made of at least one material selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, carbon allotropes, resins, dyes, and pigments, and examples thereof include metals such as aluminum, silver, copper, and metallic silicon, metal oxides such as alumina, zinc oxide, magnesium oxide, silicon dioxide, cerium oxide, and iron oxide, metal hydroxides such as aluminum hydroxide and cerium hydroxide, metal nitrides such as aluminum nitride and boron nitride, metal carbides such as silicon carbide, diamond, graphite, and carbon nanotubes.
  • suitable materials include carbon allotropes such as graphene, tubes, and graphene; resins such as silicone resin powder; dyes such as indigo; and pigments such as red iron oxide.
  • resins such as silicone resin powder
  • dyes such as indigo
  • pigments such as red iron oxide.
  • thermal conductivity it is preferable to use aluminum, silver, alumina, zinc oxide, and aluminum nitride.
  • cerium oxide, cerium hydroxide, and iron oxide In order to impart reinforcement, it is preferable to use silicon dioxide such as hydrophobic fumed silica.
  • silicone resin powder In order to impart smoothness, it is preferable to use silicone resin powder.
  • dyes and pigments such as indigo and red iron oxide.
  • the average particle size of the filler is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and even more preferably 150 ⁇ m or less, since the composition obtained will be more uniform if it is smaller than 500 ⁇ m. It is also preferable that the average particle size is 0.01 ⁇ m or more, and particularly 0.1 ⁇ m or more.
  • the average particle size can be determined, for example, as the volume average value (or median size) in particle size distribution measurement by laser light diffraction method.
  • the shape of the filler is not particularly limited and may be spherical, irregular, acicular, plate-like, etc.
  • the amount of component (C) to be blended should be 5,000 parts by mass or less per 100 parts by mass of component (A), as this will result in a homogeneous composition that is not too viscous and is easy to handle, and is therefore recommended to be in the range of 5,000 parts by mass or less, and preferably 2,000 parts by mass or less. If component (C) is blended, it is preferable to use 0.1 parts by mass or more, and especially 1 part by mass or more.
  • the curable silicone composition of the present invention may further contain a component other than the above (A) to (C) as component (D) as necessary.
  • a non-reactive organo(poly)siloxane such as methylpolysiloxane may be contained in order to adjust the strength and viscosity of the composition.
  • a hydrolyzable organopolysiloxane, various modified silicones, or a hydrolyzable organosilane may be blended in order to improve the filling property of the filler or to impart adhesiveness to the composition.
  • a solvent may be blended in order to adjust the viscosity of the composition.
  • a conventionally known antioxidant such as 2,6-di-tert-butyl-4-methylphenol may be contained as necessary.
  • a flame retardant, a sedimentation inhibitor, a thixotropy improver, or the like may be blended as necessary.
  • the method for producing the curable silicone composition of the present invention is not particularly limited, but may be a method for producing the curable silicone composition of the present invention by a process comprising the steps of: (A) an organopolysiloxane compound having a substituent in the molecule represented by the following general formula (1); (wherein R1 is independently a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, R2 is independently a substituted or unsubstituted divalent hydrocarbon group, and R3 is a divalent linking group): 100 parts by mass, and (B) an effective amount of a metal compound capable of catalyzing a [2+2+2] cycloaddition reaction.
  • the method comprises the step of mixing together the above-mentioned components (A) and (B), and, if necessary, the component (C) and other components to prepare a curable silicone
  • the above-mentioned components (A) and (B), and optionally also component (C) and other components, are mixed using a mixer such as Awatori Rentaro (registered trademark of Thinky Corporation), Trimix, Twinmix, Planetary Mixer (all registered trademarks of mixers manufactured by Inoue Seisakusho Co., Ltd.), Ultra Mixer (registered trademarks of mixers manufactured by Mizuho Kogyo Co., Ltd.), or Hivis Dispermix (registered trademarks of mixers manufactured by Tokushu Kika Kogyo Co., Ltd.), or by hand mixing using a spatula or the like at 25°C for usually 3 minutes to 24 hours, preferably 5 minutes to 12 hours, and particularly preferably 10 minutes to 6 hours. Deaeration may also be performed during mixing.
  • a mixer such as Awatori Rentaro (registered trademark of Thinky Corporation), Trimix, Twinmix, Planetary Mixer (all registered trademarks of mixers manufactured by Inoue Seisakusho Co., Ltd.),
  • the curable silicone composition of the present invention has an absolute viscosity measured at 25°C of preferably 0.1 to 1,000 Pa ⁇ s, more preferably 1 to 700 Pa ⁇ s, and even more preferably 5 to 500 Pa ⁇ s.
  • a viscosity of 0.1 Pa ⁇ s or more improves workability, such as good shape retention.
  • a viscosity of 1,000 Pa ⁇ s or less improves workability, such as easy discharge and application.
  • the above viscosity can be obtained by adjusting the composition of each of the above-mentioned components.
  • the absolute viscosity is the value at 25°C measured using a Malcolm viscometer (rotor A at 10 rpm, shear rate 6 [1/s]).
  • JP 2015-93958 A discloses an organopolysiloxane composition containing an organopolysiloxane containing an amic acid structure having a carbon-carbon triple bond and a non-platinum catalyst that promotes a trimerization cyclization reaction, and although it is described as being heat-curable, a high temperature of 150 to 250°C is required for curing, and in addition, in order to convert the amic acid structure to a phthalimide structure, it is necessary to further heat at 250°C. Due to such high-temperature curing characteristics, there is a problem that it cannot be applied to compositions containing parts that are sensitive to heat and cannot be exposed to high temperatures during mounting.
  • the organopolysiloxane compound (A) of the curable silicone composition of the present invention does not have an amic acid structure and can provide a silicone composition that can be cured at a lower temperature, particularly at a mild condition of 100°C or less, and therefore has the advantage that it can be cured even when parts that are sensitive to heat are used.
  • the silicone cured product of the present invention is an elastic material, and since the silicone itself has excellent heat resistance and chemical resistance, it is useful as a silicone elastomer used as a coating agent, a sealant, or an encapsulant for semiconductor elements.
  • the curable silicone composition of the present invention is a liquid silicone composition during use, and curing proceeds under mild conditions in the presence of a catalyst, making it possible to produce a silicone elastomer.
  • the curing system employs a [2+2+2] cycloaddition reaction of alkynes, which uses a metal as a catalyst to form carbon-carbon bonds between multiple bonds.
  • the [2+2+2] cycloaddition reaction is a reaction that forms an aromatic ring from three triple bonds, and is a very useful reaction that does not produce any by-product gas during the reaction.
  • the present invention is the first practical example of applying this reaction to organopolysiloxane compounds and their cured products.
  • the catalyst it is possible to achieve both the desired workability and curing characteristics.
  • the composition of the present invention cures by a catalytic [2+2+2] cycloaddition reaction, and therefore, compared to conventional addition reactions using radicals, addition reactions by hydrosilylation, and condensation reactions, it has excellent curability and can produce cured products with good properties. That is, (I) unlike radical addition reactions, high temperatures are not required to generate initiating species, and it can be cured at room temperature or by heating, and it is not easily inhibited by oxygen, so it has excellent surface curability, (II) the addition reaction mechanism is different from hydrosilylation, and it is not likely to cause curing defects even if sulfur, phosphorus, nitrogen compounds, water, organometallic salts, etc.
  • the curable silicone composition of the present invention can be cured under mild conditions of 100°C or less, even when using a catalyst that is stable at room temperature. This means that it can be cured even when using heat-sensitive parts that cannot be exposed to high temperatures during mounting, making it highly useful as a material used around electrical and electronic parts and semiconductor elements. If a highly active catalyst is used, it can be cured smoothly even under milder conditions.
  • the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
  • the kinetic viscosity at 25°C is a value measured as described above
  • the catalyst concentration is based on the mass of the entire composition converted into the central metal atom
  • the average particle size is a volume-based average value in particle size distribution measurement by laser light diffraction method
  • Me represents a methyl group.
  • Component A-1 an organopolysiloxane represented by the following formula (3) having a kinetic viscosity at 25° C. of 450 mm 2 /s:
  • A-2 Organopolysiloxane represented by the following formula (4) having a kinetic viscosity at 25° C. of 80 mm 2 /s:
  • A-3 Organopolysiloxane represented by the following formula (5) having a kinetic viscosity at 25° C. of 140 mm 2 /s.
  • a-4 (for comparison): Dimethylpolysiloxane having both ends capped with ethynyl groups and a kinetic viscosity at 25° C. of 600 mm 2 /s (not corresponding to component (A) of the present invention)
  • B-1 A solution of tris(dibenzylideneacetone)dipalladium(0) dissolved in methylene chloride (catalyst concentration: 1% by mass)
  • B-2 a solution of tris(dibenzylideneacetone)dipalladium(0) capped at both ends with trimethylsilyl groups and dissolved in dimethylpolysiloxane having a kinetic viscosity of 50,000 mm 2 /s at 25° C. (catalyst concentration: 5% by mass)
  • Component C-1 Aluminum oxide powder with an average particle size of 10 ⁇ m
  • C-2 Zinc oxide powder with an average particle size of 0.4 ⁇ m
  • the silicone compositions of Examples 1 to 8 of the present invention can be cured to a rubber-like state in a short time of 0.5 hours at high temperatures of 100°C or higher, and within 48 hours at relatively low temperatures below 100°C.
  • Comparative Example 1 shows that the organopolysiloxane compounds that satisfy the requirements of the present invention are not organopolysiloxane compounds that can be cured alone, since they do not cure when they do not contain a metal catalyst that catalyzes the [2+2+2] cycloaddition reaction.
  • Comparative Examples 2 to 4 are silicone compositions that use dimethylpolysiloxanes that are blocked at both ends with ethynyl groups.
  • Curable silicone compositions were prepared by mixing the above components (A), (B), (C), and (D) in the amounts shown in Table 3 below using a Thinky Mixer. The properties of each of the resulting curable silicone compositions when cured under the temperature conditions shown in Table 3 below were examined. The results are shown in Table 3.
  • the silicone compositions of Examples 9 to 13 of the present invention can be cured into a rubber-like state in a short time of 0.5 hours at high temperatures of 100°C or higher, and within 24 hours at relatively low temperatures of less than 100°C.
  • Comparative Example 5 is a silicone composition using a dimethylpolysiloxane capped at both ends with ethynyl groups. This composition remains liquid even after 168 hours or more at the relatively low temperature of 25°C, indicating that it has poor curability at room temperature.
  • the organopolysiloxane compounds of the present invention can be cured into a rubber-like state by mixing with a metal catalyst capable of catalyzing the [2+2+2] cycloaddition reaction, and that they can be cured not only at high curing temperatures of 100°C or higher, but also at relatively low curing temperatures below 100°C.
  • a curable silicone composition (A) an organopolysiloxane compound having a substituent represented by the following general formula (1) in the molecule: 100 parts by mass, (wherein R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, R 2 is independently a substituted or unsubstituted divalent hydrocarbon group, and R 3 is a divalent linking group); and (B) an effective amount of a metal compound capable of catalyzing a [2+2+2] cycloaddition reaction,
  • a curable silicone composition comprising: [2]: The curable silicone composition according to [1], wherein R2 in the general formula (1) is a methylene group.
  • [3] The curable silicone composition according to [1] or [2], wherein R 1 in the general formula (1) is a hydrogen atom.
  • [4] The curable silicone composition of any one of [1] to [3], wherein the component (A) is an organopolysiloxane compound having, on average, two or more substituents represented by general formula (1) per molecule.
  • [5] The curable silicone composition of any one of [1] to [4], further comprising (C) one or more inorganic or organic fillers in an amount of 0.1 to 5,000 parts by mass per 100 parts by mass of component (A).
  • [6] The curable silicone composition of [5], wherein the component (C) is a filler made of one or more materials selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, carbon allotropes, resins, dyes, and pigments.
  • a method for producing a curable silicone composition comprising the steps of: (A) an organopolysiloxane compound having a substituent represented by the following general formula (1) in the molecule: 100 parts by mass, (wherein R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, R 2 is independently a substituted or unsubstituted divalent hydrocarbon group, and R 3 is a divalent linking group); and (B) an effective amount of a metal compound capable of catalyzing a [2+2+2] cycloaddition reaction, 2.
  • a method for producing a curable silicone composition comprising mixing:
  • the present invention is not limited to the above-described embodiments.
  • the above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included within the technical scope of the present invention.

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Abstract

La présente invention concerne une composition de silicone durcissable qui est caractérisée en ce qu'elle contient 100 parties en masse (A) d'un composé organopolysiloxane qui comprend un substituant représenté par la formule générale (1) dans chaque molécule et une quantité efficace (B) d'un composé métallique permettant de catalyser une réaction de cycloaddition [2 +2 +2]. (Dans la formule, R1 représente indépendamment un groupe hydrocarboné monovalent substitué ou non substitué ou un atome d'hydrogène, R2 représente indépendamment un groupe hydrocarboné divalent substitué ou non substitué, et R3 représente un groupe de liaison divalent). Par conséquent, la présente invention concerne : une composition de silicone durcissable permettant d'avoir une progression de réaction de cycloaddition [2 + 2 + 2] dans des conditions modérées ; et un produit durci à base de silicone de la composition de silicone durcissable.
PCT/JP2024/039182 2023-12-14 2024-11-05 Composition de silicone durcissable contenant un composé organopolysiloxane amino-modifié contenant un diyne Pending WO2025126719A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10101800A (ja) * 1996-09-18 1998-04-21 Wacker Chemie Gmbh アミノ基を有する有機珪素化合物及びその製造方法
JP2002521529A (ja) * 1998-07-25 2002-07-16 イギリス国 単量体及び、それらから得られる網状高分子
US20030225232A1 (en) * 2002-03-28 2003-12-04 Tang Ben Zhong Hyperbranched polymers
US20070141363A1 (en) * 2005-12-19 2007-06-21 Acosta Erick J Triazole-containing fluorocarbon-grafted polysiloxanes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10101800A (ja) * 1996-09-18 1998-04-21 Wacker Chemie Gmbh アミノ基を有する有機珪素化合物及びその製造方法
JP2002521529A (ja) * 1998-07-25 2002-07-16 イギリス国 単量体及び、それらから得られる網状高分子
US20030225232A1 (en) * 2002-03-28 2003-12-04 Tang Ben Zhong Hyperbranched polymers
US20070141363A1 (en) * 2005-12-19 2007-06-21 Acosta Erick J Triazole-containing fluorocarbon-grafted polysiloxanes

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