WO2016136245A1 - Organopolysiloxane, method for producing same, and curable silicone composition - Google Patents

Organopolysiloxane, method for producing same, and curable silicone composition Download PDF

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WO2016136245A1
WO2016136245A1 PCT/JP2016/000961 JP2016000961W WO2016136245A1 WO 2016136245 A1 WO2016136245 A1 WO 2016136245A1 JP 2016000961 W JP2016000961 W JP 2016000961W WO 2016136245 A1 WO2016136245 A1 WO 2016136245A1
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group
organopolysiloxane
carbon atoms
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component
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PCT/JP2016/000961
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French (fr)
Japanese (ja)
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森田　好次
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東レ・ダウコーニング株式会社
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Publication of WO2016136245A1 publication Critical patent/WO2016136245A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C08L83/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present invention relates to a novel organopolysiloxane having silicon-bonded hydrogen atoms at both ends of a molecular chain, a method for producing the same, and a curable silicone composition containing the organopolysiloxane.
  • a curable silicone composition that is cured by a hydrosilylation reaction to form a cured product having a high refractive index and a high light transmittance is used for semiconductor elements in optical semiconductor devices such as photocouplers, light emitting diodes (LEDs), and solid-state imaging devices. It is used as a protective agent, coating agent, or sealant.
  • Such curable silicone compositions include linear organopolysiloxanes having at least two alkenyl groups and at least one aryl group in one molecule, at least one alkenyl group and at least one in one molecule.
  • an organopolysiloxane having a high degree of polymerization having a silicon atom-bonded hydrogen atom and a silicon atom-bonded aryl group in one molecule In general, it is difficult to prepare an organopolysiloxane having a high degree of polymerization having a silicon atom-bonded hydrogen atom and a silicon atom-bonded aryl group in one molecule.
  • the linear organopolysiloxane having a bonded hydrogen atom has a relatively low degree of polymerization.
  • it in order to improve the physical properties and heat resistance of the cured silicone product obtained by curing, it has at least one silicon atom-bonded aryl group in one molecule and silicon atom bonds at both ends of the molecular chain.
  • Patent Document 2 discloses hydrosilylation reaction of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane.
  • the chain-structured organopolysiloxane described in Patent Document 2 is one in which both ends of the molecular chain are blocked with vinyl groups, while the chain-structured organopolysiloxane described in Patent Document 3 is a molecule. It is an alternating copolymer in which the siloxane chain is linked by an alkylene chain, and it is difficult to control the molecular weight during synthesis. The resulting alternating copolymer has low flexibility and does not exhibit sufficient heat resistance. is there.
  • An object of the present invention is to provide a novel organopolysiloxane having silicon-bonded hydrogen atoms at both ends of a molecular chain, and a method for producing the same. Furthermore, another object of the present invention is to provide a curable silicone composition that forms a flexible cured product.
  • the organopolysiloxane of the present invention has the general formula: HR 1 2 SiOSiR 1 2 -R 3 -R 1 2 SiO (R 2 2 SiO) m SiR 1 2 -R 3 -R 1 2 SiOSiR 1 2 H (Wherein R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, provided that all R (At least 10 mol% of 2 is the aryl group, each R 3 is independently an alkylene group having 2 to 6 carbon atoms, and m is an integer of 5 or more.) It is represented by
  • the curable silicone composition of the present invention is a hydrosilylation reaction-curable silicone composition containing the above organopolysiloxane.
  • R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, etc.
  • Examples include alkyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl, phenethyl, and phenylpropyl.
  • R 2 is the aryl group, preferably a phenyl group. That is, in the above formula, the general formula: (R 2 2 SiO) m
  • the diorganosiloxane block represented by these contains a diphenylsiloxane unit or a methylphenylsiloxane unit. This is because the refractive index of the organopolysiloxane can be increased.
  • organopolysiloxane of the present invention examples include the following organopolysiloxanes.
  • Me and Ph represent a methyl group and a phenyl group, respectively, and m represents an integer of 5 or more.
  • the (A) component organopolysiloxane has a general formula: R 4 R 1 2 SiO (R 2 2 SiO) m SiR 1 2 R 4 It is represented by
  • R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, the same groups as described above are exemplified. However, at least 10 mol% of all R 2 is the aryl group, preferably a phenyl group. This is because the refractive index of the resulting organopolysiloxane can be increased.
  • each R 4 is independently an alkenyl group having 2 to 6 carbon atoms.
  • Specific examples include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, an isopentenyl group, and a hexenyl group, and a vinyl group is preferable.
  • m is an integer of 5 or more, and preferably an integer of 10 or more. This is because the curable silicone composition containing the resulting organopolysiloxane can form a flexible cured product.
  • m is preferably an integer of 1,000 or less, or an integer of 500 or less. This is because the reactivity of silicon-bonded hydrogen atoms in the resulting organopolysiloxane is not impaired.
  • Examples of such component (A) include the following organopolysiloxanes.
  • Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively, and m represents an integer of 5 or more.
  • the organodisiloxane of component (B) has the general formula: HR 1 2 SiOSiR 1 2 H It is represented by
  • each R 1 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and examples thereof include the same groups as described above.
  • Component (B) is added in an amount such that the silicon-bonded hydrogen atom in this component exceeds 1 mol, preferably 2 mol or more, or 2 with respect to 1 mol of alkenyl group in component (A). It is the amount which becomes .5 mol or more. This is because the more the amount of component (B) added, the more efficiently the organopolysiloxane can be produced. On the other hand, since the unreacted component (B) can be efficiently removed, the amount of component (B) added is 20 moles of silicon-bonded hydrogen atoms in this component with respect to 1 mole of alkenyl group in component (A). The amount is less than or equal to a mole, and preferably less than or equal to 15 moles, less than or equal to 10 moles, or less than or equal to 8 moles.
  • a hydrosilylation reaction catalyst in the production method of the present invention.
  • the catalyst for hydrosilylation reaction is not limited, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
  • a platinum-based catalyst is preferable because the hydrosilylation reaction can be significantly accelerated.
  • the platinum-based catalyst include platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex, particularly platinum-alkenylsiloxane complex. It is preferable.
  • alkenylsiloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples include alkenyl siloxanes in which a part of the methyl groups of these alkenyl siloxanes are substituted with groups such as ethyl groups and phenyl groups, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with groups such as allyl groups and hexenyl groups. .
  • the addition amount of the catalyst for hydrosilylation reaction is not limited.
  • the catalyst metal is in the range of 0.01 to 1,000 ppm in terms of mass unit with respect to the total amount of component (A) and component (B).
  • the amount is within the range of 0.1 to 500 ppm. This is because when the amount of the hydrosilylation reaction catalyst is at least the lower limit of the above range, the hydrosilylation reaction can be sufficiently promoted. On the other hand, when it is below the upper limit of the above range, the resulting organopolysiloxane can be colored. This is because problems are less likely to occur.
  • reaction conditions in this hydrosilylation reaction are not limited, and the reaction can be promoted by heating.
  • the reaction temperature is preferably the reflux temperature of the solvent. When not used, it is preferably 200 ° C. or lower.
  • the viscosity of the reaction system can be reduced, and water can be dehydrated from the reaction system by azeotropic distillation or the like.
  • the organopolysiloxane thus obtained has silicon-bonded hydrogen atoms at both ends of the molecular chain. Therefore, by adding it to the hydrosilylation reaction-curable silicone composition, it undergoes a hydrosilylation reaction to produce a cured product. A cured product that is incorporated therein, has a small surface tack, and an appropriate elastic modulus can be formed.
  • this organopolysiloxane has an aryl group in the molecule, and thus is suitable as a component of a hydrosilylation reaction-curable silicone composition having a high refractive index.
  • a curable silicone composition for example, (I) an organopolysiloxane having at least two alkenyl groups in one molecule; (II) Organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule ⁇ the silicon atom-bonded hydrogen atom in this component is 0. 1 to 10 mol ⁇ (III) The organopolysiloxane of the present invention (0.1 to 50% by mass with respect to the present composition), and (IV) a catalyst for hydrosilylation reaction (an amount that promotes curing of the present composition) And a hydrosilylation reaction-curable silicone composition comprising at least
  • Component (I) is an organopolysiloxane having at least two alkenyl groups in one molecule.
  • alkenyl group in component (I) the number of carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group and the like is 2 to Twelve alkenyl groups are exemplified, and a vinyl group is preferable.
  • Examples of the group bonded to the silicon atom other than the alkenyl group in the component (I) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, Alkyl groups having 1 to 12 carbon atoms such as hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group; carbon such as phenyl group, tolyl group, xylyl group and naphthyl group An aryl group having 6 to 20 carbon atoms; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group, a phenethyl group, and a phenylpropyl group; a part or all of hydrogen atoms of these
  • the molecular structure of the component (I) is not limited, and examples thereof include a straight chain, a partially branched straight chain, a branched chain, a ring, or a three-dimensional network structure.
  • Component (I) may be a single organopolysiloxane having these molecular structures, or a mixture of two or more organopolysiloxanes having these molecular structures.
  • Component (II) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule.
  • the group bonded to the silicon atom other than the hydrogen atom in the component includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group Alkyl groups having 1 to 12 carbon atoms such as cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like; phenyl group, tolyl group, xylyl group, naphthyl group, etc.
  • the silicon atom in the component (II) may have a small amount of a hydroxyl group, an alkoxy group such as a methoxy group, an ethoxy group or the like as long as the object of the present invention is not impaired.
  • the molecular structure of the component (II) is not limited, and examples thereof include linear, partially branched linear, branched, cyclic, or three-dimensional network structure, and preferably partially branched linear , Branched chain, or three-dimensional network structure.
  • component (II) examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogen).
  • the content of the component (II) is such that the silicon-bonded hydrogen atom in this component is 0.1 to 10 mol, preferably 0.1 to 1 mol of the alkenyl group in the component (I).
  • the amount is 5 to 5 mol. This is because if the content of the component (II) is not more than the upper limit of the above range, it is possible to suppress a decrease in the mechanical properties of the resulting cured product, whereas, if not less than the lower limit of the above range, This is because the resulting composition is sufficiently cured.
  • the organopolysiloxane of component (III) is as described above.
  • the content of the component (III) is an amount that falls within the range of 0.1 to 50% by mass, preferably an amount that falls within the range of 5 to 35% by mass with respect to the present composition. This is because when the content of the component (III) is not less than the lower limit of the above range, sufficient flexibility can be imparted to the obtained cured product, and on the other hand, if the content is not more than the upper limit of the above range, the resulting cure can be obtained. This is because the mechanical strength of the object is not lowered.
  • the component (IV) is a hydrosilylation catalyst for promoting the hydrosilylation reaction of the composition.
  • a catalyst for hydrosilylation reaction of the component (IV) is not limited, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
  • a platinum-based catalyst is preferable because the hydrosilylation reaction can be significantly accelerated.
  • Examples of the platinum-based catalyst include the same catalysts as described above.
  • the content of the component (IV) is an amount that promotes the curing of the present composition, and preferably the platinum atom in the component (IV) is in the range of 0.01 to 500 ppm by mass with respect to the present composition. Is an amount that falls within the range of 0.01 to 100 ppm, or an amount that falls within the range of 0.1 to 50 ppm. This is because the composition obtained is sufficiently cured when the content of the component (IV) is equal to or higher than the lower limit of the above range, and on the other hand, when the content is equal to or lower than the upper limit of the above range, the resulting cured product is colored. It is because it is suppressed.
  • This composition may contain (E) a hydrosilylation reaction inhibitor as an optional component for extending the pot life at room temperature and improving the storage stability.
  • component (E) include 1-ethynylcyclohexane-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl- Alkyne alcohols such as 3-butyn-2-ol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7 A methyl alkenyl siloxane oligomer such as tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; Alkyneoxysilanes such as dimethylbis (1,1-dimethylbutyneoxy) si
  • the group other than the alkoxy group bonded to the silicon atom of the organosilicon compound includes halogen-substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups.
  • Glycidoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl
  • Examples include an epoxycyclohexylalkyl group such as a group; an epoxyalkyl group such as a 4-epoxybutyl group and an 8-epoxyoctyl group; a 3-methacryloxypropyl group; an isocyanate group; an isocyanurate group; and a hydrogen atom.
  • one or more inorganic fillers selected from silica, glass, alumina and the like as other optional components silicone rubber powder; Resin powder such as silicone resin and polymethacrylate resin; one or more components selected from heat-resistant agents, dyes, pigments, flame retardants, surfactants, solvents and the like may be contained.
  • the organopolysiloxane of the present invention will be described in detail with reference to examples.
  • the viscosity in an Example is a value in 25 degreeC.
  • Me, Ph, Vi, and Ep represent a methyl group, a phenyl group, a vinyl group, and a 3-glycidoxypropyl group, respectively.
  • Example 1 In a reaction vessel, 199.97 g of toluene, formula: ViMe 2 SiO (PhMeSiO) 20 SiMe 2 Vi 167.51 g of a diorganopolysiloxane represented by the following formula (refractive index 1.5438, viscosity 2,625 mPa ⁇ s, mass average molecular weight 4,042), and the formula: HMe 2 SiOSiMe 2 H 15.00 g of disiloxane represented by the formula (in which 3 mol of silicon-bonded hydrogen atoms in this component is 3 mol with respect to 1 mol of vinyl group in the diorganopolysiloxane) is azeotroped at 106 ° C. After dehydration, it was cooled to room temperature.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in this complex is expressed in mass units with respect to the total amount of the diorganopolysiloxane and the disiloxane). 5 ppm) was added, and the mixture was reacted at a toluene reflux temperature of 111 ° C. to 112 ° C. for 3 hours. Then, after cooling to room temperature and mixing 7.4g of activated carbon, it filtered with the glass filter. Toluene and unreacted disiloxane were distilled off from the filtrate by heating under reduced pressure at 4 mmHg and 100 ° C.
  • This liquid has the formula: HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) 20 SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H It was found that the organopolysiloxane represented by
  • Example 2 In a reaction vessel, 172.91 g of toluene, general formula: ViMe 2 SiO (PhMeSiO) n SiMe 2 Vi (In the formula, n is about 100.) Diorganopolysiloxane (mass average molecular weight 15,800, refractive index 1.5512, viscosity 41,250 mPa ⁇ s) 124.72 g, and formula: HMe 2 SiOSiMe 2 H After adding 2.50 g of disiloxane represented by the following formula (amount in which 4 moles of silicon-bonded hydrogen atoms in this component are 4 moles per mole of vinyl groups in the diorganopolysiloxane): And cooled to room temperature.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in this complex is expressed in mass units with respect to the total amount of the diorganopolysiloxane and the disiloxane). 5 ppm) was added, and the reaction was carried out at a toluene reflux temperature of 107 ° C. to 111 ° C. for 2.2 hours. Thereafter, the mixture was cooled to room temperature, mixed with 8.1 g of activated carbon, and filtered through a glass filter. Toluene and unreacted disiloxane were distilled off from the filtrate by heating under reduced pressure at 4 mmHg and 119 ° C.
  • This liquid has the general formula: HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) n SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H (In the formula, n is about 100.) It was found that the organopolysiloxane represented by
  • Example 3 In a reaction vessel, 172.91 g of toluene, general formula: ViMe 2 SiO (PhMeSiO) m SiMe 2 Vi (Where m is about 8) Diorganopolysiloxane (mass average molecular weight 1,250, refractive index 1.565, viscosity 1,000 mPa ⁇ s) 163.03 g, and formula: HMe 2 SiOSiMe 2 H 49.9 g of disiloxane represented by the formula (in which the amount of silicon-bonded hydrogen atoms in this component is 2.6 mol with respect to 1 mol of vinyl group in the diorganopolysiloxane) is added, and azeotropic dehydration is performed. And then cooled to room temperature.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in this complex is expressed in mass units with respect to the total amount of the diorganopolysiloxane and the disiloxane). 5 ppm) was added, and the mixture was reacted at a toluene reflux temperature of 100 ° C. to 120 ° C. for 2.5 hours. Thereafter, the mixture was cooled to room temperature, mixed with 13.3 g of activated carbon, and then filtered through a glass filter. Toluene and unreacted disiloxane were distilled off from the filtrate by heating under reduced pressure at 6 mmHg and 100 ° C.
  • This liquid has the general formula: HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) m SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H (Where m is about 8) It was found that the organopolysiloxane represented by
  • Example 4 In a reaction vessel, 124.89 g of toluene, formula: ViMePhSiO (Ph 2 SiO) 13 (Me 2 SiO) 19 SiMePhVi 61.07 g of a liquid diorganopolysiloxane that is viscous at room temperature (mass average molecular weight 5,100, refractive index 1.5823), and HMe 2 SiOSiMe 2 H After adding 8.81 g of disiloxane represented by the formula (amount of silicon-bonded hydrogen atoms in this component to 7 mol with respect to 1 mol of vinyl groups in the diorganopolysiloxane), And cooled to room temperature.
  • toluene formula: ViMePhSiO (Ph 2 SiO) 13 (Me 2 SiO) 19 SiMePhVi 61.07 g of a liquid diorganopolysiloxane that is viscous at room temperature (mass average molecular weight 5,100
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in this complex is expressed in mass units with respect to the total amount of the diorganopolysiloxane and the disiloxane). 5 ppm) was added, and the mixture was reacted at a toluene reflux temperature of 110 ° C. to 111 ° C. for 3 hours. Thereafter, the mixture was cooled to room temperature, mixed with 10.5 g of activated carbon, and filtered through a glass filter. Toluene and unreacted disiloxane were distilled off from the filtrate by heating under reduced pressure at 63 mmHg and 99 ° C.
  • This liquid has the formula: HMe 2 SiOSiMe 2 —C 2 H 4 —MePhSiO (Ph 2 SiO) 13 (Me 2 SiO) 19 SiMePh—C 2 H 4 —Me 2 SiOSiMe 2 H It was the organopolysiloxane represented by these.
  • platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (the platinum metal in this complex is the above-mentioned vinyl group-containing diorganopolysiloxane and the above silicon-bonded hydrogen atom-containing diorgano
  • the amount of 5 ppm in terms of mass unit with respect to the total amount of polysiloxane) was added, and the color was slightly brown due to heat generation. This was heated in a 150 ° C. oven for 1 hour and then cooled to room temperature.
  • a slightly brown transparent liquid having a refractive index of 1.5311, a viscosity of 10,400 mPa ⁇ s, and a weight average molecular weight of 8,120 was obtained.
  • This liquid has the formula: HMe 2 SiOPh 2 SiOSiMe 2- [C 2 H 4 -Me 2 SiOPh 2 SiOSiMe 2 -C 2 H 4 -Me 2 SiOPh 2 SiOSiMe 2- ] m -C 2 H 4 -Me 2 SiOPh 2 SiOSiMe 2 -C 2 H 4- Me 2 SiOPh 2 SiOSiMe 2 H (In the formula, m is 8.) It was found that the organopolysiloxane represented by
  • This curable silicone composition was cured into a plate having a thickness of 1 mm, a length of 20 mm, and a length of 10 mm, and the obtained cured product was measured at an interval of 15 mm using an ARES viscoelasticity measuring apparatus (RDA700 manufactured by Reometric Scientific).
  • the storage elastic modulus of the storage elastic modulus at room temperature was measured under the conditions of a twist of 0.5% and a frequency of 1 Hz.
  • the storage elastic modulus was 350 MPa.
  • Example 5 A curable silicone composition was prepared by blending 20 parts by mass of the organopolysiloxane prepared in Example 1 with 80 parts by mass of the curable silicone composition prepared in Reference Example 1.
  • the cured product obtained by curing this curable silicone composition had a storage elastic modulus of 3 MPa, and the surface of the cured product was not sticky.
  • the organopolysiloxane of the present invention has silicon-bonded hydrogen atoms at both ends of the molecular chain, it can be used as a component of the hydrosilylation reaction-curable silicone composition. Since such a curable silicone composition can form a flexible cured product, it can be used as an adhesive for electric and electronic, a potting agent, a protective coating agent, and an underfill agent. It is suitable as an element adhesive, potting agent, protective coating agent, and underfill agent.

Abstract

The present invention is a novel organopolysiloxane having a silicon-atom-bonded hydrogen atom at both ends of the molecular chain, and is represented by the general formula: HR1 2SiOSiR1 2-R3-R1 2SiO(R2 2SiO)mSiR1 2-R2-R1 2SiOSiR1 2H. (In the formula, R1 and R2 each independently represent a C1-12 alkyl group, a C6-20 aryl group, or a C7-20 aralkyl group, wherein at least 10 mol% of all R2s is said aryl group; R3s each independently represent a C2-6 alkylene group; and m is an integer of 5 or greater.)

Description

オルガノポリシロキサン、その製造方法、および硬化性シリコーン組成物Organopolysiloxane, process for producing the same, and curable silicone composition
　本発明は、分子鎖両末端にケイ素原子結合水素原子を有する新規なオルガノポリシロキサン、その製造方法、および前記オルガノポリシロキサンを含有する硬化性シリコーン組成物に関する。 The present invention relates to a novel organopolysiloxane having silicon-bonded hydrogen atoms at both ends of a molecular chain, a method for producing the same, and a curable silicone composition containing the organopolysiloxane.
　ヒドロシリル化反応により硬化して、屈折率が高く、光透過率が高い硬化物を形成する硬化性シリコーン組成物は、フォトカップラー、発光ダイオード（ＬＥＤ）、固体撮像素子等の光半導体装置における半導体素子の保護剤、被覆剤、または封止剤として使用されている。このような硬化性シリコーン組成物としては、一分子中に少なくとも２個のアルケニル基と少なくとも１個のアリール基を有する直鎖状オルガノポリシロキサン、一分子中に少なくとも１個のアルケニル基と少なくとも１個のアリール基を有し、一般式：ＲＳｉＯ３／２（式中、Ｒは置換または非置換の一価炭化水素基である。）で表されるシロキサン単位を有する分岐鎖状オルガノポリシロキサン、一分子中に少なくとも１個のケイ素原子結合アリール基を有し、分子鎖両末端にケイ素原子結合水素原子を有する直鎖状オルガノポリシロキサン、およびヒドロシリル化反応用触媒から少なくともなる硬化性シリコーン組成物（特許文献１参照）が知られている。 A curable silicone composition that is cured by a hydrosilylation reaction to form a cured product having a high refractive index and a high light transmittance is used for semiconductor elements in optical semiconductor devices such as photocouplers, light emitting diodes (LEDs), and solid-state imaging devices. It is used as a protective agent, coating agent, or sealant. Such curable silicone compositions include linear organopolysiloxanes having at least two alkenyl groups and at least one aryl group in one molecule, at least one alkenyl group and at least one in one molecule. A branched organopolysiloxane having an aryl group and having a siloxane unit represented by the general formula: RSiO 3/2 (wherein R is a substituted or unsubstituted monovalent hydrocarbon group), Curable silicone composition comprising at least one linear organopolysiloxane having at least one silicon-bonded aryl group in one molecule and silicon-bonded hydrogen atoms at both ends of the molecular chain, and a catalyst for hydrosilylation reaction (See Patent Document 1).
　一般に、ケイ素原子結合水素原子とケイ素原子結合アリール基を一分子中に有する高重合度のオルガノポリシロキサンを調製することは困難であるため、上記の組成物においては、分子鎖両末端にケイ素原子結合水素原子を有する直鎖状オルガノポリシロキサンは、比較的低重合度のものが使用されている。しかしながら、硬化して得られるシリコーン硬化物の物理特性の改良や耐熱性を向上させるためには、一分子中に少なくとも１個のケイ素原子結合アリール基を有し、分子鎖両末端にケイ素原子結合水素原子を有する比較的高重合度の直鎖状オルガノポリシロキサンが求められている。 In general, it is difficult to prepare an organopolysiloxane having a high degree of polymerization having a silicon atom-bonded hydrogen atom and a silicon atom-bonded aryl group in one molecule. The linear organopolysiloxane having a bonded hydrogen atom has a relatively low degree of polymerization. However, in order to improve the physical properties and heat resistance of the cured silicone product obtained by curing, it has at least one silicon atom-bonded aryl group in one molecule and silicon atom bonds at both ends of the molecular chain. There is a need for a linear organopolysiloxane having a hydrogen atom and a relatively high degree of polymerization.
　一方、特許文献２には、１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンと３,３－ジフェニル－１,１,５,５－テトラメチルトリシロキサンとをヒドロシリル化反応して、ビニル基を有する鎖状構造のオルガノポリシロキサンを調製することが記載され、また、特許文献３には、３,３－ジフェニル－１,５－ジビニル－１,１,３,３－テトラメチルジシロキサンと３,３－ジフェニル－１,１,５,５－テトラメチルトリシロキサンとをヒドロシリル化反応して、分子鎖両末端にケイ素原子結合水素原子を有する鎖状構造のオルガノポリシロキサンを調製することが記載されている。 On the other hand, Patent Document 2 discloses hydrosilylation reaction of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane. Patent Document 3 describes preparation of organopolysiloxane having a chain structure having a vinyl group, and Patent Document 3 discloses 3,3-diphenyl-1,5-divinyl-1,1,3,3- An organopolysiloxane having a chain structure in which tetramethyldisiloxane and 3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane are hydrosilylated to have silicon-bonded hydrogen atoms at both ends of the molecular chain Is described.
　しかし、特許文献２に記載された鎖状構造のオルガノポリシロキサンは分子鎖両末端がビニル基で封鎖されたものであり、一方、特許文献３に記載された鎖状構造のオルガノポリシロキサンは分子中のシロキサン鎖がアルキレン鎖により連結された交互共重合体であり、合成時の分子量制御が困難で、得られた交互共重合体は柔軟性が低く、十分な耐熱性を示さないという課題がある。 However, the chain-structured organopolysiloxane described in Patent Document 2 is one in which both ends of the molecular chain are blocked with vinyl groups, while the chain-structured organopolysiloxane described in Patent Document 3 is a molecule. It is an alternating copolymer in which the siloxane chain is linked by an alkylene chain, and it is difficult to control the molecular weight during synthesis. The resulting alternating copolymer has low flexibility and does not exhibit sufficient heat resistance. is there.
特開２００５－１０５２１７号公報JP 2005-105217 A 特開２０１２－０２１１５７号公報JP 2012-021157 A 特開２０１２－１４０６１７号公報JP 2012-140617 A
　本発明の目的は、分子鎖両末端にケイ素原子結合水素原子を有する新規なオルガノポリシロキサン、およびその製造方法を提供することにある。さらに、本発明の他の目的は、柔軟な硬化物を形成する硬化性シリコーン組成物を提供することにある。 An object of the present invention is to provide a novel organopolysiloxane having silicon-bonded hydrogen atoms at both ends of a molecular chain, and a method for producing the same. Furthermore, another object of the present invention is to provide a curable silicone composition that forms a flexible cured product.
　本発明のオルガノポリシロキサンは、一般式：
ＨＲ１ ２ＳｉＯＳｉＲ１ ２－Ｒ３－Ｒ１ ２ＳｉＯ(Ｒ２ ２ＳｉＯ)ｍＳｉＲ１ ２－Ｒ３－Ｒ１ ２ＳｉＯＳｉＲ１ ２Ｈ
（式中、Ｒ１およびＲ２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、または炭素数７～２０のアラルキル基であり、但し、全Ｒ２の少なくとも１０モル％は前記アリール基であり、Ｒ３は、それぞれ独立して、炭素数２～６のアルキレン基であり、ｍは５以上の整数である。）
で表される。 The organopolysiloxane of the present invention has the general formula:
HR 1 2 SiOSiR 1 2 -R 3 -R 1 2 SiO (R 2 2 SiO) m SiR 1 2 -R 3 -R 1 2 SiOSiR 1 2 H
(Wherein R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, provided that all R (At least 10 mol% of 2 is the aryl group, each R 3 is independently an alkylene group having 2 to 6 carbon atoms, and m is an integer of 5 or more.)
It is represented by
　また、本発明のオルガノポリシロキサンの製造方法は、
（Ａ）一般式：
Ｒ４Ｒ１ ２ＳｉＯ(Ｒ２ ２ＳｉＯ)ｍＳｉＲ１ ２Ｒ４
（式中、Ｒ１およびＲ２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、または炭素数７～２０のアラルキル基であり、但し、全Ｒ２の少なくとも１０モル％は前記アリール基であり、Ｒ４は、それぞれ独立して、炭素数２～６のアルケニル基であり、ｍは５以上の整数である。）
で表されるオルガノポリシロキサンと
（Ｂ）一般式：
ＨＲ１ ２ＳｉＯＳｉＲ１ ２Ｈ
（式中、Ｒ１は前記と同じである。）
で表されるオルガノジシロキサンを、（Ａ）成分中のアルケニル基１モルに対して、（Ｂ）成分中のケイ素原子結合水素原子が１モルを超える量でヒドロシリル化反応してなることを特徴とする。 In addition, the method for producing the organopolysiloxane of the present invention includes:
(A) General formula:
R 4 R 1 2 SiO (R 2 2 SiO) m SiR 1 2 R 4
(Wherein R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, provided that all R (At least 10 mol% of 2 is the aryl group, each R 4 is independently an alkenyl group having 2 to 6 carbon atoms, and m is an integer of 5 or more.)
And (B) the general formula:
HR 1 2 SiOSiR 1 2 H
(In the formula, R 1 is the same as described above.)
The organodisiloxane represented by the formula (A) is obtained by hydrosilylation reaction in an amount exceeding 1 mol of silicon-bonded hydrogen atoms in the component (B) with respect to 1 mol of the alkenyl group in the component (A). And
　また、本発明の硬化性シリコーン組成物は、上記のオルガノポリシロキサンを含有するヒドロシリル化反応硬化性シリコーン組成物である。 The curable silicone composition of the present invention is a hydrosilylation reaction-curable silicone composition containing the above organopolysiloxane.
　本発明のオルガノポリシロキサンは、分子鎖両末端にケイ素原子結合水素原子を有する新規なオルガノポリシロキサンであり、また、本発明の製造方法は、このような新規なオルガノポリシロキサンを効率よく製造できるという特徴がある。さらに、本発明の硬化性シリコーン組成物は、柔軟な硬化物を形成できるという特徴がある。 The organopolysiloxane of the present invention is a novel organopolysiloxane having silicon-bonded hydrogen atoms at both ends of the molecular chain, and the production method of the present invention can efficiently produce such a novel organopolysiloxane. There is a feature. Furthermore, the curable silicone composition of the present invention is characterized in that a flexible cured product can be formed.
［オルガノポリシロキサン］
　はじめに、本発明のオルガノポリシロキサンを詳細に説明する。
　本発明のオルガノポリシロキサンは、一般式：
ＨＲ１ ２ＳｉＯＳｉＲ１ ２－Ｒ３－Ｒ１ ２ＳｉＯ(Ｒ２ ２ＳｉＯ)ｍＳｉＲ１ ２－Ｒ３－Ｒ１ ２ＳｉＯＳｉＲ１ ２Ｈ
で表される。 [Organopolysiloxane]
First, the organopolysiloxane of the present invention will be described in detail.
The organopolysiloxane of the present invention has the general formula:
HR 1 2 SiOSiR 1 2 -R 3 -R 1 2 SiO (R 2 2 SiO) m SiR 1 2 -R 3 -R 1 2 SiOSiR 1 2 H
It is represented by
　式中、Ｒ１およびＲ２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、または炭素数７～２０のアラルキル基である。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェネチル基、フェニルプロピル基等のアラルキル基が例示される。但し、全Ｒ２の少なくとも１０モル％は前記アリール基であり、好ましくは、フェニル基である。すなわち、上式中、一般式：
(Ｒ２ ２ＳｉＯ)ｍ
で表されるジオルガノシロキサンブロックが、ジフェニルシロキサン単位またはメチルフェニルシロキサン単位を含むことが好ましい。これは、本オルガノポリシロキサンの屈折率を高くすることができるからである。 In the formula, R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, etc. Examples include alkyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl, phenethyl, and phenylpropyl. However, at least 10 mol% of all R 2 is the aryl group, preferably a phenyl group. That is, in the above formula, the general formula:
(R 2 2 SiO) m
It is preferable that the diorganosiloxane block represented by these contains a diphenylsiloxane unit or a methylphenylsiloxane unit. This is because the refractive index of the organopolysiloxane can be increased.
　また、式中、Ｒ３は、それぞれ独立して、炭素数２～６のアルキレン基である。具体的には、エチレン基、メチルメチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ｔｅｒｔ－ブチレン基、ペンチレン基、イソペンチレン基、ヘキシレン基が例示され、好ましくは、エチレン基である。 In the formula, each R 3 is independently an alkylene group having 2 to 6 carbon atoms. Specific examples include an ethylene group, a methylmethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a tert-butylene group, a pentylene group, an isopentylene group, and a hexylene group, and an ethylene group is preferable.
　また、式中、ｍは５以上の整数であり、好ましくは、１０以上の整数である。これは、本オルガノポリシロキサンを配合する硬化性シリコーン組成物が、柔軟な硬化物を形成できるからである。一方、ｍは、好ましくは、１,０００以下の整数、または５００以下の整数である。これは、本オルガノポリシロキサン中のケイ素原子結合水素原子の反応性が損なわれないからである。 In the formula, m is an integer of 5 or more, and preferably an integer of 10 or more. This is because the curable silicone composition containing the organopolysiloxane can form a flexible cured product. On the other hand, m is preferably an integer of 1,000 or less, or an integer of 500 or less. This is because the reactivity of silicon-bonded hydrogen atoms in the organopolysiloxane is not impaired.
　このような本発明のオルガノポリシロキサンとしては、次のようなオルガノポリシロキサンが例示される。なお、式中、ＭｅおよびＰｈはそれぞれメチル基およびフェニル基を示し、ｍは５以上の整数を示す。
ＨＭｅ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)２０ＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＳｉＭｅ２Ｈ
ＨＭｅ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)ｍＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＳｉＭｅ２Ｈ
ＨＭｅ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)ｍＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＳｉＭｅ２Ｈ
ＨＭｅ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯ(Ｍｅ２ＳｉＯ)ｍＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＳｉＭｅ２Ｈ Examples of the organopolysiloxane of the present invention include the following organopolysiloxanes. In the formulae, Me and Ph represent a methyl group and a phenyl group, respectively, and m represents an integer of 5 or more.
HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) 20 SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H
HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) m SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H
HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) m SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H
HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (Me 2 SiO) m SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H
　このような本発明のオルガノポリシロキサンの可視光（５８９ｎｍ）における屈折率（２５℃）は限定されないが、１.５０以上であることが好ましい。これは、本発明のオルガノポリシロキサンを高屈折率の光学材料に好適に使用できるからである。 The refractive index (25 ° C.) of visible light (589 nm) of the organopolysiloxane of the present invention is not limited, but is preferably 1.50 or more. This is because the organopolysiloxane of the present invention can be suitably used for an optical material having a high refractive index.
［オルガノポリシロキサンの製造方法］
　次に、本発明のオルガノポリシロキサンの製造方法を詳細に説明する。
　（Ａ）成分のオルガノポリシロキサンは、一般式：
Ｒ４Ｒ１ ２ＳｉＯ(Ｒ２ ２ＳｉＯ)ｍＳｉＲ１ ２Ｒ４
で表される。 [Method for producing organopolysiloxane]
Next, the method for producing the organopolysiloxane of the present invention will be described in detail.
The (A) component organopolysiloxane has a general formula:
R 4 R 1 2 SiO (R 2 2 SiO) m SiR 1 2 R 4
It is represented by
　式中、Ｒ１およびＲ２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、または炭素数７～２０のアラルキル基である。具体的には、前記と同様の基が例示される。但し、全Ｒ２の少なくとも１０モル％は前記アリール基であり、好ましくは、フェニル基である。これは、得られるオルガノポリシロキサンの屈折率を高くすることができるからである。 In the formula, R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, the same groups as described above are exemplified. However, at least 10 mol% of all R 2 is the aryl group, preferably a phenyl group. This is because the refractive index of the resulting organopolysiloxane can be increased.
　また、式中、Ｒ４は、それぞれ独立して、炭素数２～６のアルケニル基である。具体的には、ビニル基、アリル基、イソプロペニル基、ブテニル基、イソブテニル基、ｔｅｒｔ－ブテニル基、ペンテニル基、イソペンテニル基、ヘキセニル基が例示され、好ましくは、ビニル基である。 In the formula, each R 4 is independently an alkenyl group having 2 to 6 carbon atoms. Specific examples include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, an isopentenyl group, and a hexenyl group, and a vinyl group is preferable.
　また、式中、ｍは５以上の整数であり、好ましくは、１０以上の整数である。これは、得られるオルガノポリシロキサンを配合する硬化性シリコーン組成物が、柔軟な硬化物を形成できるからである。一方、ｍは、好ましくは、１,０００以下の整数、または５００以下の整数である。これは、得られるオルガノポリシロキサン中のケイ素原子結合水素原子の反応性が損なわれないからである。 In the formula, m is an integer of 5 or more, and preferably an integer of 10 or more. This is because the curable silicone composition containing the resulting organopolysiloxane can form a flexible cured product. On the other hand, m is preferably an integer of 1,000 or less, or an integer of 500 or less. This is because the reactivity of silicon-bonded hydrogen atoms in the resulting organopolysiloxane is not impaired.
　このような（Ａ）成分としては、次のようなオルガノポリシロキサンが例示される。なお、式中、Ｍｅ、Ｐｈ、およびＶｉはそれぞれメチル基、フェニル基、およびビニル基を示し、ｍは５以上の整数を示す。
ＶｉＭｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)ｍＳｉＭｅ２Ｖｉ
ＶｉＭｅ２ＳｉＯ(Ｍｅ２ＳｉＯ)ｍＳｉＭｅ２Ｖｉ Examples of such component (A) include the following organopolysiloxanes. In the formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively, and m represents an integer of 5 or more.
ViMe 2 SiO (PhMeSiO) m SiMe 2 Vi
ViMe 2 SiO (Me 2 SiO) m SiMe 2 Vi
　（Ｂ）成分のオルガノジシロキサンは、一般式：
ＨＲ１ ２ＳｉＯＳｉＲ１ ２Ｈ
で表される。 The organodisiloxane of component (B) has the general formula:
HR 1 2 SiOSiR 1 2 H
It is represented by
　式中、Ｒ１は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、または炭素数７～２０のアラルキル基であり、前記と同様の基が例示される。 In the formula, each R 1 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and examples thereof include the same groups as described above. The
　このような（Ｂ）成分としては、次のようなオルガノジシロキサンが例示される。なお、式中、ＭｅおよびＰｈはそれぞれメチル基およびフェニル基を示す。
ＨＭｅ２ＳｉＯＳｉＭｅ２Ｈ
ＨＭｅＰｈＳｉＯＳｉＭｅＰｈＨ Examples of such component (B) include the following organodisiloxanes. In the formula, Me and Ph represent a methyl group and a phenyl group, respectively.
HMe 2 SiOSiMe 2 H
HMePhSiOSiMePhH
　（Ｂ）成分の添加量は、（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が１モルを超える量であり、好ましくは、２モル以上、または２.５モル以上となる量である。これは、（Ｂ）成分の添加量が過剰であればあるほど、効率よくオルガノポリシロキサンを製造することができるからである。一方、未反応の（Ｂ）成分を効率よく除去できることから、（Ｂ）成分の添加量は、（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が２０モル以下となる量であり、好ましくは、１５モル以下、１０モル以下、または８モル以下となる量である。 Component (B) is added in an amount such that the silicon-bonded hydrogen atom in this component exceeds 1 mol, preferably 2 mol or more, or 2 with respect to 1 mol of alkenyl group in component (A). It is the amount which becomes .5 mol or more. This is because the more the amount of component (B) added, the more efficiently the organopolysiloxane can be produced. On the other hand, since the unreacted component (B) can be efficiently removed, the amount of component (B) added is 20 moles of silicon-bonded hydrogen atoms in this component with respect to 1 mole of alkenyl group in component (A). The amount is less than or equal to a mole, and preferably less than or equal to 15 moles, less than or equal to 10 moles, or less than or equal to 8 moles.
　（Ａ）成分と（Ｂ）成分とのヒドロシリル化反応を促進するため、本発明の製造方法ではヒドロシリル化反応用触媒を用いることが好ましい。このヒドロシリル化反応用触媒は限定されず、白金系触媒、ロジウム系触媒、パラジウム系触媒が例示される。特に、ヒドロシリル化反応を著しく促進できることから白金系触媒であることが好ましい。この白金系触媒としては、白金微粉末、塩化白金酸、塩化白金酸のアルコール溶液、白金－アルケニルシロキサン錯体、白金－オレフィン錯体、白金－カルボニル錯体が例示され、特に、白金－アルケニルシロキサン錯体であることが好ましい。このアルケニルシロキサンとしては、１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン、１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン、これらのアルケニルシロキサンのメチル基の一部をエチル基、フェニル基等の基で置換したアルケニルシロキサン、これらのアルケニルシロキサンのビニル基をアリル基、ヘキセニル基等の基で置換したアルケニルシロキサンが例示される。 In order to promote the hydrosilylation reaction between the component (A) and the component (B), it is preferable to use a hydrosilylation reaction catalyst in the production method of the present invention. The catalyst for hydrosilylation reaction is not limited, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. In particular, a platinum-based catalyst is preferable because the hydrosilylation reaction can be significantly accelerated. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex, particularly platinum-alkenylsiloxane complex. It is preferable. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples include alkenyl siloxanes in which a part of the methyl groups of these alkenyl siloxanes are substituted with groups such as ethyl groups and phenyl groups, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with groups such as allyl groups and hexenyl groups. .
　このヒドロシリル化反応用触媒の添加量は限定されず、例えば、（Ａ）成分と（Ｂ）成分の合計量に対して、触媒金属が質量単位で０.０１～１,０００ｐｐｍの範囲内となる量であることが好ましく、さらには、０.１～５００ｐｐｍの範囲内となる量であることが好ましい。これは、ヒドロシリル化反応用触媒の添加量が上記範囲の下限以上であると、ヒドロシリル化反応を十分に促進でき、一方、上記範囲の上限以下であると、得られるオルガノポリシロキサンに着色等の問題を生じにくくなるからである。 The addition amount of the catalyst for hydrosilylation reaction is not limited. For example, the catalyst metal is in the range of 0.01 to 1,000 ppm in terms of mass unit with respect to the total amount of component (A) and component (B). Preferably, the amount is within the range of 0.1 to 500 ppm. This is because when the amount of the hydrosilylation reaction catalyst is at least the lower limit of the above range, the hydrosilylation reaction can be sufficiently promoted. On the other hand, when it is below the upper limit of the above range, the resulting organopolysiloxane can be colored. This is because problems are less likely to occur.
　このヒドロシリル化反応における反応条件は限定されず、加熱により反応を促進することができる。また、この反応において、トルエン、キシレン等の芳香族系溶剤；ヘプタン、ヘキサン等の脂肪族系溶剤等の溶剤を用いる場合には、反応温度は溶剤の還流温度であることが好ましく、有機溶媒を用いない場合には、２００℃以下であることが好ましい。なお、この反応において、有機溶剤を用いることにより、反応系の粘度を低下させると共に、反応系から水を共沸等により脱水することができる。 The reaction conditions in this hydrosilylation reaction are not limited, and the reaction can be promoted by heating. In this reaction, when an aromatic solvent such as toluene or xylene; a solvent such as an aliphatic solvent such as heptane or hexane is used, the reaction temperature is preferably the reflux temperature of the solvent. When not used, it is preferably 200 ° C. or lower. In this reaction, by using an organic solvent, the viscosity of the reaction system can be reduced, and water can be dehydrated from the reaction system by azeotropic distillation or the like.
　このようにして得られるオルガノポリシロキサンは、分子鎖両末端にケイ素原子結合水素原子を有しているので、ヒドロシリル化反応硬化性シリコーン組成物に配合することにより、ヒドロシリル化反応して、硬化物中に組み込まれ、表面タックが小さく、適度な弾性率を有する硬化物を形成することができる。特に、このオルガノポリシロキサンは、分子中にアリール基を有するので、屈折率の高いヒドロシリル化反応硬化性シリコーン組成物の構成成分として好適である。 The organopolysiloxane thus obtained has silicon-bonded hydrogen atoms at both ends of the molecular chain. Therefore, by adding it to the hydrosilylation reaction-curable silicone composition, it undergoes a hydrosilylation reaction to produce a cured product. A cured product that is incorporated therein, has a small surface tack, and an appropriate elastic modulus can be formed. In particular, this organopolysiloxane has an aryl group in the molecule, and thus is suitable as a component of a hydrosilylation reaction-curable silicone composition having a high refractive index.
　このような硬化性シリコーン組成物としては、例えば、
（Ｉ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、
（II）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン｛（Ｉ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０.１～１０モルとなる量｝、
（III）本発明のオルガノポリシロキサン（本組成物に対して０.１～５０質量％）、および
（IV）ヒドロシリル化反応用触媒（本組成物の硬化を促進する量）
から少なくともなるヒドロシリル化反応硬化性シリコーン組成物が挙げられる。 As such a curable silicone composition, for example,
(I) an organopolysiloxane having at least two alkenyl groups in one molecule;
(II) Organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule {the silicon atom-bonded hydrogen atom in this component is 0. 1 to 10 mol}
(III) The organopolysiloxane of the present invention (0.1 to 50% by mass with respect to the present composition), and (IV) a catalyst for hydrosilylation reaction (an amount that promotes curing of the present composition)
And a hydrosilylation reaction-curable silicone composition comprising at least
　（Ｉ）成分は一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサンである。（Ｉ）成分中のアルケニル基としては、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基等の炭素数が２～１２個のアルケニル基が例示され、好ましくは、ビニル基である。また、（Ｉ）成分中のアルケニル基以外のケイ素原子に結合する基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の炭素数が１～１２個のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等の炭素数が６～２０個のアリール基；ベンジル基、フェネチル基、フェニルプロピル基等の炭素数が７～２０個のアラルキル基；これらの基の水素原子の一部または全部をフッ素原子、塩素原子、臭素原子等のハロゲン原子で置換した基が例示される。なお、（Ｉ）成分中のケイ素原子には、本発明の目的を損なわない範囲で、少量の水酸基やメトキシ基、エトキシ基等のアルコキシ基を有していてもよい。 Component (I) is an organopolysiloxane having at least two alkenyl groups in one molecule. As the alkenyl group in component (I), the number of carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group and the like is 2 to Twelve alkenyl groups are exemplified, and a vinyl group is preferable. Examples of the group bonded to the silicon atom other than the alkenyl group in the component (I) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, Alkyl groups having 1 to 12 carbon atoms such as hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group; carbon such as phenyl group, tolyl group, xylyl group and naphthyl group An aryl group having 6 to 20 carbon atoms; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group, a phenethyl group, and a phenylpropyl group; a part or all of hydrogen atoms of these groups may be a fluorine atom, a chlorine atom, Examples thereof include a group substituted with a halogen atom such as a bromine atom. In addition, the silicon atom in the component (I) may have a small amount of an alkoxy group such as a hydroxyl group, a methoxy group, and an ethoxy group within a range not impairing the object of the present invention.
　（Ｉ）成分の分子構造は限定されないが、例えば、直鎖状、一部分岐を有する直鎖状、分岐鎖状、環状、または三次元網状構造が挙げられる。（Ｉ）成分は、これらの分子構造を有する単独のオルガノポリシロキサン、あるいはこれらの分子構造を有する二種以上のオルガノポリシロキサンの混合物であってもよい。 The molecular structure of the component (I) is not limited, and examples thereof include a straight chain, a partially branched straight chain, a branched chain, a ring, or a three-dimensional network structure. Component (I) may be a single organopolysiloxane having these molecular structures, or a mixture of two or more organopolysiloxanes having these molecular structures.
　（II）成分は一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサンである。（II）成分中の水素原子以外のケイ素原子に結合する基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の炭素数が１～１２個のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等の炭素数が６～２０個のアリール基；ベンジル基、フェネチル基、フェニルプロピル基等の炭素数が７～２０個のアラルキル基；これらの基の水素原子の一部または全部をフッ素原子、塩素原子、臭素原子等のハロゲン原子で置換した基が例示される。なお、（II）成分中のケイ素原子には、本発明の目的を損なわない範囲で、少量の水酸基やメトキシ基、エトキシ基等のアルコキシ基を有していてもよい。 Component (II) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. (II) The group bonded to the silicon atom other than the hydrogen atom in the component includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group Alkyl groups having 1 to 12 carbon atoms such as cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like; phenyl group, tolyl group, xylyl group, naphthyl group, etc. 6 to 20 aryl groups; aralkyl groups having 7 to 20 carbon atoms such as benzyl group, phenethyl group and phenylpropyl group; some or all of hydrogen atoms of these groups are fluorine atom, chlorine atom, bromine atom And a group substituted with a halogen atom such as In addition, the silicon atom in the component (II) may have a small amount of a hydroxyl group, an alkoxy group such as a methoxy group, an ethoxy group or the like as long as the object of the present invention is not impaired.
　（II）成分の分子構造は限定されないが、例えば、直鎖状、一部分岐を有する直鎖状、分岐鎖状、環状、または三次元網状構造が挙げられ、好ましくは、一部分岐を有する直鎖状、分岐鎖状、または三次元網状構造である。 The molecular structure of the component (II) is not limited, and examples thereof include linear, partially branched linear, branched, cyclic, or three-dimensional network structure, and preferably partially branched linear , Branched chain, or three-dimensional network structure.
　（II）成分としては、例えば、１,１,３,３－テトラメチルジシロキサン、１,３,５,７－テトラメチルシクロテトラシロキサン、トリス(ジメチルハイドロジェンシロキシ)メチルシラン、トリス(ジメチルハイドロジェンシロキシ)フェニルシラン、１－グリシドキシプロピル－１,３,５,７－テトラメチルシクロテトラシロキサン、１,５－ジグリシドキシプロピル－１,３,５,７－テトラメチルシクロテトラシロキサン、１－グリシドキシプロピル－５－トリメトキシシリルエチル－１,３,５,７－テトラメチルシクロテトラシロキサン、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、(ＣＨ３)２ＨＳiＯ１/２単位とＳiＯ４/２単位とからなる共重合体、および(ＣＨ３)２ＨＳiＯ１/２単位とＳiＯ４/２単位と(Ｃ６Ｈ５)ＳiＯ３/２単位とからなる共重合体等からなる群から選ばれる１種又は２種以上が挙げられる。 Examples of the component (II) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogen). Siloxy) phenylsilane, 1-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-diglycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1 -Glycidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, molecular chain both ends trimethylsiloxy group blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group blocked dimethyl Siloxane / methylhydrogensiloxane copolymer, dimethyl high at both ends of the molecular chain Drogensiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, molecule Trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer having both chain ends, a copolymer comprising (CH 3 ) 2 HSiO 1/2 unit and SiO 4/2 unit, and (CH 3 ) 2 One type or two or more types selected from the group consisting of copolymers composed of HSiO 1/2 units, SiO 4/2 units, and (C 6 H 5 ) SiO 3/2 units may be mentioned.
　（II）成分の含有量は、（Ｉ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０.１～１０モルとなる量であり、好ましくは、０.５～５モルとなる量である。これは、（II）成分の含有量が上記範囲の上限以下であると、得られる硬化物の機械的特性の低下を抑えることができるからであり、一方、上記範囲の下限以上であると、得られる組成物が十分に硬化するからである。 The content of the component (II) is such that the silicon-bonded hydrogen atom in this component is 0.1 to 10 mol, preferably 0.1 to 1 mol of the alkenyl group in the component (I). The amount is 5 to 5 mol. This is because if the content of the component (II) is not more than the upper limit of the above range, it is possible to suppress a decrease in the mechanical properties of the resulting cured product, whereas, if not less than the lower limit of the above range, This is because the resulting composition is sufficiently cured.
　（III）成分のオルガノポリシロキサンは上記のとおりである。（III）成分の含有量は、本組成物に対して、０.１～５０質量％の範囲内となる量、好ましくは、５～３５質量％の範囲内となる量である。これは、（III）成分の含有量が上記範囲の下限以上であると、得られる硬化物に十分な柔軟性を付与できるからであり、一方、上記範囲の上限以下であると、得られる硬化物の機械的強度を低下させないからである。 The organopolysiloxane of component (III) is as described above. The content of the component (III) is an amount that falls within the range of 0.1 to 50% by mass, preferably an amount that falls within the range of 5 to 35% by mass with respect to the present composition. This is because when the content of the component (III) is not less than the lower limit of the above range, sufficient flexibility can be imparted to the obtained cured product, and on the other hand, if the content is not more than the upper limit of the above range, the resulting cure can be obtained. This is because the mechanical strength of the object is not lowered.
　（IV）成分は、本組成物のヒドロシリル化反応を促進するためのヒドロシリル化反応用触媒である。このような（IV）成分のヒドロシリル化反応用触媒は限定されず、白金系触媒、ロジウム系触媒、パラジウム系触媒が例示される。特に、ヒドロシリル化反応を著しく促進できることから白金系触媒であることが好ましい。この白金系触媒としては、前記と同様の触媒が例示される。 The component (IV) is a hydrosilylation catalyst for promoting the hydrosilylation reaction of the composition. Such a catalyst for hydrosilylation reaction of the component (IV) is not limited, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. In particular, a platinum-based catalyst is preferable because the hydrosilylation reaction can be significantly accelerated. Examples of the platinum-based catalyst include the same catalysts as described above.
　（IV）成分の含有量は、本組成物の硬化を促進する量であり、好ましくは、本組成物に対して、（IV）成分中の白金原子が質量単位で０.０１～５００ｐｐｍの範囲内となる量、０.０１～１００ｐｐｍの範囲内となる量、または、０.１～５０ｐｐｍの範囲内となる量である。これは、（IV）成分の含有量が上記範囲の下限以上であると、得られる組成物が十分に硬化するからであり、一方、上記範囲の上限以下であると、得られる硬化物の着色が抑えられるからである。 The content of the component (IV) is an amount that promotes the curing of the present composition, and preferably the platinum atom in the component (IV) is in the range of 0.01 to 500 ppm by mass with respect to the present composition. Is an amount that falls within the range of 0.01 to 100 ppm, or an amount that falls within the range of 0.1 to 50 ppm. This is because the composition obtained is sufficiently cured when the content of the component (IV) is equal to or higher than the lower limit of the above range, and on the other hand, when the content is equal to or lower than the upper limit of the above range, the resulting cured product is colored. It is because it is suppressed.
　本組成物には、常温での可使時間を延長し、保存安定性を向上させるための任意の成分として、（Ｅ）ヒドロシリル化反応抑制剤を含有してもよい。このような（Ｅ）成分としては、１－エチニルシクロヘキサン－１－オール、２－メチル－３－ブチン－２－オール、３,５－ジメチル－１－ヘキシン－３－オール、および２－フェニル－３－ブチン－２－オール等のアルキンアルコール；３－メチル－３－ペンテン－１－イン、および３,５－ジメチル－３－ヘキセン－１－イン等のエンイン化合物；１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン、および１,３,５,７－テトラメチル－１,３,５,７－テトラヘキセニルシクロテトラシロキサン等のメチルアルケニルシロキサンオリゴマー；ジメチルビス(１,１－ジメチルブチンオキシ)シラン、およびメチルビニルビス(１,１－ジメチルブチンオキシ)シラン等のアルキンオキシシラン、並びにトリアリルイソシアヌレート系化合物が例示される。 This composition may contain (E) a hydrosilylation reaction inhibitor as an optional component for extending the pot life at room temperature and improving the storage stability. Examples of such component (E) include 1-ethynylcyclohexane-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl- Alkyne alcohols such as 3-butyn-2-ol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7 A methyl alkenyl siloxane oligomer such as tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; Alkyneoxysilanes such as dimethylbis (1,1-dimethylbutyneoxy) silane and methylvinylbis (1,1-dimethylbutyneoxy) silane; Isocyanurate-based compounds.
　また、本組成物には、硬化中に接触している基材への接着性を更に向上させるために、接着促進剤を含有してもよい。この接着促進剤としては、ケイ素原子に結合したアルコキシ基を一分子中に１個以上有する有機ケイ素化合物が好ましい。このアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、およびメトキシエトキシ基等が例示され、特に、メトキシ基またはエトキシ基が好ましい。また、この有機ケイ素化合物のケイ素原子に結合するアルコキシ基以外の基としては、アルキル基、アルケニル基、アリール基、アラルキル基、およびハロゲン化アルキル基等のハロゲン置換もしくは非置換の一価炭化水素基；３－グリシドキシプロピル基、および４－グリシドキシブチル基等のグリシドキシアルキル基；２－(３,４－エポキシシクロヘキシル)エチル基、および３－(３,４－エポキシシクロヘキシル)プロピル基等のエポキシシクロヘキシルアルキル基；４－エポキシブチル基、および８－エポキシオクチル基等のエポキシアルキル基；３－メタクリロキシプロピル基；イソシアネート基；イソシアヌレート基；並びに水素原子が例示される。 The composition may also contain an adhesion promoter in order to further improve the adhesion to the substrate that is in contact during curing. As this adhesion promoter, an organosilicon compound having at least one alkoxy group bonded to a silicon atom in one molecule is preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group or an ethoxy group is particularly preferable. The group other than the alkoxy group bonded to the silicon atom of the organosilicon compound includes halogen-substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups. Glycidoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl Examples include an epoxycyclohexylalkyl group such as a group; an epoxyalkyl group such as a 4-epoxybutyl group and an 8-epoxyoctyl group; a 3-methacryloxypropyl group; an isocyanate group; an isocyanurate group; and a hydrogen atom.
　また、本組成物には、本発明の目的を損なわない限り、その他の任意の成分として、シリカ、ガラス、およびアルミナ等から選択される１種又は２種以上の無機質充填剤；シリコーンゴム粉末；シリコーン樹脂、およびポリメタクリレート樹脂等の樹脂粉末；耐熱剤、染料、顔料、難燃性付与剤、界面活性剤、溶剤等から選択される１種以上の成分を含有してもよい。 In addition, in the present composition, as long as the object of the present invention is not impaired, one or more inorganic fillers selected from silica, glass, alumina and the like as other optional components; silicone rubber powder; Resin powder such as silicone resin and polymethacrylate resin; one or more components selected from heat-resistant agents, dyes, pigments, flame retardants, surfactants, solvents and the like may be contained.
　本発明のオルガノポリシロキサン、その製造方法、および硬化性シリコーン組成物を実施例により詳細に説明する。なお、実施例中の粘度は２５℃における値である。また、式中、Ｍｅ、Ｐｈ、Ｖｉ、およびＥｐはそれぞれメチル基、フェニル基、ビニル基、および３－グリシドキシプロピル基を示す。 The organopolysiloxane of the present invention, its production method, and curable silicone composition will be described in detail with reference to examples. In addition, the viscosity in an Example is a value in 25 degreeC. In the formula, Me, Ph, Vi, and Ep represent a methyl group, a phenyl group, a vinyl group, and a 3-glycidoxypropyl group, respectively.
［実施例１］
　反応容器に、トルエン　１９９.９７ｇ、式：
ＶｉＭｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)２０ＳｉＭｅ２Ｖｉ
で表されるジオルガノポリシロキサン（屈折率１.５４３８、粘度２,６２５ｍＰａ・ｓ、質量平均分子量４,０４２）　１６７.５１ｇ、および式：
ＨＭｅ２ＳｉＯＳｉＭｅ２Ｈ
で表されるジシロキサン　１５.００ｇ（上記ジオルガノポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が３モルとなる量）を投入し、１０６℃で共沸脱水した後、室温に冷却した。 [Example 1]
In a reaction vessel, 199.97 g of toluene, formula:
ViMe 2 SiO (PhMeSiO) 20 SiMe 2 Vi
167.51 g of a diorganopolysiloxane represented by the following formula (refractive index 1.5438, viscosity 2,625 mPa · s, mass average molecular weight 4,042), and the formula:
HMe 2 SiOSiMe 2 H
15.00 g of disiloxane represented by the formula (in which 3 mol of silicon-bonded hydrogen atoms in this component is 3 mol with respect to 1 mol of vinyl group in the diorganopolysiloxane) is azeotroped at 106 ° C. After dehydration, it was cooled to room temperature.
　次に、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン錯体（本錯体中の白金金属が上記ジオルガノポリシロキサンと上記ジシロキサンの合計量に対して質量単位で５ｐｐｍとなる量）を添加し、１１１℃～１１２℃のトルエン還流温度で３時間反応させた。その後、室温に冷却し、活性炭　７.４ｇを混合した後、ガラスフィルターでろ過した。ろ液を４ｍｍＨｇ、１００℃の加熱減圧によりトルエンと未反応ジシロキサンを留去し、屈折率１.５３３９、粘度１,４５３ｍＰａ・ｓ、質量平均分子量５,１４０の透明液体を得た。この液体は、式：
ＨＭｅ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)２０ＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＳｉＭｅ２Ｈ
で表されるオルガノポリシロキサンであることがわかった。 Next, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in this complex is expressed in mass units with respect to the total amount of the diorganopolysiloxane and the disiloxane). 5 ppm) was added, and the mixture was reacted at a toluene reflux temperature of 111 ° C. to 112 ° C. for 3 hours. Then, after cooling to room temperature and mixing 7.4g of activated carbon, it filtered with the glass filter. Toluene and unreacted disiloxane were distilled off from the filtrate by heating under reduced pressure at 4 mmHg and 100 ° C. to obtain a transparent liquid having a refractive index of 1.5339, a viscosity of 1,453 mPa · s, and a mass average molecular weight of 5,140. This liquid has the formula:
HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) 20 SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H
It was found that the organopolysiloxane represented by
［実施例２］
　反応容器に、トルエン　１７２.９１ｇ、一般式：
ＶｉＭｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)ｎＳｉＭｅ２Ｖｉ
（式中、ｎは約１００である。）
で表されるジオルガノポリシロキサン（質量平均分子量１５,８００、屈折率１.５５１２、粘度４１,２５０ｍＰａ・ｓ）　１２４.７２ｇ、および式：
ＨＭｅ２ＳｉＯＳｉＭｅ２Ｈ
で表されるジシロキサン　２.５０ｇ（上記ジオルガノポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が４モルとなる量）を投入し、共沸脱水した後、室温に冷却した。 [Example 2]
In a reaction vessel, 172.91 g of toluene, general formula:
ViMe 2 SiO (PhMeSiO) n SiMe 2 Vi
(In the formula, n is about 100.)
Diorganopolysiloxane (mass average molecular weight 15,800, refractive index 1.5512, viscosity 41,250 mPa · s) 124.72 g, and formula:
HMe 2 SiOSiMe 2 H
After adding 2.50 g of disiloxane represented by the following formula (amount in which 4 moles of silicon-bonded hydrogen atoms in this component are 4 moles per mole of vinyl groups in the diorganopolysiloxane): And cooled to room temperature.
　次に、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン錯体（本錯体中の白金金属が上記ジオルガノポリシロキサンと上記ジシロキサンの合計量に対して質量単位で５ｐｐｍとなる量）を添加し、１０７℃～１１１℃のトルエン還流温度で２.２時間反応させた。その後、室温に冷却し、活性炭　８.１ｇを混合した後、ガラスフィルターでろ過した。ろ液を４ｍｍＨｇ、１１９℃の加熱減圧によりトルエンと未反応ジシロキサンを留去し、屈折率１.５４７７、粘度５１,６２５ｍＰａ・ｓ、質量平均分子量が２０,４８２の透明液体を得た。この液体は、一般式：
ＨＭｅ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)ｎＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＳｉＭｅ２Ｈ
（式中、ｎは約１００である。）
で表されるオルガノポリシロキサンであることがわかった。 Next, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in this complex is expressed in mass units with respect to the total amount of the diorganopolysiloxane and the disiloxane). 5 ppm) was added, and the reaction was carried out at a toluene reflux temperature of 107 ° C. to 111 ° C. for 2.2 hours. Thereafter, the mixture was cooled to room temperature, mixed with 8.1 g of activated carbon, and filtered through a glass filter. Toluene and unreacted disiloxane were distilled off from the filtrate by heating under reduced pressure at 4 mmHg and 119 ° C. to obtain a transparent liquid having a refractive index of 1.5477, a viscosity of 51,625 mPa · s, and a mass average molecular weight of 20,482. This liquid has the general formula:
HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) n SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H
(In the formula, n is about 100.)
It was found that the organopolysiloxane represented by
［実施例３］
　反応容器に、トルエン　１７２.９１ｇ、一般式：
ＶｉＭｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)ｍＳｉＭｅ２Ｖｉ
（式中、ｍは約８である。）
で表されるジオルガノポリシロキサン（質量平均分子量１,２５０、屈折率１.５６５、粘度１,０００ｍＰａ・ｓ）　１６３.０３ｇ、および式：
ＨＭｅ２ＳｉＯＳｉＭｅ２Ｈ
で表されるジシロキサン　４７.９９ｇ（上記ジオルガノポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が２.６モルとなる量）を投入し、共沸脱水した後、室温に冷却した。 [Example 3]
In a reaction vessel, 172.91 g of toluene, general formula:
ViMe 2 SiO (PhMeSiO) m SiMe 2 Vi
(Where m is about 8)
Diorganopolysiloxane (mass average molecular weight 1,250, refractive index 1.565, viscosity 1,000 mPa · s) 163.03 g, and formula:
HMe 2 SiOSiMe 2 H
49.9 g of disiloxane represented by the formula (in which the amount of silicon-bonded hydrogen atoms in this component is 2.6 mol with respect to 1 mol of vinyl group in the diorganopolysiloxane) is added, and azeotropic dehydration is performed. And then cooled to room temperature.
　次に、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン錯体（本錯体中の白金金属が上記ジオルガノポリシロキサンと上記ジシロキサンの合計量に対して質量単位で５ｐｐｍとなる量）を添加し、１００℃～１２０℃のトルエン還流温度で２.５時間反応させた。その後、室温に冷却し、活性炭　１３.３ｇを混合した後、ガラスフィルターでろ過した。ろ液を６ｍｍＨｇ、１００℃の加熱減圧によりトルエンと未反応ジシロキサンを留去し、屈折率１.５１１４、粘度１,０２０ｍＰａ・ｓ、質量平均分子量１,８８０の透明液体を得た。この液体は、一般式：
ＨＭｅ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)ｍＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＳｉＭｅ２Ｈ
（式中、ｍは約８である。）
で表されるオルガノポリシロキサンであることがわかった。 Next, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in this complex is expressed in mass units with respect to the total amount of the diorganopolysiloxane and the disiloxane). 5 ppm) was added, and the mixture was reacted at a toluene reflux temperature of 100 ° C. to 120 ° C. for 2.5 hours. Thereafter, the mixture was cooled to room temperature, mixed with 13.3 g of activated carbon, and then filtered through a glass filter. Toluene and unreacted disiloxane were distilled off from the filtrate by heating under reduced pressure at 6 mmHg and 100 ° C. to obtain a transparent liquid having a refractive index of 1.5114, a viscosity of 1,020 mPa · s, and a mass average molecular weight of 1,880. This liquid has the general formula:
HMe 2 SiOSiMe 2 —C 2 H 4 —Me 2 SiO (PhMeSiO) m SiMe 2 —C 2 H 4 —Me 2 SiOSiMe 2 H
(Where m is about 8)
It was found that the organopolysiloxane represented by
［実施例４］
　反応容器に、トルエン　１２４.８９ｇ、式：：
ＶｉＭｅＰｈＳｉＯ(Ｐｈ２ＳｉＯ)１３(Ｍｅ２ＳｉＯ)１９ＳｉＭｅＰｈＶｉ
で表される、室温で粘稠な液状のジオルガノポリシロキサン（質量平均分子量５,１００、屈折率１.５８２３）　６１.０７ｇ、および式：
ＨＭｅ２ＳｉＯＳｉＭｅ２Ｈ
で表されるジシロキサン　８.８１ｇ（上記ジオルガノポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が７モルとなる量）を投入し、共沸脱水した後、室温に冷却した。 [Example 4]
In a reaction vessel, 124.89 g of toluene, formula:
ViMePhSiO (Ph 2 SiO) 13 (Me 2 SiO) 19 SiMePhVi
61.07 g of a liquid diorganopolysiloxane that is viscous at room temperature (mass average molecular weight 5,100, refractive index 1.5823), and
HMe 2 SiOSiMe 2 H
After adding 8.81 g of disiloxane represented by the formula (amount of silicon-bonded hydrogen atoms in this component to 7 mol with respect to 1 mol of vinyl groups in the diorganopolysiloxane), And cooled to room temperature.
　次に、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン錯体（本錯体中の白金金属が上記ジオルガノポリシロキサンと上記ジシロキサンの合計量に対して質量単位で５ｐｐｍとなる量）を添加し、１１０℃～１１１℃のトルエン還流温度で３時間反応させた。その後、室温に冷却し、活性炭　１０.５ｇを混合した後、ガラスフィルターでろ過した。ろ液を６３ｍｍＨｇ、９９℃の加熱減圧によりトルエンと未反応ジシロキサンを留去し、屈折率１.５７２５、質量平均分子量５,７６０、室温で粘稠な透明液体を得た。この液体は、式：
ＨＭｅ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－ＭｅＰｈＳｉＯ(Ｐｈ２ＳｉＯ)１３(Ｍｅ２ＳｉＯ)１９ＳｉＭｅＰｈ－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＳｉＭｅ２Ｈ
で表されるオルガノポリシロキサンであった。 Next, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in this complex is expressed in mass units with respect to the total amount of the diorganopolysiloxane and the disiloxane). 5 ppm) was added, and the mixture was reacted at a toluene reflux temperature of 110 ° C. to 111 ° C. for 3 hours. Thereafter, the mixture was cooled to room temperature, mixed with 10.5 g of activated carbon, and filtered through a glass filter. Toluene and unreacted disiloxane were distilled off from the filtrate by heating under reduced pressure at 63 mmHg and 99 ° C. to obtain a transparent transparent liquid having a refractive index of 1.5725, a mass average molecular weight of 5,760, and room temperature. This liquid has the formula:
HMe 2 SiOSiMe 2 —C 2 H 4 —MePhSiO (Ph 2 SiO) 13 (Me 2 SiO) 19 SiMePh—C 2 H 4 —Me 2 SiOSiMe 2 H
It was the organopolysiloxane represented by these.
［比較例１］
　５０ｃｃガラス瓶に、式：
ＶｉＭｅ２ＳｉＯＰｈ２ＳｉＯＳｉＭｅ２Ｖｉ
で表されるビニル基含有ジオルガノポリシロキサン　１７.７０ｇ、および式：
ＨＭｅ２ＳｉＯＰｈ２ＳｉＯＳｉＭｅ２Ｈ
で表されるケイ素原子結合水素原子含有ジオルガノポリシロキサン（質量平均分子量１,５６０）　１７.１２ｇ（上記ビニル基含有ジオルガノポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が１.１モルとなる量）を投入し、室温下、マグネチックスターラーで攪拌混合した。 [Comparative Example 1]
In a 50cc glass bottle, the formula:
ViMe 2 SiOPh 2 SiOSiMe 2 Vi
17.70 g of a vinyl group-containing diorganopolysiloxane represented by the formula:
HMe 2 SiOPh 2 SiOSiMe 2 H
17. A silicon atom-bonded hydrogen atom-containing diorganopolysiloxane represented by the formula (mass average molecular weight 1,560) 17.12 g (the silicon atom in this component with respect to 1 mol of vinyl group in the vinyl group-containing diorganopolysiloxane) The amount of bonded hydrogen atoms to 1.1 mol) was added, and the mixture was stirred and mixed with a magnetic stirrer at room temperature.
　次に、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン錯体（本錯体中の白金金属が上記ビニル基含有ジオルガノポリシロキサンと上記ケイ素原子結合水素原子含有ジオルガノポリシロキサンの合計量に対して質量単位で５ｐｐｍとなる量）を添加し、発熱してやや褐色に変化した。これを１５０℃オーブンで１時間加熱した後、室温に冷却した。屈折率１.５３１１、粘度１０,４００ｍＰａ・ｓ、質量平均分子量が８,１２０のやや褐色の透明液体を得た。この液体は、式：
ＨＭｅ２ＳｉＯＰｈ２ＳｉＯＳｉＭｅ２－[Ｃ２Ｈ４－Ｍｅ２ＳｉＯＰｈ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＰｈ２ＳｉＯＳｉＭｅ２－]ｍ－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＰｈ２ＳｉＯＳｉＭｅ２－Ｃ２Ｈ４－Ｍｅ２ＳｉＯＰｈ２ＳｉＯＳｉＭｅ２Ｈ
（式中、ｍは８である。）
で表されるオルガノポリシロキサンであることがわかった。 Next, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (the platinum metal in this complex is the above-mentioned vinyl group-containing diorganopolysiloxane and the above silicon-bonded hydrogen atom-containing diorgano The amount of 5 ppm in terms of mass unit with respect to the total amount of polysiloxane) was added, and the color was slightly brown due to heat generation. This was heated in a 150 ° C. oven for 1 hour and then cooled to room temperature. A slightly brown transparent liquid having a refractive index of 1.5311, a viscosity of 10,400 mPa · s, and a weight average molecular weight of 8,120 was obtained. This liquid has the formula:
HMe 2 SiOPh 2 SiOSiMe 2- [C 2 H 4 -Me 2 SiOPh 2 SiOSiMe 2 -C 2 H 4 -Me 2 SiOPh 2 SiOSiMe 2- ] m -C 2 H 4 -Me 2 SiOPh 2 SiOSiMe 2 -C 2 H 4- Me 2 SiOPh 2 SiOSiMe 2 H
(In the formula, m is 8.)
It was found that the organopolysiloxane represented by
［参考例１］
　平均単位式：
(ＶｉＭｅ２ＳｉＯ１／２)０.２５(ＰｈＳｉＯ３／２)０.７５
で表される、２５℃で固体状のオルガノポリシロキサン　６８.５質量部、式：
ＨＭｅ２ＳｉＯＰｈ２ＳｉＯＳｉＨＭｅ２
で表されるオルガノトリシロキサン　２３.８質量部、平均単位式：
(ＨＭｅ２ＳｉＯ１／２)０.６(ＰｈＳｉＯ３／２)０.４
で表されるオルガノポリシロキサン　２.９質量部、平均単位式：
(ＶｉＭｅ２ＳｉＯ１／２)０.２０(ＰｈＳｉＯ３／２)０.５５(ＥｐＭｅＳｉＯ２／２)０.２５
で表されるオルガノポリシロキサン　２.９質量部、１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン　１.０質量部、式：
(ＶｉＭｅ２ＳｉＯ)３ＳｉＰｈ
で表されるオルガノポリシロキサン　１.０質量部、
白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン錯体（本錯体中の白金金属が本組成物に対して質量単位で５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物を調製した。この硬化性シリコーン組成物を厚み１ｍｍ、長さ２０ｍｍ、１０ｍｍの板状に硬化して、得られた硬化物をＡＲＥＳ粘弾性測定装置（Ｒｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社製のＲＤＡ７００）を使用して、測定間隔１５ｍｍ、ねじれ０.５％、振動数１Ｈｚの条件で室温での貯蔵弾性率の貯蔵弾性率を測定した。その貯蔵弾性率は３５０ＭＰａであった。 [Reference Example 1]
Average unit formula:
(ViMe 2 SiO 1/2 ) 0.25 (PhSiO 3/2 ) 0.75
68.5 parts by mass of an organopolysiloxane solid at 25 ° C. represented by the formula:
HMe 2 SiOPh 2 SiOSiHMe 2
23.8 parts by mass of an organotrisiloxane represented by the formula:
(HMe 2 SiO 1/2 ) 0.6 (PhSiO 3/2 ) 0.4
2.9 parts by mass of an organopolysiloxane represented by the formula:
(ViMe 2 SiO 1/2 ) 0.20 (PhSiO 3/2 ) 0.55 (EpMeSiO 2/2 ) 0.25
2.9 parts by mass of an organopolysiloxane represented by the formula: 1.0 part by mass of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, the formula:
(ViMe 2 SiO) 3 SiPh
1.0 part by mass of an organopolysiloxane represented by
Mixing with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (amount in which platinum metal in this complex is 5 ppm in mass units with respect to the composition) A silicone composition was prepared. This curable silicone composition was cured into a plate having a thickness of 1 mm, a length of 20 mm, and a length of 10 mm, and the obtained cured product was measured at an interval of 15 mm using an ARES viscoelasticity measuring apparatus (RDA700 manufactured by Reometric Scientific). The storage elastic modulus of the storage elastic modulus at room temperature was measured under the conditions of a twist of 0.5% and a frequency of 1 Hz. The storage elastic modulus was 350 MPa.
［実施例５］
　参考例１で調製した硬化性シリコーン組成物　８０質量部に、実施例１で調製したオルガノポリシロキサン　２０質量部を配合して、硬化性シリコーン組成物を調製した。この硬化性シリコーン組成物を硬化して得られた硬化物の貯蔵弾性率は３ＭＰａであり、硬化物の表面には粘着性がなかった。 [Example 5]
A curable silicone composition was prepared by blending 20 parts by mass of the organopolysiloxane prepared in Example 1 with 80 parts by mass of the curable silicone composition prepared in Reference Example 1. The cured product obtained by curing this curable silicone composition had a storage elastic modulus of 3 MPa, and the surface of the cured product was not sticky.
［比較例２］
　参考例１で調製した硬化性シリコーン組成物　８０質量部に、式：
ＶｉＭｅ２ＳｉＯ(ＰｈＭｅＳｉＯ)２０ＳｉＭｅ２Ｖｉ
で表されるジオルガノポリシロキサン（屈折率１.５４３８、粘度２,６２５ｍＰａ・ｓ、質量平均分子量４,０４２）　２０質量部を配合して、硬化性シリコーン組成物を調製した。この硬化性シリコーン組成物を硬化して得られた硬化物の貯蔵弾性率は１１ＭＰａであった。 [Comparative Example 2]
In 80 parts by mass of the curable silicone composition prepared in Reference Example 1, the formula:
ViMe 2 SiO (PhMeSiO) 20 SiMe 2 Vi
Embedded image (refractive index 1.5438, viscosity 2,625 mPa · s, mass average molecular weight 4,042) 20 parts by mass was blended to prepare a curable silicone composition. The storage elastic modulus of the cured product obtained by curing this curable silicone composition was 11 MPa.
　本発明のオルガノポリシロキサンは、分子鎖両末端にケイ素原子結合水素原子を有するので、ヒドロシリル化反応硬化性シリコーン組成物の構成成分として使用することができる。このような硬化性シリコーン組成物は、柔軟な硬化物を形成できるので、電気・電子用の接着剤、ポッティング剤、保護コーティング剤、アンダーフィル剤として使用することができ、特に、光学用途の半導体素子の接着剤、ポッティング剤、保護コーティング剤、アンダーフィル剤として好適である。 Since the organopolysiloxane of the present invention has silicon-bonded hydrogen atoms at both ends of the molecular chain, it can be used as a component of the hydrosilylation reaction-curable silicone composition. Since such a curable silicone composition can form a flexible cured product, it can be used as an adhesive for electric and electronic, a potting agent, a protective coating agent, and an underfill agent. It is suitable as an element adhesive, potting agent, protective coating agent, and underfill agent.

Claims (7)

  1. 　一般式：
    ＨＲ１ ２ＳｉＯＳｉＲ１ ２－Ｒ３－Ｒ１ ２ＳｉＯ(Ｒ２ ２ＳｉＯ)ｍＳｉＲ１ ２－Ｒ３－Ｒ１ ２ＳｉＯＳｉＲ１ ２Ｈ
    （式中、Ｒ１およびＲ２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、または炭素数７～２０のアラルキル基であり、但し、全Ｒ２の少なくとも１０モル％は前記アリール基であり、Ｒ３は、それぞれ独立して、炭素数２～６のアルキレン基であり、ｍは５以上の整数である。）
    で表されるオルガノポリシロキサン。     General formula:
    HR 1 2 SiOSiR 1 2 -R 3 -R 1 2 SiO (R 2 2 SiO) m SiR 1 2 -R 3 -R 1 2 SiOSiR 1 2 H
    (Wherein R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, provided that all R (At least 10 mol% of 2 is the aryl group, each R 3 is independently an alkylene group having 2 to 6 carbon atoms, and m is an integer of 5 or more.)
    An organopolysiloxane represented by
  2. 　一般式：
    (Ｒ２ ２ＳｉＯ)ｍ
    で表されるジオルガノシロキサンブロックが、ジフェニルシロキサン単位またはメチルフェニルシロキサン単位を含む、請求項１に記載のオルガノポリシロキサン。     General formula:
    (R 2 2 SiO) m
    The organopolysiloxane of Claim 1 in which the diorganosiloxane block represented by these contains a diphenylsiloxane unit or a methylphenylsiloxane unit.
  3. 　ｍが１０以上の整数である、請求項１または２に記載のオルガノポリシロキサン。 The organopolysiloxane according to claim 1 or 2, wherein m is an integer of 10 or more.
  4. 　可視光（５８９ｎｍ）における屈折率（２５℃）が１.５０以上である、請求項１乃至３のいずれか１項に記載のオルガノポリシロキサン。 The organopolysiloxane according to any one of claims 1 to 3, wherein a refractive index (25 ° C) in visible light (589 nm) is 1.50 or more.
  5. （Ａ）一般式：
    Ｒ４Ｒ１ ２ＳｉＯ(Ｒ２ ２ＳｉＯ)ｍＳｉＲ１ ２Ｒ４
    （式中、Ｒ１およびＲ２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、または炭素数７～２０のアラルキル基であり、但し、全Ｒ２の少なくとも１０モル％は前記アリール基であり、Ｒ４は、それぞれ独立して、炭素数２～６のアルケニル基であり、ｍは５以上の整数である。）
    で表されるオルガノポリシロキサンと
    （Ｂ）一般式：
    ＨＲ１ ２ＳｉＯＳｉＲ１ ２Ｈ
    （式中、Ｒ１は前記と同じである。）
    で表されるオルガノジシロキサンを、（Ａ）成分中のアルケニル基１モルに対して、（Ｂ）成分中のケイ素原子結合水素原子が１モルを超える量でヒドロシリル化反応してなる、請求項１記載のオルガノポリシロキサンの製造方法。     (A) General formula:
    R 4 R 1 2 SiO (R 2 2 SiO) m SiR 1 2 R 4
    (Wherein R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, provided that all R (At least 10 mol% of 2 is the aryl group, each R 4 is independently an alkenyl group having 2 to 6 carbon atoms, and m is an integer of 5 or more.)
    And (B) the general formula:
    HR 1 2 SiOSiR 1 2 H
    (In the formula, R 1 is the same as described above.)
    The organodisiloxane represented by the formula (1) is obtained by hydrosilylation reaction in such an amount that the silicon-bonded hydrogen atom in the component (B) exceeds 1 mol with respect to 1 mol of the alkenyl group in the component (A). The method for producing an organopolysiloxane according to 1.
  6. 　請求項１乃至４のいずれか１項に記載のオルガノポリシロキサンを含有するヒドロシリル化反応硬化性シリコーン組成物。 A hydrosilylation reaction-curable silicone composition containing the organopolysiloxane according to any one of claims 1 to 4.
  7. 　ヒドロシリル化反応硬化性シリコーン組成物が、
    （Ｉ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、
    （II）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン｛（Ｉ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０.１～１０モルとなる量｝、
    （III）請求項１乃至４のいずれか１項に記載のオルガノポリシロキサン（本組成物に対して０.１～５０質量％）、および
    （IV）ヒドロシリル化反応用触媒（本組成物の硬化を促進する量）
    から少なくともなる、請求項６記載のヒドロシリル化反応硬化性シリコーン組成物。     The hydrosilylation reaction curable silicone composition is
    (I) an organopolysiloxane having at least two alkenyl groups in one molecule;
    (II) Organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule {the silicon atom-bonded hydrogen atom in this component is 0. 1 to 10 mol}
    (III) The organopolysiloxane according to any one of claims 1 to 4 (0.1 to 50% by mass relative to the present composition), and (IV) a catalyst for hydrosilylation reaction (curing of the present composition) Promoting amount)
    The hydrosilylation reaction-curable silicone composition according to claim 6, comprising at least
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