WO2017043328A1 - Crosslinkable organopolysiloxane composition and cured object obtained therefrom - Google Patents

Crosslinkable organopolysiloxane composition and cured object obtained therefrom Download PDF

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WO2017043328A1
WO2017043328A1 PCT/JP2016/074899 JP2016074899W WO2017043328A1 WO 2017043328 A1 WO2017043328 A1 WO 2017043328A1 JP 2016074899 W JP2016074899 W JP 2016074899W WO 2017043328 A1 WO2017043328 A1 WO 2017043328A1
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sio
group
component
alkenyl
organopolysiloxane
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PCT/JP2016/074899
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French (fr)
Japanese (ja)
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明彦 白幡
広之 内田
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ケイ素材料開発株式会社
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  • the present invention relates to a crosslinkable organopolysiloxane composition that can be rapidly crosslinked by a hydrosilylation reaction to form a cured product having no surface tack and sufficient flexibility.
  • Aryl group-containing curable silicone composition that cures by hydrosilylation reaction is a photocoupler and light-emitting diode, taking advantage of its high refractive index and high transparency. It is used as a protective material or coating agent for a semiconductor element in an optical semiconductor device such as a solid-state imaging element or a lens material for an optical device.
  • a curable silicone composition for example, a linear organopolysiloxane having at least two silicon atom-bonded alkenyl groups and at least one silicon atom-bonded aryl group in one molecule, at least in one molecule A branched organopolysiloxane having one silicon atom-bonded alkenyl group and at least one silicon atom-bonded aryl group, and having a siloxane unit represented by the general formula: RSiO 3/2 , at least two in one molecule
  • a curable organopolysiloxane composition comprising an organopolysiloxane having a silicon-bonded hydrogen atom and a hydrosilylation catalyst (see Patent Document 1); It has at least two silicon-bonded alkenyl groups and at least one silicon-bonded aryl group in one molecule, and the content of silicon-bonded aryl groups with respect to all silicon-bonded organic groups in this component is 45 mol% or more.
  • a linear organopolysiloxane which has at least one silicon atom-bonded alkenyl group and at least one silicon atom-bonded aryl group in one molecule, and a siloxane unit represented by the general formula: RSiO 3/2
  • aryl group-containing curable silicone compositions contain an alkenyl-functional linear organopolysiloxane as an essential component, so that the content of the curing catalyst is such that the cured product does not cause problems such as coloring at high temperatures.
  • a relatively long time was required as a curing time (even for a composition not added with a reaction inhibitor), and the curing was not completed easily, and the surface tack of the cured product remained. Therefore, the curable silicone composition containing an aryl group cannot be molded by a highly productive device that requires a short time curing, such as injection molding, because the molded cured products adhere to each other and the workability decreases. There was a shortcoming.
  • JP 2004-143361 A JP 2005-105217 A JP 2013-1794 A JP 2014-88513 A JP 2012-129315 A Japanese Patent No. 5708824 JP 2010-132895 A JP 2011-225715 A
  • the present invention relates to a crosslinkable organopolysiloxane composition that forms a cured product by an aryl group-containing hydrosilylation reaction. Even if the curing catalyst has a content that does not cause problems such as coloring at high temperatures, short curing can be achieved.
  • An object of the present invention is to provide a crosslinkable organopolysiloxane composition that can complete a reaction in time, has no surface tack, and can form a cured product having sufficient flexibility.
  • the crosslinkable organopolysiloxane composition of the present invention comprises: (A) Average unit formula: (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (R 2 O 1/2 ) e (where R 1 Is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, at least one is an alkenyl group having 2 to 6 carbon atoms, and R 2 is a hydrogen atom or 1 to 6 carbon atoms
  • An alkyl group, a, b, c, d, and e are 0 ⁇ a ⁇ 0.1, 0.2 ⁇ b ⁇ 0.9, 0.1 ⁇ c ⁇ 0.6, and 0 ⁇ d ⁇ 0.
  • the crosslinkable organopolysiloxane composition of the present invention can be cured in a short time under the curing conditions at the same temperature and the same amount of curing catalyst as compared with the conventional crosslinkable composition that forms a cured product by an aryl group-containing hydrosilylation reaction.
  • a cured product having no surface tack and sufficient flexibility can be provided.
  • Siloxane A compound having a Si—O—Si bond.
  • Polysiloxane A compound having a plurality of Si—O—Si bonds.
  • Organopolysiloxane A polysiloxane having a structure in which organic groups are bonded to Si atoms constituting Si—O—Si bonds.
  • Organopolysiloxane composition A composition containing at least an organopolysiloxane and formulated for specific performance.
  • a linear organopolysiloxane is an organopolysiloxane that does not have a structure in which the main chain —Si—O—Si—O— chain has a structure in which a siloxane chain is connected to an Si atom via an atom linking group. Say. Also called linear component.
  • the branched organopolysiloxane means one containing at least one T-type or cross-type branch point.
  • the conventional crosslinkable organopolysiloxane composition has an alkenyl functional linear organopolysiloxane (particularly, a linear organopolysiloxane which is a vinyl polymer at both terminals) as an essential constituent.
  • an alkenyl functional linear organopolysiloxane particularly, a linear organopolysiloxane which is a vinyl polymer at both terminals
  • a branched organopolysiloxane having a specific structure capable of reducing the viscosity is used, a long curing time is required, and although it is a cause of surface tack, it has conventionally been an essential constituent component.
  • Flexibility means a property that is flexible and does not break even when bent (synonymous with being not brittle). For example, when a cured product having a thickness of 1 mm is formed, a cured product in which cracks do not spread from the cut portion to the periphery even if the cured product is cut with a cutter can be said to be a cured product having sufficient flexibility. When used as a sealing material, the cured product having sufficient flexibility has a practical performance that is less likely to crack during curing or peel off without being able to follow a temperature change during operation.
  • crosslinkable organopolysiloxane composition of the present invention it is further preferable to obtain a stable cured product in which mechanical properties, hardness and the like do not change after curing. Moreover, according to the preferable aspect of the crosslinkable organopolysiloxane composition of this invention, it is preferable that the hardened
  • the component (A) is an important component that is combined with the component (B) and affects the physical properties of the crosslinkable organopolysiloxane composition.
  • (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (R 2 O 1/2 ) e Is an alkenyl functional branched organopolysiloxane.
  • R 1 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, and at least one is an alkenyl group having 2 to 6 carbon atoms.
  • the plurality of R 1 may be the same as or different from each other.
  • the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group and an ethyl group are preferable.
  • the aryl group include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, preferably a methyl group or an ethyl group. is there.
  • the plurality of R 2 may be the same as or different from each other.
  • a is a number indicating the ratio of the siloxane unit represented by the general formula: R 1 3 SiO 1/2 and satisfies 0 ⁇ a ⁇ 0.1, preferably 0 ⁇ a ⁇ 0.08. Is a number. This is because sufficient strength and hardness at room temperature of a cured product obtained by excessively high fluidity when a exceeds the upper limit of the above range (in this specification, cured product is synonymous with crosslinked product) can be obtained. Because it disappears.
  • b is a number indicating the ratio of siloxane units represented by the general formula: R 1 2 SiO 2/2 , and a number satisfying 0.2 ⁇ b ⁇ 0.9, preferably 0.3 ⁇ b ⁇ 0.7. It is.
  • c is a number indicating the ratio of siloxane units (silsesquioxane units) represented by the general formula: R 1 SiO 3/2 , and 0.1 ⁇ c ⁇ 0.6, preferably 0 .2 ⁇ c ⁇ 0.6.
  • D is a number indicating the ratio of siloxane units represented by the general formula: SiO 4/2 , and is a number satisfying 0 ⁇ d ⁇ 0.2, preferably 0 ⁇ d ⁇ 0.1. This is because when d exceeds the upper limit of the above range, the flexibility of the obtained cured product becomes insufficient.
  • e is a number indicating the ratio of siloxane units represented by the general formula: R 2 O 1/2 and is a number satisfying 0 ⁇ e ⁇ 0.1. This is because sufficient hardness at room temperature of the obtained cured product cannot be obtained when e exceeds the upper limit of the above range.
  • the component (B) is an important second component that is combined with the component (A) and determines the physical properties of the crosslinkable organopolysiloxane composition, and includes at least two alkenyl groups and at least one aryl in one molecule.
  • Siloxane preferably has fluidity with a viscosity of 20 Pa ⁇ s or less at 25 ° C.
  • R 3 is a substituted or unsubstituted monovalent hydrocarbon group.
  • Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group and an ethyl group are preferable.
  • Examples of the aryl group include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group.
  • Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • a plurality of R 3 may be the same as or different from each other.
  • the viscosity is 100 Pa ⁇ s at 25 ° C. (that is, 100000 mPa ⁇ s).
  • a polysiloxane having the following fluidity can be obtained. Further, by controlling the production method of the component (B), the molecular weight of the alkenyl functional branched organopolysiloxane having a three-dimensional structure can be controlled within a preferable range, and the fluidity at a viscosity of 25 ° C. or less is preferable.
  • a polysiloxane having While having this branched structure and having fluidity at 25 ° C., a composition having a high curing speed and no surface tack of the cured product can be obtained. It is obvious to those skilled in the art that when the viscosity is 100 Pa ⁇ s at 25 ° C., it has fluidity at 25 ° C.
  • the component (B) has a viscosity of preferably 50000 mPa ⁇ s or less at 25 ° C., more preferably 30000 mPa ⁇ s or less, and particularly preferably 20000 mPa ⁇ s or less.
  • R 4 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, of which at least two are alkenyl groups having 2 to 6 carbon atoms, and at least one is an aryl group.
  • Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group and an ethyl group are preferable.
  • Examples of the aryl group include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group.
  • Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • a plurality of R 4 may be different from one another the same.
  • f is a number that defines the amount of terminal siloxane units of the polysiloxane represented by the general formula: R 4 3 SiO 1/2 for obtaining fluidity of 20 Pa ⁇ s or less at 25 ° C.
  • h and i Is a number that defines the component for the organopolysiloxane to take a branched structure, and both f and h + i must be greater than zero.
  • a general formula for the branch point In order to obtain fluidity of 20 Pa ⁇ s or less at 25 ° C., a general formula for the branch point:
  • the ratio f / (h + i) of the amount of terminal siloxane units of the polysiloxane represented by R 3 3 SiO 1/2 must be 0.5 or more, and the maximum is 4.
  • the linear component represented by the general formula: R 4 2 SiO 2/2 is not necessarily an essential component, but may be introduced as a component in the polymer in order to obtain a necessary viscosity, and 0 ⁇ g ⁇ 0 It may be in the range of .96, but 0 ⁇ g ⁇ 0.90 is preferable.
  • Component (B) is an average composition formula (R 4 3 SiO (R 4 2 SiO) m ) e SiR 4 (4-e) (wherein R 4 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, At least 2 is an alkenyl group having 2 to 6 carbon atoms, at least one is an aryl group, m is 0 or more and 200 or less, and e is an integer represented by 3 to 4)
  • R 4 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, At least 2 is an alkenyl group having 2 to 6 carbon atoms, at least one is an aryl group, and e is an integer represented by 3 to 4)
  • An embodiment that is a functional branched organopolysiloxane is also preferred.
  • m represents the number of linear siloxane units, and is a number satisfying 0 ⁇ m ⁇ 200, preferably 0 ⁇ m ⁇ 100.
  • e is an integer represented by 3 to 4, and is a number that defines the structure for forming the branch point of the branched organopolysiloxane.
  • e is 3
  • e is At 4
  • it becomes a cross-shaped branch point.
  • R 7 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, j is an integer represented by 3 to 4
  • R 5 is an alkenyl group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • R 6 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of which is an aryl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Group, an ethyl group.
  • aryl group examples include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group.
  • the plurality of R 5 , R 6 and R 7 may be the same as or different from each other.
  • n represents the number of linear siloxane units, n is 0 or more and 200 or less, and preferably 0 ⁇ n ⁇ 100. This is because when n exceeds the upper limit of the above range, the viscosity of the obtained branched organopolysiloxane exceeds 20 Pa ⁇ s at 25 ° C.
  • R 7 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a substituted or unsubstituted phenyl group, a naphthyl group, An aryl group such as an anthracenyl group is exemplified.
  • R 7 does not contain an alkenyl group.
  • j is an integer represented by 3 to 4, and is a number defining a structure for forming a branch point of the branched organopolysiloxane. When j is 3, a T-type branch point is obtained. When j is 4, it becomes a cross-shaped branch point.
  • the mixing ratio of the component (A) and the component (B) is such that the weight ratio of A / B is 1/100 to 100/1, and 1/50 to 50/1. It is preferable that the ratio is 1/20 to 20/1.
  • the amounts of the component (A) and the component (B) are described in parts by weight, and those skilled in the art will show the mixing ratio of the component (A) and the component (B) in the present specification by weight ratio. It is self-evident.
  • Component (C) is a crosslinking agent of the crosslinkable organopolysiloxane composition of the present invention (hereinafter also referred to as the present composition), and has at least two silicon atom-bonded hydrogen atoms in one molecule.
  • Organopolysiloxane in which 12 to 70 mol% of the combined organic groups are aryl groups.
  • an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a phenyl group
  • Examples include aryl groups such as tolyl group, naphthyl group, anthracenyl group and biphenyl group.
  • 12 to 70 mol% of the silicon-bonded organic group is an aryl group.
  • a silicon atom-bonded hydrogen atom is synonymous with Si—H.
  • R 8 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, A hexyl group etc. are illustrated, Preferably they are a methyl group and an ethyl group.
  • aryl group examples include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group.
  • a plurality of R 8 may be the same as or different from each other.
  • the aryl group content is in the range of 12 to 70 mol%.
  • the content of component (C) is such that the molar ratio of silicon-bonded hydrogen atoms in this component to the total of alkenyl groups in component (A) and component (B) is 0.5-2.
  • the component (D) is a hydrosilylation reaction catalyst for accelerating the hydrosilylation reaction between the alkenyl groups of the components (A) and (B) and the silicon atom-bonded hydrogen atom in the component (C).
  • the component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferred because they can significantly accelerate the crosslinking of the composition.
  • a platinum-alkenylsiloxane complex is preferable because of its high catalytic activity, and since the stability of the complex is good, it has 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as a ligand. Platinum complexes are preferred.
  • the content of the component (D) is an amount sufficient to promote the hydrosilylation reaction between the alkenyl group of the component (A), the component (B), and the silicon atom-bonded hydrogen atom of the component (C).
  • the amount of the metal atom in component (D) in the composition (D) is in the range of 0.1 ppm to 100 ppm in terms of weight (usually synonymous with mass). This is because if the content of component (D) is less than the lower limit of the above range, the resulting composition will not be sufficiently crosslinked, or will not be crosslinked at a sufficient rate, while exceeding the upper limit of the above range. This is because problems such as coloring may occur in the obtained cured product.
  • the composition comprises at least the component (A) to the component (D), but a reaction inhibitor (also referred to as a curing retarder) is added as an optional component for the purpose of arbitrarily changing the curing rate. May be.
  • Reaction inhibitors include 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, alkyne alcohols such as ethynylcyclohexanol, 1,3,5,7-tetramethyl-1 , 3,5,7-tetravinylcyclotetrasiloxane, benzotriazole and the like.
  • the content of these reaction inhibitors is not particularly limited, but is preferably in the range of 1 ppm to 1000 ppm with respect to the weight of the present composition.
  • the composition may contain an adhesion promoter (also referred to as an adhesion promoter).
  • adhesion promoter include trialkoxysilyl groups (for example, trimethoxysilyl group and triethoxysilyl group), hydrosilyl groups, epoxy groups (for example, 3-glycidoxypropyl group), alkenyl groups (for example, vinyl group and allyl group). Group) in one molecule, and the like.
  • the present composition includes, as the other optional components, organopolysiloxanes other than the components (A) to (C), inorganic fillers (for example, silica, glass, alumina), as long as the object of the present invention is not impaired. , Zinc oxide, etc.), organic resin fine powder such as polymethacrylate resin, heat-resistant agent, dye, pigment, phosphor, flame retardant, solvent and the like.
  • organopolysiloxane other than the component (A) to the component (C) include alkenyl functional linear organopolysiloxanes.
  • the crosslinkable organopolysiloxane composition of the present invention is an alkenyl functional linear chain. No organopolysiloxane.
  • a crosslinkable organopolysiloxane composition having good characteristics can be obtained by using the component (B) without using an alkenyl functional linear organopolysiloxane which has been conventionally considered as an essential component. be able to.
  • the preferable range of the viscosity of the present composition is the same as the preferable range of the viscosity of the component (B).
  • the composition is rapidly cross-linked by heating, has no surface tack, forms a cured product having sufficient flexibility, and preferably can form a hard cured product. When the composition is completely cured by heating, the composition can be made to have a more preferable hardness depending on the application, and particularly high hardness can be obtained.
  • the crosslinkable organopolysiloxane composition of the present invention preferably has a type D durometer hardness of 45 or more as defined in JIS K 6253 when heated at 150 ° C. for 30 minutes, depending on the desired application.
  • the Type D durometer hardness can be 45-60, and the Type D durometer hardness can be 60-80 depending on other desired applications.
  • this composition can have a type A durometer hardness of 30 to 60 as defined in JIS K 6253 when completely cured by heating.
  • the type A durometer hardness can be 60-90 depending on the desired application.
  • the composition can form a stable cured product in which mechanical properties, hardness and the like are not changed by heating.
  • the heating temperature is preferably within the range of 80 ° C to 200 ° C. Since the curing speed is high, the composition is suitable for injection molding and the like, but the molding method is not necessarily limited.
  • It can also be used as an adhesive application by ordinary mixing, oven heating, etc., film formation, potting agent, coating agent, underfill agent.
  • potting agent since it has a high refractive index and a high light transmittance, it is suitable for lens materials for optical applications, potting agents for semiconductor elements such as light emitting diodes, coating agents, protective materials, and sealing materials.
  • the cured product of the present invention is obtained by curing the crosslinkable organopolysiloxane composition.
  • the shape of the cured product is not particularly limited, and may be various, such as a lump, sheet, or film.
  • the cured product can be handled alone, but can also be handled in a state where the optical semiconductor element or the like is covered or sealed.
  • the crosslinkable organopolysiloxane composition of the present invention will be described in detail with reference to examples.
  • the viscosity is a value at 25 ° C.
  • Me, Ph, and Vi in the formula represent a methyl group, a phenyl group, and a vinyl group, respectively.
  • the hardness of the cured product was measured with a type A durometer and a type D durometer as defined in JIS K 6253 “Hardness test method for vulcanized rubber and thermoplastic rubber”. JIS is an abbreviation for Japan Industrial Standards.
  • Example 1 Average unit formula: (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 62 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula: (ViMe 2 SiO (SiPhMeO) 15 ) 3 SiPh, the viscosity is represented by 17 parts by weight of branched methylvinylphenylpolysiloxane having a viscosity of 1200 mPa ⁇ s at 25 ° C., and the formula: (HMe 2 SiO) 2 SiPh 2 After uniformly mixing 21 parts by weight of trisiloxane, an amount of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is 5 ppm by weight with respect to the present composition. Were mixed to prepare a crosslinkable organopolysiloxane composition having
  • Example 2 Average unit formula: (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 63 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula: 40 parts by weight of an organopolysiloxane represented by ViMe 2 SiO (PhMeSiO) 38 SiMe 2 Vi and 1 part by weight of a siloxane oligomer represented by the formula: (HMe 2 SiO) 3 SiPh were synthesized by a hydrosilylation reaction.
  • a crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 3700 mPa ⁇ s was prepared by mixing a methyldisiloxane complex in an amount such that the platinum amount was 5 ppm by weight with respect to the present composition.
  • Example 5 Average unit formula: (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 62 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula: (ViMe 2 SiO (SiPhMeO) 15 ) 3 SiPh represented by 17 parts by weight of branched methylvinylphenylpolysiloxane used in Example 1, and trisiloxane 21 represented by the formula: (HMe 2 SiO) 2 SiPh 2 After uniformly mixing parts by weight, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is added in an amount such that the platinum amount is 5 ppm by weight with respect to the composition, and ethynyl A crosslinkable organopolysiloxane composition having a viscosity of 2500 mPa ⁇ s at 25
  • Example 7 Average unit formula: (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 62 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula: (ViMe 2 SiO (SiPhMeO) 15 ) 3 SiPh represented by 17 parts by weight of branched methylvinylphenylpolysiloxane used in Example 1, and trisiloxane 21 represented by the formula: (HMe 2 SiO) 2 SiPh 2 After uniformly mixing parts by weight, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was mixed with the composition in such an amount that the platinum amount was 25 ppm by weight. A crosslinkable organopolysiloxane composition having a viscosity of 2500 mPa ⁇ s at 25 ° C. was prepared.
  • This composition had a viscosity of 4500 mPa ⁇ s at 25 ° C. after 20 hours.
  • curing was completed in 40 seconds, and a rubber-like cured product having a type A durometer hardness of 60 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
  • Example 8 Average unit formula: (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 63 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula: Formula synthesized by hydrosilylation reaction of 40 parts by weight of an organopolysiloxane represented by ViMe 2 SiO (PhMeSiO) 38 SiMe 2 Vi and 1 part by weight of a siloxane oligomer represented by the formula: (HMe 2 SiO) 3 SiPh: ⁇ Branched methylvinylphenyl polysiloxane 17 used in Example 2 represented by (ViMe 2 SiO (PhMeSiO) 38 SiMe 2 C 2 H 4 Me 2 SiO) 2 SiPhC 2 H 4 Me 2 SiO (PhMeSiO) 19 ⁇ 2 1 part by weight of platinum and 1,3-divinyl
  • This composition had a viscosity of 7000 mPa ⁇ s at 25 ° C. after 20 hours.
  • curing was completed in 35 seconds, and a rubber-like cured product having a type A durometer hardness of 55 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
  • Example 9 Average unit formula: (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 64 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula: (ViMe 2 SiO (SiPhMeO) 15 ) 17 parts by weight of branched methylvinylphenylpolysiloxane used in Example 1 represented by 3 SiPh, and 19 parts by weight of tetrasiloxane represented by the formula: (HMe 2 SiO) 3 SiPh After mixing the parts uniformly, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was mixed with the composition in such an amount that the platinum amount was 5 ppm by weight. A crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 2600 mPa ⁇ s was prepared.
  • This composition was cured in 200 seconds when heated to 150 ° C., and a rubber-like cured product having a type A durometer hardness of 75 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
  • Example 10 Average unit formula: (MeViSiO 2/2) 0.3 (Ph 2 SiO 2/2) 0.3 (PhSiO 3/2) branched methyl vinyl phenyl polysiloxane 60 parts by weight represented by 0.4, the formula: (ViMe 2 SiO 1/2 ) 0.3 (Ph 2 SiO) 0.3 (PhSiO 3/2 ) Branched methylvinylphenylpolysiloxane having a viscosity represented by 0.4 of 9000 mPa ⁇ s at 25 ° C.
  • Example 11 Average unit formula: (MeViSiO 2/2) 0.3 (Ph 2 SiO 2/2) 0.3 (PhSiO 3/2) branched methyl vinyl phenyl polysiloxane 60 parts by weight represented by 0.4, the formula: (ViMe 2 SiO 1/2 ) 0.4 (Ph 2 SiO) 0.3 (PhSiO 3/2 ) Branched methyl vinyl phenyl polysiloxane having a viscosity represented by 0.3 of 2000 mPa ⁇ s at 25 ° C.
  • Example 12 Average unit formula: (Me 2 ViSiO 1/2 ) 0.05 (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.25 (PhSiO 3/2 ) 0.45 60 parts by weight of siloxane, formula: (ViMe 2 SiO 1/2 ) 0.4 (Ph 2 SiO) 0.3 (PhSiO 3/2 ) Branched methyl vinyl phenyl polysiloxane having a viscosity represented by 0.3 of 2000 mPa ⁇ s at 25 ° C.
  • Example 13 Average unit formula: (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 60 parts by weight of branched methylvinylphenyl polysiloxane represented by 0.45 , formula: (ViMe 2 SiO 1/2 ) 0.3 (Ph 2 SiO) 0.3 (PhSiO 3/2 ) Branched methyl vinyl phenyl polysiloxane having a viscosity represented by 0.4 of 8000 mPa ⁇ s at 25 ° C.
  • the crosslinkable organopolysiloxane composition of the present invention is a material that is fast in cross-linking, has no surface tack of a cured product, and has sufficient flexibility to relieve stress.
  • Potting agents, protective coating agents, and underfill agents are suitable for lens materials for optical applications.
  • potting agents for semiconductor elements such as light emitting diodes, coating agents, protective materials, and sealing materials.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A crosslinkable organopolysiloxane composition which comprises (A) an arylated alkenyl-functional branched organopolysiloxane represented by an average unit formula, (B) an arylated alkenyl-functional branched organopolysiloxane that is represented by a general formula and has at least three siloxane units in the molecule, (C) an organopolysiloxane having at least two silicon-atom-bonded hydrogen atoms in the molecule, and (D) a hydrosilylation catalyst and which is rapidly crosslinked by hydrosilylation to thereby form a cured object having sufficient flexibility; and a cured object.

Description

架橋性オルガノポリシロキサン組成物およびその硬化物Crosslinkable organopolysiloxane composition and cured product thereof
　本発明は、ヒドロシリル化反応により速やかに架橋して、表面タックがなく、十分の可とう性を有する硬化物を形成できる架橋性オルガノポリシロキサン組成物に関する。 The present invention relates to a crosslinkable organopolysiloxane composition that can be rapidly crosslinked by a hydrosilylation reaction to form a cured product having no surface tack and sufficient flexibility.
　ヒドロシリル化反応により硬化するアリール基含有の硬化性シリコーン組成物（シリコーン組成物は、オルガノポリシロキサン組成物と同義である）は、高屈折率や高透明性の特性を生かしてフォトカプラー、発光ダイオード、固体撮像素子等の光学用半導体装置における半導体素子の保護材あるいはコーティング剤や光学機器のレンズ材料など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、例えば、一分子中に少なくとも２個のケイ素原子結合アルケニル基と少なくとも１個のケイ素原子結合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個のケイ素原子結合アルケニル基と少なくとも１個のケイ素原子結合アリール基を有し、一般式：ＲＳｉＯ３／２で表されるシロキサン単位を有する分岐状オルガノポリシロキサン、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ポリシロキサン、およびヒドロシリル化反応用触媒からなる硬化性オルガノポリシロキサン組成物（特許文献１参照）；
一分子中に少なくとも２個のケイ素原子結合アルケニル基と少なくとも１個のケイ素原子結合アリール基を有し、本成分のケイ素原子結合全有機基に対するケイ素原子結合アリール基の含有率が４５モル％以上であ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個のケイ素原子結合アルケニル基と少なくとも１個のケイ素原子結合アリール基を有し、一般式：ＲＳｉＯ３／２で表されるシロキサン単位を有する分岐鎖状のオルガノポリシロキサン、一般式：ＨＳｉＲ２Ｏ（ＳｉＲ２Ｏ）ｎＳｉＲ２Ｈで表されるアリール基含有の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オルガノポリシロキサン組成物（特許文献２参照）；
平均単位式：（Ｒ３ＳｉＯ１／２）ａ（Ｒ２ＳｉＯ２／２）ｂ（ＲＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ（ＲＯ１／２）ｅで表されるフェニル基含有アルケニル官能性分岐状オルガノポリシロキサン、一般式：
Ｒ３ＳｉＯ（Ｒ２ＳｉＯ）ｍＳｉＲ３で表されるフェニル基含有アルケニル官能性直鎖状オルガノポリシロキサン、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し、ケイ素原子結合有機基の３０～７０モル％がフェニル基である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架橋性シリコーン組成物（特許文献３参照）；
平均単位式：（Ｒ３ＳｉＯ１／２）ａ（Ｒ２ＳｉＯ２／２）ｂ（ＲＳｉＯ３／２）ｃで表され、一分子中に少なくとも２個のアルケニル基を有するアリール基含有アルケニル官能性分岐状オルガノポリシロキサン、一分子中に少なくとも２個のアルケニル基を有し、ケイ素原子結合水素原子を有さない直鎖状オルガノポリシロキサン、一般式：ＨＳｉＲ２Ｏ（ＳｉＲ２Ｏ）ｎＳｉＲ２Ｈで表されるアリール基含有のオルガノポリシロキサン、平均単位式：
（ＨＲ２ＳｉＯ１／２）ｄ（ＨＲ２ＳｉＯ１／２）ｅ（Ｒ２ＳｉＯ２／２）ｆ（ＲＳｉＯ３／２）ｇで表されるアリール基含有オルガノポリシロキサン、および、有効量の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４参照）；
式：（Ｒ３ＳｉＯ１／２）ａ（Ｒ２ＳｉＯ２／２）ｂ（ＲＳｉＯ３／２）ｃで表され、実質的にアルコキシ基を有さず、少なくとも１個のアリール基と少なくとも１個のアルケニル基を含有する直鎖状、または分岐状アリール基含有アルケニル官能性オルガノポリシロキサン、
（Ｒ３ＳｉＯ１／２）ｐ（Ｒ２ＳｉＯ２／２）ｑ（ＲＳｉＯ３／２）ｒで表され、実質的にアルコキシ基を有さず、少なくとも１個のアリール基と少なくとも１個のケイ素原子結合水素原子を含有する分岐状アリール基含有ケイ素原子結合水素原子官能性オルガノポリシロキサンとヒドロシリル化反応用触媒を含む光半導体装置用封止剤（特許文献５参照）；
ＨＳｉＲ２Ｏ（ＳｉＲ２Ｏ）ｎＳｉＲ２Ｈで表される一分子中に２個のケイ素原子結合水素原子および少なくとも１個のアリール基を有し、重合度が１０超であ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３個のアルケニル基および少なくとも１個のアリール基を有する分岐状オルガノポリシロキサンとヒドロシリル化反応用触媒を含有する硬化性樹脂組成物（特許文献６参照）；
式：Ｒ１Ｒ２ ２ＳｉＯ（Ｐｈ２ＳｉＯ）ｎＳｉＲ２ ２Ｒ１で示されＲ１が不飽和基でｎが１～２０の不飽和基末端ポリジフェニルシロキサン、式：ＨＲ２ＳｉＯ（ＨＲＳｉＯ）ｃＳｉＲ２ＨおよびＨＲ２ＳｉＯ（ＨＲＳｉＯ）ｃ（Ｒ２ＳｉＯ）ｄＳｉＲ２Ｈで示される化合物から選ばれる、１分子あたり少なくとも２個のケイ素原子結合水素原子を有する有機ケイ素化合物、および、ヒドロシリル化触媒を含む付加硬化型シリコーン組成物（特許文献７参照）；
一分子中に少なくとも２個のアルケニル基を有しＲＳｉＯ３／２で表されるシロキサン単位を５～７０モル％含有する液状であるアルケニル官能性分岐状オルガノポリシロキサン、一分子中に少なくとも２個のアルケニル基を有し、ＲＳｉＯ３／２で表されるシロキサン単位を少なくとも７０モル％を超えて含有する固体状であるアルケニル官能性分岐状オルガノポリシロキサン、平均組成式：ＲａＨｂＳｉＯ（４－ａ－ｂ）／２で表され、１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直鎖状オルガノハイドロジェンポリシロキサン、付加反応触媒を含有することを特徴とする硬化性オルガノポリシロキサン組成物（特許文献８参照）が挙げられる。 Aryl group-containing curable silicone composition that cures by hydrosilylation reaction (silicone composition is synonymous with organopolysiloxane composition) is a photocoupler and light-emitting diode, taking advantage of its high refractive index and high transparency. It is used as a protective material or coating agent for a semiconductor element in an optical semiconductor device such as a solid-state imaging element or a lens material for an optical device. As such a curable silicone composition, for example, a linear organopolysiloxane having at least two silicon atom-bonded alkenyl groups and at least one silicon atom-bonded aryl group in one molecule, at least in one molecule A branched organopolysiloxane having one silicon atom-bonded alkenyl group and at least one silicon atom-bonded aryl group, and having a siloxane unit represented by the general formula: RSiO 3/2 , at least two in one molecule A curable organopolysiloxane composition comprising an organopolysiloxane having a silicon-bonded hydrogen atom and a hydrosilylation catalyst (see Patent Document 1);
It has at least two silicon-bonded alkenyl groups and at least one silicon-bonded aryl group in one molecule, and the content of silicon-bonded aryl groups with respect to all silicon-bonded organic groups in this component is 45 mol% or more. A linear organopolysiloxane which has at least one silicon atom-bonded alkenyl group and at least one silicon atom-bonded aryl group in one molecule, and a siloxane unit represented by the general formula: RSiO 3/2 A branched organopolysiloxane having an aryl group-containing organopolysiloxane represented by the general formula: HSiR 2 O (SiR 2 O) n SiR 2 H, and a hydrosilylation reaction catalyst Composition (see Patent Document 2);
Average unit formula: (R 3 SiO 1/2) a (R 2 SiO 2/2) b (RSiO 3/2) c phenyl group-containing represented by (SiO 4/2) d (RO 1/2 ) e Alkenyl-functional branched organopolysiloxane, general formula:
A phenyl group-containing alkenyl functional linear organopolysiloxane represented by R 3 SiO (R 2 SiO) m SiR 3 , having at least two silicon-bonded hydrogen atoms in one molecule, and a silicon-bonded organic group A crosslinkable silicone composition comprising at least 30 to 70 mol% of an organopolysiloxane having a phenyl group and a hydrosilylation reaction catalyst (see Patent Document 3);
Average unit formula: (R 3 SiO 1/2 ) a (R 2 SiO 2/2 ) b (RSiO 3/2 ) An aryl group-containing alkenyl function represented by c and having at least two alkenyl groups in one molecule Branched organopolysiloxane, linear organopolysiloxane having at least two alkenyl groups in one molecule and having no silicon-bonded hydrogen atom, general formula: HSiR 2 O (SiR 2 O) n SiR An aryl group-containing organopolysiloxane represented by 2 H, average unit formula:
An aryl group-containing organopolysiloxane represented by (HR 2 SiO 1/2 ) d (HR 2 SiO 1/2 ) e (R 2 SiO 2/2 ) f (RSiO 3/2 ) g , and an effective amount of A curable silicone composition comprising at least a hydrosilylation reaction catalyst (see Patent Document 4);
Formula: (R 3 SiO 1/2 ) a (R 2 SiO 2/2 ) b (RSiO 3/2 ) c , substantially having no alkoxy group, at least one aryl group and at least 1 Linear or branched aryl group-containing alkenyl functional organopolysiloxanes containing one alkenyl group,
(R 3 SiO 1/2 ) p (R 2 SiO 2/2 ) q (RSiO 3/2 ) r , substantially having no alkoxy group, at least one aryl group and at least one An encapsulant for optical semiconductor devices comprising a branched aryl group-containing silicon atom-bonded hydrogen atom-functional organopolysiloxane containing a silicon atom-bonded hydrogen atom and a hydrosilylation catalyst (see Patent Document 5);
HSiR 2 O (SiR 2 O) n A linear organoorganism having two silicon-bonded hydrogen atoms and at least one aryl group in one molecule represented by SiR 2 H and having a degree of polymerization of more than 10 A curable resin composition containing a polysiloxane, a branched organopolysiloxane having at least three alkenyl groups and at least one aryl group in one molecule, and a catalyst for hydrosilylation reaction (see Patent Document 6);
Formula: R 1 R 2 2 SiO ( Ph 2 SiO) n SiR 2 2 R 1 is represented by R 1 is an unsaturated group n is 1-20 unsaturated group-terminated polydiphenylsiloxane formula: HR 2 SiO (HRSiO ) C SiR 2 H and HR 2 SiO (HRSiO) c (R 2 SiO) An organosilicon compound having at least two silicon-bonded hydrogen atoms per molecule, selected from compounds represented by d SiR 2 H, and An addition-curable silicone composition containing a hydrosilylation catalyst (see Patent Document 7);
An alkenyl-functional branched organopolysiloxane which is a liquid containing at least two alkenyl groups in one molecule and containing 5 to 70 mol% of siloxane units represented by RSiO 3/2 , at least two in one molecule have alkenyl groups, solid at a alkenyl-functional branched organopolysiloxane containing in excess of at least 70 mol% of siloxane units represented by RSiO 3/2, average composition formula: R a H b SiO ( A linear organohydrogenpolysiloxane represented by 4-ab) / 2 and having at least two silicon-bonded hydrogen atoms in one molecule, and an addition reaction catalyst. Polysiloxane composition (refer patent document 8) is mentioned.
　これらのアリール基含有の硬化性シリコーン組成物はアルケニル官能性直鎖状オルガノポリシロキサンが必須構成成分として含まれるため、硬化物が高温時の着色等の問題を起こさない程度の硬化触媒の含有量で硬化させると、（反応抑制剤を添加していない組成物でも）硬化時間として比較的長時間を必要とし、硬化がなかなか完了せず、硬化物の表面タックが残るという不具合があった。そのため、アリール基含有の硬化性シリコーン組成物は成型された硬化物同士が付着して作業性が低下したり、射出成型などの短時間硬化を必要とする高生産性の機器による成型ができなかったりという欠点があった。
　一方、アルケニル官能性オルガノポリシロキサンが分岐状オルガノポリシロキサンのみから構成された硬化性オルガノポリシロキサン組成物でシルセスキオキサン単位が７０モル％を超えるような高架橋密度の硬化物の場合（特許文献８参照）、特許文献８の範囲での組成物ではアリール基を含有すると硬化物が可とう性が得られず用途に大きな制約が出てしまう不具合があった。 These aryl group-containing curable silicone compositions contain an alkenyl-functional linear organopolysiloxane as an essential component, so that the content of the curing catalyst is such that the cured product does not cause problems such as coloring at high temperatures. When cured with (1), a relatively long time was required as a curing time (even for a composition not added with a reaction inhibitor), and the curing was not completed easily, and the surface tack of the cured product remained. Therefore, the curable silicone composition containing an aryl group cannot be molded by a highly productive device that requires a short time curing, such as injection molding, because the molded cured products adhere to each other and the workability decreases. There was a shortcoming.
On the other hand, in the case of a curable organopolysiloxane composition in which the alkenyl functional organopolysiloxane is composed only of a branched organopolysiloxane and a cured product having a high crosslinking density such that the silsesquioxane unit exceeds 70 mol% (patent document) 8), the composition within the range of Patent Document 8 has a problem that if an aryl group is contained, the cured product cannot obtain flexibility and the use is greatly restricted.
特開２００４－１４３３６１号公報JP 2004-143361 A 特開２００５－１０５２１７号公報JP 2005-105217 A 特開２０１３－１７９４号公報JP 2013-1794 A 特開２０１４－８８５１３号公報JP 2014-88513 A 特開２０１２－１２９３１５号公報JP 2012-129315 A 特許第５７０８８２４号Japanese Patent No. 5708824 特開２０１０－１３２７９５号公報JP 2010-132895 A 特開２０１１－２２５７１５号公報JP 2011-225715 A
　本発明は、アリール基含有のヒドロシリル化反応により硬化物を形成する架橋性オルガノポリシロキサン組成物において、硬化触媒が高温時の着色等の問題が生じない程度の含有量であっても、短い硬化時間で反応が完了し、表面タックがなく、十分の可とう性を有する硬化物を形成できる架橋性オルガノポリシロキサン組成物を提供することを目的とする。 The present invention relates to a crosslinkable organopolysiloxane composition that forms a cured product by an aryl group-containing hydrosilylation reaction. Even if the curing catalyst has a content that does not cause problems such as coloring at high temperatures, short curing can be achieved. An object of the present invention is to provide a crosslinkable organopolysiloxane composition that can complete a reaction in time, has no surface tack, and can form a cured product having sufficient flexibility.
　本発明の架橋性オルガノポリシロキサン組成物は、
　（Ａ）平均単位式：
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ（Ｒ２Ｏ１／２）ｅ（式中Ｒ１は炭素数１～１４の一価炭化水素基で、少なくとも１個はアリール基、また、少なくとも１個は炭素数２～６のアルケニル基であり、Ｒ２は水素原子または炭素数１～６のアルキル基であり、ａ、ｂ、ｃ、ｄ、およびｅは、０≦ａ≦０．１、０．２≦ｂ≦０．９、０．１≦ｃ≦０．６、０≦ｄ≦０．２、０≦ｅ≦０．１、かつａ＋ｂ＋ｃ＋ｄ＋ｅ＝１を満たす数である。）で示されるアリール基を含有するアルケニル官能性分岐状オルガノポリシロキサン、
（Ｂ）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し、下記一般式（１）で表されるシロキサン単位を一分子中に少なくとも３個有する、（好ましくは２５℃において粘度が２０Ｐａ・ｓ以下の流動性を有する）アリール基を含有するアルケニル官能性分岐状オルガノポリシロキサン｛（Ａ）成分と（Ｂ）成分の比が１／１００～１００／１｝、
Ｒ３ ３ＳｉＯ１／２　　　一般式（１）（式中、Ｒ３は置換又は非置換の一価炭化水素基である。）
（Ｃ）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し、ケイ素原子結合有機基の１２～７０モル％がアリール基であるオルガノポリシロキサン｛（Ａ）成分中と（Ｂ）成分中のアルケニル基の合計に対する本成分中のケイ素原子結合水素原子のモル比が０．５～２となる量｝、および
（Ｄ）ヒドロシリル化反応用触媒｛（Ａ）成分と（Ｂ）成分のアルケニル基と（Ｃ）成分のケイ素原子結合水素原子とのヒドロシリル化反応を促進するに十分の量｝を少なくとも含み、
　アルケニル官能性直鎖状オルガノポリシロキサンを含まない架橋性オルガノポリシロキサン組成物である。 The crosslinkable organopolysiloxane composition of the present invention comprises:
(A) Average unit formula:
(R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (R 2 O 1/2 ) e (where R 1 Is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, at least one is an alkenyl group having 2 to 6 carbon atoms, and R 2 is a hydrogen atom or 1 to 6 carbon atoms An alkyl group, a, b, c, d, and e are 0 ≦ a ≦ 0.1, 0.2 ≦ b ≦ 0.9, 0.1 ≦ c ≦ 0.6, and 0 ≦ d ≦ 0. ., 2, 0 ≦ e ≦ 0.1, and a number satisfying a + b + c + d + e = 1.)
(B) having at least two alkenyl groups and at least one aryl group in one molecule, and having at least three siloxane units represented by the following general formula (1) in one molecule (preferably An alkenyl-functional branched organopolysiloxane having an aryl group (having a fluidity of a viscosity of 20 Pa · s or less at 25 ° C.) (the ratio of the component (A) to the component (B) is 1/100 to 100/1),
R 3 3 SiO 1/2 general formula (1) (wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group)
(C) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule and 12 to 70 mol% of silicon-bonded organic groups being aryl groups {in component (A) and component (B) In an amount such that the molar ratio of silicon-bonded hydrogen atoms in this component to the total of alkenyl groups in the component is 0.5 to 2}, and (D) hydrosilylation catalyst {components (A) and (B) An amount sufficient to promote the hydrosilylation reaction between the alkenyl group and the silicon-bonded hydrogen atom of component (C)},
A crosslinkable organopolysiloxane composition that does not contain an alkenyl functional linear organopolysiloxane.
　本発明の架橋性オルガノポリシロキサン組成物は、従来のアリール基含有ヒドロシリル化反応により硬化物を形成する架橋性組成物に比べて同温、同硬化触媒量における硬化条件で短時間に硬化が完了し、表面タックがなく、十分の可とう性を有する硬化物を提供することができる特徴を有する。 The crosslinkable organopolysiloxane composition of the present invention can be cured in a short time under the curing conditions at the same temperature and the same amount of curing catalyst as compared with the conventional crosslinkable composition that forms a cured product by an aryl group-containing hydrosilylation reaction. In addition, there is a feature that a cured product having no surface tack and sufficient flexibility can be provided.
　本明細書中、各用語の意味は以下のとおりである。
　シロキサン：Ｓｉ－Ｏ－Ｓｉ結合を持つ化合物。
　ポリシロキサン：Ｓｉ－Ｏ－Ｓｉ結合を複数個持つ化合物。
　オルガノポリシロキサン：Ｓｉ－Ｏ－Ｓｉ結合を構成するＳｉ原子に有機基が結合した構造を有するポリシロキサン。
　オルガノポリシロキサン組成物：オルガノポリシロキサンを少なくとも含む、特定の性能を求めて配合された組成物。
　直鎖状オルガノポリシロキサンとは、主鎖の－Ｓｉ－Ｏ－Ｓｉ－Ｏ－鎖に対し、Ｓｉ原子上に原子連結基を介してシロキサン鎖が連結した構造を有さないオルガノポリシロキサンのことを言う。リニア成分とも言われる。
　分岐状オルガノポリシロキサンとは、Ｔ型または十字型の分岐点を少なくとも1個以上含むものをいう。 In this specification, the meaning of each term is as follows.
Siloxane: A compound having a Si—O—Si bond.
Polysiloxane: A compound having a plurality of Si—O—Si bonds.
Organopolysiloxane: A polysiloxane having a structure in which organic groups are bonded to Si atoms constituting Si—O—Si bonds.
Organopolysiloxane composition: A composition containing at least an organopolysiloxane and formulated for specific performance.
A linear organopolysiloxane is an organopolysiloxane that does not have a structure in which the main chain —Si—O—Si—O— chain has a structure in which a siloxane chain is connected to an Si atom via an atom linking group. Say. Also called linear component.
The branched organopolysiloxane means one containing at least one T-type or cross-type branch point.
　従来の架橋性オルガノポリシロキサン組成物は、アルケニル官能性直鎖状オルガノポリシロキサン（特に両末端ビニルポリマーである直鎖状オルガノポリシロキサン）を必須構成成分としていた。
　これに対し、本発明によれば、低粘度化できる特定の構造の分岐状オルガノポリシロキサンを用いるため、硬化時間が長く必要であり、表面タックの原因であるにも関わらず従来は必須構成成分と考えられていたアルケニル官能性直鎖状オルガノポリシロキサンを除くことができる。
　特定の構造の分岐状オルガノポリシロキサンを用いる結果、十分の可とう性を有する硬化物を得ることができる。 The conventional crosslinkable organopolysiloxane composition has an alkenyl functional linear organopolysiloxane (particularly, a linear organopolysiloxane which is a vinyl polymer at both terminals) as an essential constituent.
On the other hand, according to the present invention, since a branched organopolysiloxane having a specific structure capable of reducing the viscosity is used, a long curing time is required, and although it is a cause of surface tack, it has conventionally been an essential constituent component. The alkenyl functional linear organopolysiloxane that was considered to be
As a result of using a branched organopolysiloxane having a specific structure, a cured product having sufficient flexibility can be obtained.
　可とう性（ｆｌｅｘｉｂｉｌｉｔｙ）とは、柔軟性があり、曲げても折れない性質のことを言う（脆くないことと同義）。例えば１ｍｍ厚さの硬化物を形成した場合に、硬化物をカッターで切断しても切断部分から周囲にひび割れが広がらない硬化物などは、十分の可とう性を有する硬化物と言える。十分の可とう性を有する硬化物は、封止材として用いた場合に硬化時に割れたり、運転時の温度変化に追随できず剥離したりすることが少ない実用性能を持つ。
　本発明の架橋性オルガノポリシロキサン組成物の好ましい態様によれば、さらに、機械的物性、硬さなどが硬化後に変化しない安定した硬化物を得られることが好ましい。また、本発明の架橋性オルガノポリシロキサン組成物の好ましい態様によれば、さらに、高い硬さの硬化物を得られることが好ましい。 Flexibility means a property that is flexible and does not break even when bent (synonymous with being not brittle). For example, when a cured product having a thickness of 1 mm is formed, a cured product in which cracks do not spread from the cut portion to the periphery even if the cured product is cut with a cutter can be said to be a cured product having sufficient flexibility. When used as a sealing material, the cured product having sufficient flexibility has a practical performance that is less likely to crack during curing or peel off without being able to follow a temperature change during operation.
According to a preferred embodiment of the crosslinkable organopolysiloxane composition of the present invention, it is further preferable to obtain a stable cured product in which mechanical properties, hardness and the like do not change after curing. Moreover, according to the preferable aspect of the crosslinkable organopolysiloxane composition of this invention, it is preferable that the hardened | cured material of higher hardness can be obtained further.
　初めに、本発明の架橋性オルガノポリシロキサン組成物を詳細に説明する。
（Ａ）成分は、（Ｂ）成分と組み合わされて架橋性オルガノポリシロキサン組成物の物性を左右する重要な成分であり、平均単位式：
（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ（Ｒ２Ｏ１／２）ｅで示されるアリール基を含有するアルケニル官能性分岐状オルガノポリシロキサンである。 First, the crosslinkable organopolysiloxane composition of the present invention will be described in detail.
The component (A) is an important component that is combined with the component (B) and affects the physical properties of the crosslinkable organopolysiloxane composition.
(R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (R 2 O 1/2 ) e Is an alkenyl functional branched organopolysiloxane.
　式中、Ｒ１は炭素数１～１４の一価炭化水素基で、少なくとも１個はアリール基、また少なくとも１個は炭素数２～６のアルケニル基である。複数のＲ１は互いに同じであっても異なっていてもよい。一価炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基などが例示され、好ましくはメチル基、エチル基である。また、アリール基としては置換または無置換のフェニル基、ナフチル基、アントラセニル基が例示される。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、ヘキセニル基が例示される。式中、Ｒ２は水素原子または炭素数１～６のアルキル基であり、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基などが例示され、好ましくはメチル基、エチル基である。複数のＲ２は互いに同じであっても異なっていてもよい。 In the formula, R 1 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, and at least one is an alkenyl group having 2 to 6 carbon atoms. The plurality of R 1 may be the same as or different from each other. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group and an ethyl group are preferable. Examples of the aryl group include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. In the formula, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, preferably a methyl group or an ethyl group. is there. The plurality of R 2 may be the same as or different from each other.
　また、式中、ａは一般式：Ｒ１ ３ＳｉＯ１／２で表されるシロキサン単位の割合を示す数であり、０≦ａ≦０．１、好ましくは０≦ａ≦０．０８を満たす数である。これは、ａが上記範囲の上限を超えると流動性が高くなりすぎて得られる硬化物（本明細書中、硬化物は架橋物と同義）の室温での十分の強度と硬さが得られなくなるからである。ｂは一般式：Ｒ１ ２ＳｉＯ２／２で表されるシロキサン単位の割合を示す数であり、０．２≦ｂ≦０．９、好ましくは０．３≦ｂ≦０．７を満たす数である。これは、ｂが上記範囲の下限未満であると屈折率が好ましい高屈折率にならないからであり、上記範囲の上限を超えると、得られる硬化物の室温での十分の硬さが得られなくなるからである。また、式中、ｃは一般式：Ｒ１ＳｉＯ３／２で表されるシロキサン単位（シルセスキオキサン単位）の割合を示す数であり、０．１≦ｃ≦０．６、好ましくは０．２≦ｃ≦０．６を満たす数である。これは、ｃが上記範囲の下限未満であると、得られる硬化物の室温での十分な硬さが得られなくなるためであり、一方、上記範囲の上限を超える、すなわちシルセスキオキサン単位が６０モル％を超えると、得られる硬化物の可とう性が不十分となるためである。また、ｄは、一般式：ＳｉＯ４／２で表されるシロキサン単位の割合を示す数であり、０≦ｄ≦０．２、好ましくは０≦ｄ≦０．１を満たす数である。これは、ｄが上記範囲の上限を超えると、得られる硬化物の可とう性が不十分となるためである。また、ｅは、一般式：Ｒ２Ｏ１／２で表されるシロキサン単位の割合を示す数であり、０≦ｅ≦０．１を満たす数である。これは，ｅが上記範囲の上限を超えると得られる硬化物の室温での十分な硬さが得られなくなるからである。なお、式中、ａ、ｂ、ｃ、ｄおよびｅの合計は１である（ａ＋ｂ＋ｃ＋ｄ＋ｅ＝１を満たす）。 In the formula, a is a number indicating the ratio of the siloxane unit represented by the general formula: R 1 3 SiO 1/2 and satisfies 0 ≦ a ≦ 0.1, preferably 0 ≦ a ≦ 0.08. Is a number. This is because sufficient strength and hardness at room temperature of a cured product obtained by excessively high fluidity when a exceeds the upper limit of the above range (in this specification, cured product is synonymous with crosslinked product) can be obtained. Because it disappears. b is a number indicating the ratio of siloxane units represented by the general formula: R 1 2 SiO 2/2 , and a number satisfying 0.2 ≦ b ≦ 0.9, preferably 0.3 ≦ b ≦ 0.7. It is. This is because if b is less than the lower limit of the above range, the refractive index does not become a preferable high refractive index, and if it exceeds the upper limit of the above range, sufficient hardness at room temperature of the resulting cured product cannot be obtained. Because. In the formula, c is a number indicating the ratio of siloxane units (silsesquioxane units) represented by the general formula: R 1 SiO 3/2 , and 0.1 ≦ c ≦ 0.6, preferably 0 .2 ≦ c ≦ 0.6. This is because when c is less than the lower limit of the above range, sufficient hardness at room temperature of the resulting cured product cannot be obtained, while on the other hand, the upper limit of the above range is exceeded, that is, silsesquioxane units are present. This is because the flexibility of the resulting cured product is insufficient when it exceeds 60 mol%. D is a number indicating the ratio of siloxane units represented by the general formula: SiO 4/2 , and is a number satisfying 0 ≦ d ≦ 0.2, preferably 0 ≦ d ≦ 0.1. This is because when d exceeds the upper limit of the above range, the flexibility of the obtained cured product becomes insufficient. Further, e is a number indicating the ratio of siloxane units represented by the general formula: R 2 O 1/2 and is a number satisfying 0 ≦ e ≦ 0.1. This is because sufficient hardness at room temperature of the obtained cured product cannot be obtained when e exceeds the upper limit of the above range. In the formula, the sum of a, b, c, d and e is 1 (a + b + c + d + e = 1 is satisfied).
　（Ｂ）成分は（Ａ）成分と組み合わされて架橋性オルガノポリシロキサン組成物の物性を左右する重要な第２成分であり、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し、一般式（１）：Ｒ３ ３ＳｉＯ１／２で表されるポリシロキサンの末端シロキサン単位を一分子中に少なくとも３個有する、アリール基を含有するアルケニル官能性分岐状オルガノポリシロキサンである。（Ｂ）成分は、２５℃において粘度が２０Ｐａ・ｓ以下の流動性を有することが好ましい。式中、Ｒ３は置換又は非置換の一価炭化水素基である。一価炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基などが例示され、好ましくはメチル基、エチル基である。また、アリール基としては置換または無置換のフェニル基、ナフチル基、アントラセニル基が例示される。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、ヘキセニル基が例示される。複数のＲ３は互いに同じであっても異なっていてもよい。分岐状オルガノポリシロキサンでも一般式：Ｒ３ ３ＳｉＯ１／２で表されるポリシロキサンの末端シロキサン単位を一分子中に少なくとも３個有することで、２５℃において粘度が１００Ｐａ・ｓ（すなわち１０００００ｍＰａ・ｓ）以下の流動性を有するポリシロキサンとすることができる。また、（Ｂ）成分の製造方法を制御することによって、三次元構造のアルケニル官能性分岐状オルガノポリシロキサンの分子量を好ましい範囲に制御することができ、２５℃において粘度が好ましい範囲以下の流動性を有するポリシロキサンとすることができる。この分岐状構造を持ちながら、かつ２５℃で流動性を有することから、速い硬化速度、また硬化物の表面タックのない組成物を得ることができる。
　なお、２５℃において粘度が１００Ｐａ・ｓであると、２５℃で流動性を有することは当業者にとって自明である。
　（Ｂ）成分は、２５℃において粘度が５００００ｍＰａ・ｓ以下であることが好ましく、３００００ｍＰａ・ｓ以下であることがより好ましく、２００００ｍＰａ・ｓ以下であることが特に好ましい。 The component (B) is an important second component that is combined with the component (A) and determines the physical properties of the crosslinkable organopolysiloxane composition, and includes at least two alkenyl groups and at least one aryl in one molecule. An alkenyl-functional branched organopolyethylene having an aryl group and having at least three terminal siloxane units of a polysiloxane represented by the general formula (1): R 3 3 SiO 1/2 in one molecule. Siloxane. The component (B) preferably has fluidity with a viscosity of 20 Pa · s or less at 25 ° C. In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group and an ethyl group are preferable. Examples of the aryl group include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. A plurality of R 3 may be the same as or different from each other. Even in the branched organopolysiloxane, by having at least three terminal siloxane units of polysiloxane represented by the general formula: R 3 3 SiO 1/2 in one molecule, the viscosity is 100 Pa · s at 25 ° C. (that is, 100000 mPa · s). s) A polysiloxane having the following fluidity can be obtained. Further, by controlling the production method of the component (B), the molecular weight of the alkenyl functional branched organopolysiloxane having a three-dimensional structure can be controlled within a preferable range, and the fluidity at a viscosity of 25 ° C. or less is preferable. A polysiloxane having While having this branched structure and having fluidity at 25 ° C., a composition having a high curing speed and no surface tack of the cured product can be obtained.
It is obvious to those skilled in the art that when the viscosity is 100 Pa · s at 25 ° C., it has fluidity at 25 ° C.
The component (B) has a viscosity of preferably 50000 mPa · s or less at 25 ° C., more preferably 30000 mPa · s or less, and particularly preferably 20000 mPa · s or less.
　このような（Ｂ）成分としては、平均単位式：
（Ｒ４ ３ＳｉＯ１／２）ｆ（Ｒ４ ２ＳｉＯ２／２）ｇ（Ｒ４ＳｉＯ３／２）ｈ（ＳｉＯ４／２）ｉで示されるアリール基を含有するアルケニル官能性分岐状オルガノポリシロキサンが例示される。ここでＲ４は炭素数１～１４の一価炭化水素基で、そのうち少なくとも２個は炭素数２～６のアルケニル基であり、少なくとも１個はアリール基である。一価炭化水素基としてはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基などが例示され、好ましくはメチル基、エチル基である。また、アリール基としては置換または無置換のフェニル基、ナフチル基、アントラセニル基が例示される。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、ヘキセニル基が例示される。複数のＲ４は互いに同じであっても異なっていてもよい。式中、ｆ、ｇ、ｈ、ｉは、０＜ｆ≦０．８、０≦ｇ≦０．９６、０＜（ｈ＋ｉ）、０．５≦ｆ／（ｈ＋ｉ）≦４、ｆ＋ｇ＋ｈ＋ｉ＝１を満たす数である。ここでｆは２５℃で２０Ｐａ・ｓ以下の流動性を得るための一般式：Ｒ４ ３ＳｉＯ１／２で表されるポリシロキサンの末端シロキサン単位の量を規定する数であり、ｈとｉはオルガノポリシロキサンが分岐状構造をとるための成分を規定する数であって、ｆとｈ＋ｉのいずれも０よりも大きい数でなければならない。また、２５℃で２０Ｐａ・ｓ以下の流動性を得るためには、分岐点に対する一般式：
Ｒ３ ３ＳｉＯ１／２で表されるポリシロキサンの末端シロキサン単位の量の比ｆ／（ｈ＋ｉ）は０．５以上でなければならず、最大は４である。一般式：Ｒ４ ２ＳｉＯ２／２で表される直鎖状成分は必ずしも必須構成成分ではないが、必要な粘度を得るためにポリマー内の成分として導入してもよく、０≦ｇ≦０．９６の範囲であればよいが、０≦ｇ≦０．９０であることが好ましい。
　（Ｂ）成分が、平均組成式（Ｒ４ ３ＳｉＯ（Ｒ４ ２ＳｉＯ）ｍ）ｅＳｉＲ４ （４－ｅ）（式中、Ｒ４は炭素数１～１４の一価炭化水素基で、少なくとも２個は炭素数２～６のアルケニル基であり、少なくとも１個はアリール基であり、ｍは０以上２００以下、ｅは３ないし４で示される整数）で示されるアリール基を含有するアルケニル官能性分岐状オルガノポリシロキサンである態様も好ましい。式中、ｍは直鎖状シロキサン単位の数を示し、０≦ｍ≦２００、好ましくは０≦ｍ≦１００を満たす数である。式中、ｅは３ないし４で示される整数で、分岐状オルガノポリシロキサンの分岐点を形成するための構造を規定する数字であり、ｅが３の時、Ｔ型の分岐点となり、ｅが４の時、十字型の分岐点となる。 As such component (B), the average unit formula:
(R 4 3 SiO 1/2 ) f (R 4 2 SiO 2/2 ) g (R 4 SiO 3/2 ) h (SiO 4/2 ) i- containing alkenyl functional branched organo Polysiloxane is exemplified. Here, R 4 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, of which at least two are alkenyl groups having 2 to 6 carbon atoms, and at least one is an aryl group. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group and an ethyl group are preferable. Examples of the aryl group include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. A plurality of R 4 may be different from one another the same. In the formula, f, g, h, i are 0 <f ≦ 0.8, 0 ≦ g ≦ 0.96, 0 <(h + i), 0.5 ≦ f / (h + i) ≦ 4, and f + g + h + i = 1. It is a number that satisfies. Here, f is a number that defines the amount of terminal siloxane units of the polysiloxane represented by the general formula: R 4 3 SiO 1/2 for obtaining fluidity of 20 Pa · s or less at 25 ° C., and h and i Is a number that defines the component for the organopolysiloxane to take a branched structure, and both f and h + i must be greater than zero. Moreover, in order to obtain fluidity of 20 Pa · s or less at 25 ° C., a general formula for the branch point:
The ratio f / (h + i) of the amount of terminal siloxane units of the polysiloxane represented by R 3 3 SiO 1/2 must be 0.5 or more, and the maximum is 4. The linear component represented by the general formula: R 4 2 SiO 2/2 is not necessarily an essential component, but may be introduced as a component in the polymer in order to obtain a necessary viscosity, and 0 ≦ g ≦ 0 It may be in the range of .96, but 0 ≦ g ≦ 0.90 is preferable.
Component (B) is an average composition formula (R 4 3 SiO (R 4 2 SiO) m ) e SiR 4 (4-e) (wherein R 4 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, At least 2 is an alkenyl group having 2 to 6 carbon atoms, at least one is an aryl group, m is 0 or more and 200 or less, and e is an integer represented by 3 to 4) An embodiment that is a functional branched organopolysiloxane is also preferred. In the formula, m represents the number of linear siloxane units, and is a number satisfying 0 ≦ m ≦ 200, preferably 0 ≦ m ≦ 100. In the formula, e is an integer represented by 3 to 4, and is a number that defines the structure for forming the branch point of the branched organopolysiloxane. When e is 3, it becomes a T-type branch point, and e is At 4, it becomes a cross-shaped branch point.
　また、（Ｂ）成分の例として、式：Ｒ５Ｒ６ ２ＳｉＯ（Ｒ６ ２ＳｉＯ）ｎＳｉＲ５Ｒ６ ２で示されるアリール基を含有するアルケニル官能性直鎖状オルガノポリシロキサンと、式：
（ＨＲ７ ２ＳｉＯ）ｊＳｉＲ７ （４－ｊ）（Ｒ７は炭素数１～１４の一価炭化水素基であり、ｊは３ないし４で示される整数。）で示されるケイ素原子結合水素原子を含有するシロキサンオリゴマーを、ヒドロシリル化反応してなる、生成物一分子中にアルケニル基を少なくとも３個有し、ケイ素原子結合水素原子が無い、アリール基を含有するアルケニル官能性分岐状オルガノポリシロキサンを挙げることができる。式中、Ｒ５は炭素数２～６のアルケニル基であり、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基が例示される。Ｒ６は炭素数１～１４の一価炭化水素基で、少なくとも１個はアリール基であり、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基などが例示され、好ましくはメチル基、エチル基である。また、アリール基としては置換または無置換のフェニル基、ナフチル基、アントラセニル基が例示される。複数のＲ５、Ｒ６およびＲ７はそれぞれ互いに同じであっても異なっていてもよい。式中、ｎは直鎖状シロキサン単位の数を示し、ｎは０以上２００以下であり、好ましくは０≦ｎ≦１００を満たす数である。これは、ｎが上記範囲の上限を超えると、得られる分岐状オルガノポリシロキサンの粘度が２５℃で２０Ｐａ・ｓを超えるためである。式中、Ｒ７は炭素数１～１４の一価炭化水素基であり、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基や、置換または無置換のフェニル基、ナフチル基、アントラセニル基などのアリール基が例示される。Ｒ７はアルケニル基を含まない。また、式中、ｊは３ないし４で示される整数で、分岐状オルガノポリシロキサンの分岐点を形成するための構造を規定する数字であり、ｊが３の時、Ｔ型の分岐点となり、ｊが４の時、十字型の分岐点となる。 As an example of the component (B), an alkenyl functional linear organopolysiloxane containing an aryl group represented by the formula: R 5 R 6 2 SiO (R 6 2 SiO) n SiR 5 R 6 2 , :
(HR 7 2 SiO) j SiR 7 (4-j) (R 7 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, j is an integer represented by 3 to 4) An alkenyl functional branched organopolysiloxane containing an aryl group containing at least three alkenyl groups in one molecule of the product and having no silicon-bonded hydrogen atoms, which is obtained by hydrosilylating a siloxane oligomer containing atoms. Mention may be made of siloxane. In the formula, R 5 is an alkenyl group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. R 6 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of which is an aryl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Group, an ethyl group. Examples of the aryl group include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group. The plurality of R 5 , R 6 and R 7 may be the same as or different from each other. In the formula, n represents the number of linear siloxane units, n is 0 or more and 200 or less, and preferably 0 ≦ n ≦ 100. This is because when n exceeds the upper limit of the above range, the viscosity of the obtained branched organopolysiloxane exceeds 20 Pa · s at 25 ° C. Wherein, R 7 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a substituted or unsubstituted phenyl group, a naphthyl group, An aryl group such as an anthracenyl group is exemplified. R 7 does not contain an alkenyl group. In the formula, j is an integer represented by 3 to 4, and is a number defining a structure for forming a branch point of the branched organopolysiloxane. When j is 3, a T-type branch point is obtained. When j is 4, it becomes a cross-shaped branch point.
　本発明の効果を発揮するためには（Ａ）成分と（Ｂ）成分の混合比率は、Ａ／Ｂの重量比が１／１００から１００／１であり、１／５０～５０／１であることが好ましく、１／２０～２０／１であることがより好ましい。
　実施例では（Ａ）成分と（Ｂ）成分の量が重量部で記載されており、当業者であれば本明細書中の（Ａ）成分と（Ｂ）成分の混合比率は重量比で示されていることは自明である。 In order to exert the effect of the present invention, the mixing ratio of the component (A) and the component (B) is such that the weight ratio of A / B is 1/100 to 100/1, and 1/50 to 50/1. It is preferable that the ratio is 1/20 to 20/1.
In the examples, the amounts of the component (A) and the component (B) are described in parts by weight, and those skilled in the art will show the mixing ratio of the component (A) and the component (B) in the present specification by weight ratio. It is self-evident.
　（Ｃ）成分は、本発明の架橋性オルガノポリシロキサン組成物（以下、本組成物とも言う）の架橋剤であり、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し、ケイ素原子結合有機基の１２～７０モル％がアリール基であるオルガノポリシロキサンである。（Ｃ）成分中のケイ素原子結合水素原子は少なくとも２個である。これはケイ素原子結合水素原子が一分子中に２個未満であると、得られる硬化物の室温での十分な機械的強度が得られなくなるからである。（Ｃ）成分中のケイ素原子結合有機基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フェニル基、トリル基、ナフチル基、アントラセニル基、ビフェニル基などのアリール基などが例示される。（Ｃ）成分は、ケイ素原子結合有機基の１２～７０モル％がアリール基である。これは、アリール基の含有量が上記範囲を逸脱すると（Ａ）成分と（Ｂ）成分の混合物との相溶性が悪くなって得られる硬化物の透明性が失われ、機械的特性も悪くなるからである。ケイ素原子結合水素原子は、Ｓｉ－Ｈと同義である。 Component (C) is a crosslinking agent of the crosslinkable organopolysiloxane composition of the present invention (hereinafter also referred to as the present composition), and has at least two silicon atom-bonded hydrogen atoms in one molecule. Organopolysiloxane in which 12 to 70 mol% of the combined organic groups are aryl groups. There are at least two silicon-bonded hydrogen atoms in component (C). This is because if the number of silicon-bonded hydrogen atoms is less than 2 in one molecule, sufficient mechanical strength at room temperature of the resulting cured product cannot be obtained. As the silicon atom-bonded organic group in the component (C), an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a phenyl group, Examples include aryl groups such as tolyl group, naphthyl group, anthracenyl group and biphenyl group. In the component (C), 12 to 70 mol% of the silicon-bonded organic group is an aryl group. This is because if the content of the aryl group deviates from the above range, the compatibility of the mixture of the component (A) and the component (B) is deteriorated and the transparency of the resulting cured product is lost, and the mechanical properties are also deteriorated. Because. A silicon atom-bonded hydrogen atom is synonymous with Si—H.
　このような（Ｃ）成分としては、一般式：
（ＨＲ８ ２ＳｉＯ）２ＳｉＲ８ ２、（ＨＲ８ ２ＳｉＯＳｉＲ８ ２）２Ｏ、
（ＨＲ８ ２ＳｉＯ）３ＳｉＲ８、（（ＨＲ８ ２ＳｉＯ）２ＳｉＲ８）２Ｏなどが例示される。式中、Ｒ８は炭素数１～１４の一価炭化水素基で、少なくとも１個はアリール基で、一価炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基などが例示され、好ましくはメチル基、エチル基である。また、アリール基としては、置換又は無置換のフェニル基、ナフチル基、アントラセニル基が例示される。複数のＲ８は互いに同じであっても異なっていてもよい。なお、Ｒ８の内、アリール基の含有量は１２～７０モル％の範囲である。 As such component (C), the general formula:
(HR 8 2 SiO) 2 SiR 8 2 , (HR 8 2 SiOSiR 8 2 ) 2 O,
Examples include (HR 8 2 SiO) 3 SiR 8 , ((HR 8 2 SiO) 2 SiR 8 ) 2 O, and the like. In the formula, R 8 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, A hexyl group etc. are illustrated, Preferably they are a methyl group and an ethyl group. Examples of the aryl group include a substituted or unsubstituted phenyl group, naphthyl group, and anthracenyl group. A plurality of R 8 may be the same as or different from each other. Of R 8 , the aryl group content is in the range of 12 to 70 mol%.
　本組成物において、（Ｃ）成分の含有量は、（Ａ）成分中と（Ｂ）成分中のアルケニル基の合計に対する本成分中のケイ素原子結合水素原子のモル比が０．５～２の範囲内となる量であり、好ましくは、０．５～１．５の範囲内となる量である。これは（Ｃ）成分の含有量が上記範囲外であると、得られる硬化物の室温での機械的強度が不十分となるためである。 In this composition, the content of component (C) is such that the molar ratio of silicon-bonded hydrogen atoms in this component to the total of alkenyl groups in component (A) and component (B) is 0.5-2. An amount that falls within the range, and preferably an amount that falls within the range of 0.5 to 1.5. This is because the mechanical strength at room temperature of the resulting cured product is insufficient when the content of the component (C) is outside the above range.
　（Ｄ）成分は、（Ａ）成分と（Ｂ）成分のアルケニル基と（Ｃ）成分中のケイ素原子結合水素原子と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。（Ｄ）成分としては、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が、本組成物の架橋を著しく促進できることから白金系触媒が好ましい。特に触媒活性の高さから、白金－アルケニルシロキサン錯体が好ましく、錯体の安定性が良好なことから、１，３－ジビニル－１，１，３，３－テトラメチルジシロキサンを配位子として持つ白金錯体が好ましい。 The component (D) is a hydrosilylation reaction catalyst for accelerating the hydrosilylation reaction between the alkenyl groups of the components (A) and (B) and the silicon atom-bonded hydrogen atom in the component (C). Examples of the component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferred because they can significantly accelerate the crosslinking of the composition. In particular, a platinum-alkenylsiloxane complex is preferable because of its high catalytic activity, and since the stability of the complex is good, it has 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as a ligand. Platinum complexes are preferred.
　本組成物において、（Ｄ）成分の含有量は、（Ａ）成分と（Ｂ）成分のアルケニル基と（Ｃ）成分のケイ素原子結合水素原子とのヒドロシリル化反応を促進するに十分の量であれば特に限定されない。好ましくは、本組成物に対して、（Ｄ）成分中の金属原子が重量（通常は質量と同義）単位で０．１ｐｐｍから１００ｐｐｍの範囲内である量であることが好ましい。これは（Ｄ）成分の含有量が上記範囲の下限未満であると、得られる組成物が十分に架橋しなくなる、または十分な速度で架橋しなくなるからであり、一方、上記範囲の上限を超えると得られる硬化物に着色等の問題を生じる恐れがあるからである。 In this composition, the content of the component (D) is an amount sufficient to promote the hydrosilylation reaction between the alkenyl group of the component (A), the component (B), and the silicon atom-bonded hydrogen atom of the component (C). If there is no particular limitation. Preferably, the amount of the metal atom in component (D) in the composition (D) is in the range of 0.1 ppm to 100 ppm in terms of weight (usually synonymous with mass). This is because if the content of component (D) is less than the lower limit of the above range, the resulting composition will not be sufficiently crosslinked, or will not be crosslinked at a sufficient rate, while exceeding the upper limit of the above range. This is because problems such as coloring may occur in the obtained cured product.
　本組成物は、上記（Ａ）成分から（Ｄ）成分から少なくともなるが、その他任意の成分として硬化速度を任意に変化させる目的で反応抑制剤（ｉｎｈｉｂｉｔｏｒ；硬化遅延剤とも言われる）を添加してもよい。反応抑制剤としては、２－メチル－３－ブチン－２－オール、２－フェニル－３－ブチン－２－オール、エチニルシクロヘキサノール等のアルキンアルコール、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、ベンゾトリアゾールなどが例示される。これらの反応抑制剤の含有量は特に限定されないが、本組成物の重量に対して１ｐｐｍ～１０００ｐｐｍの範囲内であることが好ましい。 The composition comprises at least the component (A) to the component (D), but a reaction inhibitor (also referred to as a curing retarder) is added as an optional component for the purpose of arbitrarily changing the curing rate. May be. Reaction inhibitors include 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, alkyne alcohols such as ethynylcyclohexanol, 1,3,5,7-tetramethyl-1 , 3,5,7-tetravinylcyclotetrasiloxane, benzotriazole and the like. The content of these reaction inhibitors is not particularly limited, but is preferably in the range of 1 ppm to 1000 ppm with respect to the weight of the present composition.
　また、用途に応じて基材との接着性を要求される場合には本組成物に接着促進剤（ａｄｈｅｓｉｏｎ　ｐｒｏｍｏｔｅｒ；接着付与剤とも言われる）を含有してもよい。この接着促進剤としては、トリアルコキシシリル基（例えばトリメトキシシリル基やトリエトキシシリル基）とヒドロシリル基、エポキシ基（例えば、３－グリシドキシプロピル基）、アルケニル基（例えば、ビニル基やアリル基）を一分子中に有するオルガノシランやオルガノシロキサンオリゴマーなどがあげられる。 In addition, when the adhesiveness with the base material is required depending on the use, the composition may contain an adhesion promoter (also referred to as an adhesion promoter). Examples of the adhesion promoter include trialkoxysilyl groups (for example, trimethoxysilyl group and triethoxysilyl group), hydrosilyl groups, epoxy groups (for example, 3-glycidoxypropyl group), alkenyl groups (for example, vinyl group and allyl group). Group) in one molecule, and the like.
　さらに、本組成物には、本発明の目的を損なわない限り、その他任意の成分として、前記（Ａ）成分から（Ｃ）成分以外のオルガノポリシロキサン、無機質充填剤（例えば、シリカ、ガラス、アルミナ、酸化亜鉛等）、ポリメタクリレート樹脂等の有機樹脂微粉末、耐熱剤、染料、顔料、蛍光体、難燃性付与剤、溶剤等を含有してもよい。
　前記（Ａ）成分から（Ｃ）成分以外のオルガノポリシロキサンとして、アルケニル官能性直鎖状オルガノポリシロキサンを挙げることができるが、本発明の架橋性オルガノポリシロキサン組成物は、アルケニル官能性直鎖状オルガノポリシロキサンを含まない。本発明では、従来は必須構成成分と考えられていたアルケニル官能性直鎖状オルガノポリシロキサンを用いなくても、（Ｂ）成分を用いることで良好な特性の架橋性オルガノポリシロキサン組成物を得ることができる。 Further, the present composition includes, as the other optional components, organopolysiloxanes other than the components (A) to (C), inorganic fillers (for example, silica, glass, alumina), as long as the object of the present invention is not impaired. , Zinc oxide, etc.), organic resin fine powder such as polymethacrylate resin, heat-resistant agent, dye, pigment, phosphor, flame retardant, solvent and the like.
Examples of the organopolysiloxane other than the component (A) to the component (C) include alkenyl functional linear organopolysiloxanes. The crosslinkable organopolysiloxane composition of the present invention is an alkenyl functional linear chain. No organopolysiloxane. In the present invention, a crosslinkable organopolysiloxane composition having good characteristics can be obtained by using the component (B) without using an alkenyl functional linear organopolysiloxane which has been conventionally considered as an essential component. be able to.
　本組成物の粘度の好ましい範囲は、（Ｂ）成分の粘度の好ましい範囲と同様である。
　本組成物は加熱により速やかに架橋が進行し、表面タックがなく、十分の可とう性を有する硬化物を形成し、好ましくは硬い硬化物を形成できる。
　本組成物は加熱により完全硬化した場合に用途に応じてより好ましい硬さにすることができ、特に高い硬さも得ることができる。本発明の架橋性オルガノポリシロキサン組成物は１５０℃で３０分間の加熱をされた場合にＪＩＳ　Ｋ　６２５３で規定されるタイプＤデュロメータ硬さが４５以上となることが好ましく、所望の用途に応じてタイプＤデュロメータ硬さを４５～６０とすることができ、また別の所望の用途に応じてタイプＤデュロメータ硬さを６０～８０とすることができる。逆に、ゴム状の硬化物を得たい場合は、本組成物は加熱により完全硬化した場合にＪＩＳ　Ｋ　６２５３で規定されるタイプＡデュロメータ硬さを３０～６０とすることができ、また別の所望の用途に応じてタイプＡデュロメータ硬さを６０～９０とすることができる。
　本組成物は、加熱により、機械的物性、硬度などが変化しない安定した硬化物を形成することができる。加熱温度としては８０℃～２００℃での範囲内で行うことが好ましい。硬化速度が速いので、射出成型などに好適な組成物であるが、必ずしも成型方法に制限があるわけではない。通常の混合、オーブン加熱等による接着剤用途、フィルム形成、ポッティング剤、コーティング剤、アンダーフィル剤として使用することもできる。特に、高屈折率で光透過率が高いので光学用途のレンズ材料や、発光ダイオードなどの半導体素子のポッティング剤、コーティング剤、保護材、封止材などの用途に好適である。 The preferable range of the viscosity of the present composition is the same as the preferable range of the viscosity of the component (B).
The composition is rapidly cross-linked by heating, has no surface tack, forms a cured product having sufficient flexibility, and preferably can form a hard cured product.
When the composition is completely cured by heating, the composition can be made to have a more preferable hardness depending on the application, and particularly high hardness can be obtained. The crosslinkable organopolysiloxane composition of the present invention preferably has a type D durometer hardness of 45 or more as defined in JIS K 6253 when heated at 150 ° C. for 30 minutes, depending on the desired application. The Type D durometer hardness can be 45-60, and the Type D durometer hardness can be 60-80 depending on other desired applications. Conversely, when it is desired to obtain a rubber-like cured product, this composition can have a type A durometer hardness of 30 to 60 as defined in JIS K 6253 when completely cured by heating. The type A durometer hardness can be 60-90 depending on the desired application.
The composition can form a stable cured product in which mechanical properties, hardness and the like are not changed by heating. The heating temperature is preferably within the range of 80 ° C to 200 ° C. Since the curing speed is high, the composition is suitable for injection molding and the like, but the molding method is not necessarily limited. It can also be used as an adhesive application by ordinary mixing, oven heating, etc., film formation, potting agent, coating agent, underfill agent. In particular, since it has a high refractive index and a high light transmittance, it is suitable for lens materials for optical applications, potting agents for semiconductor elements such as light emitting diodes, coating agents, protective materials, and sealing materials.
　次に、本発明の硬化物について詳細に説明する。
　本発明の硬化物は、上記の架橋性オルガノポリシロキサン組成物を硬化してなることを特徴とする。硬化物の形状は特に限定されず、例えば、塊状、シート状、フィルム状、など多岐にわたる。硬化物は、これを単体で取り扱うこともできるが、光半導体素子等を被覆もしくは封止した状態で取り扱うことも可能である。 Next, the cured product of the present invention will be described in detail.
The cured product of the present invention is obtained by curing the crosslinkable organopolysiloxane composition. The shape of the cured product is not particularly limited, and may be various, such as a lump, sheet, or film. The cured product can be handled alone, but can also be handled in a state where the optical semiconductor element or the like is covered or sealed.
　本発明の架橋性オルガノポリシロキサン組成物を実施例により詳細に説明する。なお、粘度は２５℃における値である。また、式中のＭｅ、Ｐｈ、およびＶｉは、それぞれメチル基、フェニル基、およびビニル基を表している。なお、硬化物の硬さを、ＪＩＳ　Ｋ　６２５３「加硫ゴム及び熱可塑性ゴムの硬さ試験方法」に既定のタイプＡデュロメータおよびタイプＤデュロメータにより測定した。ＪＩＳは、Ｊａｐａｎｅｓｅ　Ｉｎｄｕｓｔｒｉａｌ　Ｓｔａｎｄａｒｄｓの略称である。 The crosslinkable organopolysiloxane composition of the present invention will be described in detail with reference to examples. The viscosity is a value at 25 ° C. Moreover, Me, Ph, and Vi in the formula represent a methyl group, a phenyl group, and a vinyl group, respectively. The hardness of the cured product was measured with a type A durometer and a type D durometer as defined in JIS K 6253 “Hardness test method for vulcanized rubber and thermoplastic rubber”. JIS is an abbreviation for Japan Industrial Standards.
［実施例１］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６２重量部、式：
（ＶｉＭｅ２ＳｉＯ（ＳｉＰｈＭｅＯ）１５）３ＳｉＰｈで表される粘度が２５℃で１２００ｍＰａ・ｓの分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２１重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で５ｐｐｍとなる量を混合して２５℃の粘度が２５００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 1]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 62 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
(ViMe 2 SiO (SiPhMeO) 15 ) 3 SiPh, the viscosity is represented by 17 parts by weight of branched methylvinylphenylpolysiloxane having a viscosity of 1200 mPa · s at 25 ° C., and the formula: (HMe 2 SiO) 2 SiPh 2 After uniformly mixing 21 parts by weight of trisiloxane, an amount of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is 5 ppm by weight with respect to the present composition. Were mixed to prepare a crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 2500 mPa · s.
　この組成物は、１５０℃に加熱すると２４０秒で硬化が完了し、２５℃でタイプＡデュロメータ硬さ６０のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 240 seconds, and a rubber-like cured product having a type A durometer hardness of 60 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例２］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６３重量部、式：
ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｖｉで示されるオルガノポリシロキサン４０重量部と、式：（ＨＭｅ２ＳｉＯ）３ＳｉＰｈで示されるシロキサンオリゴマー１重量部をヒドロシリル化反応して合成した、式：
｛（ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｃ２Ｈ４Ｍｅ２ＳｉＯ）２ＳｉＰｈＣ２Ｈ４Ｍｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）１９｝２で示される粘度が２５℃で５３５０ｍＰａ・ｓの分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２０重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で５ｐｐｍとなる量を混合して２５℃の粘度が３５００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 2]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 63 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
40 parts by weight of an organopolysiloxane represented by ViMe 2 SiO (PhMeSiO) 38 SiMe 2 Vi and 1 part by weight of a siloxane oligomer represented by the formula: (HMe 2 SiO) 3 SiPh were synthesized by a hydrosilylation reaction.
{(ViMe 2 SiO (PhMeSiO) 38 SiMe 2 C 2 H 4 Me 2 SiO) 2 SiPhC 2 H 4 Me 2 SiO (PhMeSiO) 19 } 2 branched methylvinylphenyl having a viscosity of 5350 mPa · s at 25 ° C. After uniformly mixing 17 parts by weight of polysiloxane and 20 parts by weight of trisiloxane represented by the formula: (HMe 2 SiO) 2 SiPh 2 , platinum 1,3-divinyl-1,1,3,3-tetra A crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 3500 mPa · s was prepared by mixing the methyldisiloxane complex in an amount of 5 ppm by weight with respect to the present composition.
　この組成物は、１５０℃に加熱すると２２０秒で硬化が完了し、２５℃でタイプＡデュロメータ硬さ５５のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 220 seconds, and a rubber-like cured product having a type A durometer hardness of 55 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例３］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６１重量部、式：
（ＶｉＭｅ２ＳｉＯ（ＳｉＰｈＭｅＯ）１５）４Ｓｉで表される粘度が２５℃で１５００ｍＰａ・ｓの分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２２重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で５ｐｐｍとなる量を混合して２５℃の粘度が２７００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 3]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 61 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
(ViMe 2 SiO (SiPhMeO) 15 ) 4 Si is represented by 17 parts by weight of branched methylvinylphenylpolysiloxane having a viscosity of 1500 mPa · s at 25 ° C. and represented by the formula: (HMe 2 SiO) 2 SiPh 2 After uniformly mixing 22 parts by weight of trisiloxane, an amount of platinum of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is 5 ppm by weight with respect to the present composition. Were mixed to prepare a crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 2700 mPa · s.
　この組成物は、１５０℃に加熱すると２００秒で硬化が完了し、２５℃でタイプＡデュロメータ硬さ６８のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 200 seconds, and a rubber-like cured product having a type A durometer hardness of 68 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例４］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６３重量部、式：
ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｖｉで示されるオルガノポリシロキサン５７部と、式：（ＨＭｅ２ＳｉＯ）４Ｓｉで示されるシロキサンオリゴマー１部をヒドロシリル化反応して合成した式：
｛（ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｃ２Ｈ４Ｍｅ２ＳｉＯ）３ＳｉＣ２Ｈ４Ｍｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）１９｝２で示される粘度が２５℃で８０００ｍＰａ・ｓの分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２０重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で５ｐｐｍとなる量を混合して２５℃の粘度が３７００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 4]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 63 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
Formula synthesized by hydrosilylation reaction of 57 parts of an organopolysiloxane represented by ViMe 2 SiO (PhMeSiO) 38 SiMe 2 Vi and 1 part of a siloxane oligomer represented by the formula: (HMe 2 SiO) 4 Si:
{(ViMe 2 SiO (PhMeSiO) 38 SiMe 2 C 2 H 4 Me 2 SiO) 3 SiC 2 H 4 Me 2 SiO (PhMeSiO) 19 } 2 , branched methylvinylphenyl having a viscosity of 8000 mPa · s at 25 ° C. After uniformly mixing 17 parts by weight of polysiloxane and 20 parts by weight of trisiloxane represented by the formula: (HMe 2 SiO) 2 SiPh 2 , platinum 1,3-divinyl-1,1,3,3-tetra A crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 3700 mPa · s was prepared by mixing a methyldisiloxane complex in an amount such that the platinum amount was 5 ppm by weight with respect to the present composition.
　この組成物は、１５０℃に加熱すると２４０秒で硬化が完了し、２５℃でタイプＡデュロメータ硬さ５７のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 240 seconds, and a rubber-like cured product having a type A durometer hardness of 57 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例５］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６２重量部、式：
（ＶｉＭｅ２ＳｉＯ（ＳｉＰｈＭｅＯ）１５）３ＳｉＰｈで表される実施例１で用いた分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２１重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で５ｐｐｍとなる量および、エチニルヘキサノールを本組成物に対して２００ｐｐｍを混合して２５℃の粘度が２５００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 5]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 62 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
(ViMe 2 SiO (SiPhMeO) 15 ) 3 SiPh represented by 17 parts by weight of branched methylvinylphenylpolysiloxane used in Example 1, and trisiloxane 21 represented by the formula: (HMe 2 SiO) 2 SiPh 2 After uniformly mixing parts by weight, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is added in an amount such that the platinum amount is 5 ppm by weight with respect to the composition, and ethynyl A crosslinkable organopolysiloxane composition having a viscosity of 2500 mPa · s at 25 ° C. was prepared by mixing 200 ppm of hexanol with respect to the present composition.
この組成物は、１５０℃に加熱すると１５分で硬化が完了し、２５℃でタイプＡデュロメータ硬さ６０のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 15 minutes, and a rubber-like cured product having a type A durometer hardness of 60 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例６］
平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６３重量部、式：
ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｖｉで示されるオルガノポリシロキサン４０重量部と、式：（ＨＭｅ２ＳｉＯ）３ＳｉＰｈで示されるシロキサンオリゴマー１重量部をヒドロシリル化反応して合成した式：
｛（ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｃ２Ｈ４Ｍｅ２ＳｉＯ）２ＳｉＰｈＣ２Ｈ４Ｍｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）１９｝２で示される実施例２で用いた分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２０重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で５ｐｐｍとなる量および、エチニルヘキサノールを本組成物に対して２００ｐｐｍを混合して２５℃の粘度が３５００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 6]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 63 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
Formula synthesized by hydrosilylation reaction of 40 parts by weight of an organopolysiloxane represented by ViMe 2 SiO (PhMeSiO) 38 SiMe 2 Vi and 1 part by weight of a siloxane oligomer represented by the formula: (HMe 2 SiO) 3 SiPh:
{Branched methylvinylphenyl polysiloxane 17 used in Example 2 represented by (ViMe 2 SiO (PhMeSiO) 38 SiMe 2 C 2 H 4 Me 2 SiO) 2 SiPhC 2 H 4 Me 2 SiO (PhMeSiO) 19 } 2 1 part by weight of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum after uniformly mixing 20 parts by weight of trisiloxane represented by the formula: (HMe 2 SiO) 2 SiPh 2 Crosslinkable organopolysiloxane composition having a platinum amount of 5 ppm by weight with respect to the present composition and 200 ppm of ethynylhexanol with respect to the present composition and having a viscosity of 3500 mPa · s at 25 ° C. A product was prepared.
この組成物は、１５０℃に加熱すると１５分で硬化が完了し、２５℃でタイプＡデュロメータ硬さ５５のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 15 minutes, and a rubber-like cured product having a type A durometer hardness of 55 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例７］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６２重量部、式：
（ＶｉＭｅ２ＳｉＯ（ＳｉＰｈＭｅＯ）１５）３ＳｉＰｈで表される実施例１で用いた分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２１重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で２５ｐｐｍとなる量を混合して２５℃の粘度が２５００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 7]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 62 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
(ViMe 2 SiO (SiPhMeO) 15 ) 3 SiPh represented by 17 parts by weight of branched methylvinylphenylpolysiloxane used in Example 1, and trisiloxane 21 represented by the formula: (HMe 2 SiO) 2 SiPh 2 After uniformly mixing parts by weight, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was mixed with the composition in such an amount that the platinum amount was 25 ppm by weight. A crosslinkable organopolysiloxane composition having a viscosity of 2500 mPa · s at 25 ° C. was prepared.
　この組成物は、２０時間後の粘度が２５℃で４５００ｍＰａ・ｓであった。１５０℃に加熱すると４０秒で硬化が完了し、２５℃でタイプＡデュロメータ硬さ６０のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 This composition had a viscosity of 4500 mPa · s at 25 ° C. after 20 hours. When heated to 150 ° C., curing was completed in 40 seconds, and a rubber-like cured product having a type A durometer hardness of 60 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例８］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６３重量部、式：
ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｖｉで示されるオルガノポリシロキサン４０重量部と、式：（ＨＭｅ２ＳｉＯ）３ＳｉＰｈで示されるシロキサンオリゴマー１重量部をヒドロシリル化反応して合成した式：
｛（ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｃ２Ｈ４Ｍｅ２ＳｉＯ）２ＳｉＰｈＣ２Ｈ４Ｍｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）１９｝２で示される実施例２で用いた分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２０重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で２５ｐｐｍとなる量を混合して２５℃の粘度が３５００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 8]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 63 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
Formula synthesized by hydrosilylation reaction of 40 parts by weight of an organopolysiloxane represented by ViMe 2 SiO (PhMeSiO) 38 SiMe 2 Vi and 1 part by weight of a siloxane oligomer represented by the formula: (HMe 2 SiO) 3 SiPh:
{Branched methylvinylphenyl polysiloxane 17 used in Example 2 represented by (ViMe 2 SiO (PhMeSiO) 38 SiMe 2 C 2 H 4 Me 2 SiO) 2 SiPhC 2 H 4 Me 2 SiO (PhMeSiO) 19 } 2 1 part by weight of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum after uniformly mixing 20 parts by weight of trisiloxane represented by the formula: (HMe 2 SiO) 2 SiPh 2 The complex was mixed with the present composition in such an amount that the platinum amount was 25 ppm by weight, thereby preparing a crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 3500 mPa · s.
　この組成物は、２０時間後の粘度が２５℃で７０００ｍＰａ・ｓであった。１５０℃に加熱すると３５秒で硬化が完了し、２５℃でタイプＡデュロメータ硬さ５５のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 This composition had a viscosity of 7000 mPa · s at 25 ° C. after 20 hours. When heated to 150 ° C., curing was completed in 35 seconds, and a rubber-like cured product having a type A durometer hardness of 55 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例９］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６４重量部、式：
（ＶｉＭｅ２ＳｉＯ（ＳｉＰｈＭｅＯ）１５）３ＳｉＰｈで表される実施例１で用いた分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）３ＳｉＰｈで表されるテトラシロキサン１９重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で５ｐｐｍとなる量を混合して２５℃の粘度が２６００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 9]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 64 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
(ViMe 2 SiO (SiPhMeO) 15 ) 17 parts by weight of branched methylvinylphenylpolysiloxane used in Example 1 represented by 3 SiPh, and 19 parts by weight of tetrasiloxane represented by the formula: (HMe 2 SiO) 3 SiPh After mixing the parts uniformly, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was mixed with the composition in such an amount that the platinum amount was 5 ppm by weight. A crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 2600 mPa · s was prepared.
　この組成物は、１５０℃に加熱すると２００秒で硬化が完了し、２５℃でタイプＡデュロメータ硬さ７５のゴム状の硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 This composition was cured in 200 seconds when heated to 150 ° C., and a rubber-like cured product having a type A durometer hardness of 75 was obtained at 25 ° C. There was no surface tack, and the hardness did not change even after heating.
［実施例１０］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．３（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４で表される分岐状メチルビニルフェニルポリシロキサン６０重量部、式：
（ＶｉＭｅ２ＳｉＯ１／２）０．３（Ｐｈ２ＳｉＯ）０．３（ＰｈＳｉＯ３／２）０．４で表される粘度が２５℃で９０００ｍＰａ・ｓの分岐状メチルビニルフェニルポリシロキサン１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２３重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で２０ｐｐｍとなる量を混合して２５℃の粘度が４０００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 10]
Average unit formula:
(MeViSiO 2/2) 0.3 (Ph 2 SiO 2/2) 0.3 (PhSiO 3/2) branched methyl vinyl phenyl polysiloxane 60 parts by weight represented by 0.4, the formula:
(ViMe 2 SiO 1/2 ) 0.3 (Ph 2 SiO) 0.3 (PhSiO 3/2 ) Branched methylvinylphenylpolysiloxane having a viscosity represented by 0.4 of 9000 mPa · s at 25 ° C. 17 weight Parts, and 23 parts by weight of trisiloxane represented by the formula: (HMe 2 SiO) 2 SiPh 2 were mixed uniformly, and then 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum A crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 4000 mPa · s was prepared by mixing an amount of 20 ppm by weight with respect to the present composition.
　この組成物は、１５０℃に加熱すると３００秒で硬化が完了し、２５℃でタイプＤデュロメータ硬さ５５の可とう性を有する硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 300 seconds, and a cured product having flexibility of type D durometer hardness 55 at 25 ° C. was obtained. There was no surface tack, and the hardness did not change even after heating.
［実施例１１］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．３（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４で表される分岐状メチルビニルフェニルポリシロキサン６０重量部、式：
（ＶｉＭｅ２ＳｉＯ１／２）０．４（Ｐｈ２ＳｉＯ）０．３（ＰｈＳｉＯ３／２）０．３で表される粘度が２５℃で２０００ｍＰａ・ｓの分岐状メチルビニルフェニルポリシロキサン１６重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２４重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で２０ｐｐｍとなる量を混合して２５℃の粘度が２５００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 11]
Average unit formula:
(MeViSiO 2/2) 0.3 (Ph 2 SiO 2/2) 0.3 (PhSiO 3/2) branched methyl vinyl phenyl polysiloxane 60 parts by weight represented by 0.4, the formula:
(ViMe 2 SiO 1/2 ) 0.4 (Ph 2 SiO) 0.3 (PhSiO 3/2 ) Branched methyl vinyl phenyl polysiloxane having a viscosity represented by 0.3 of 2000 mPa · s at 25 ° C. 16 weight And 24 parts by weight of trisiloxane represented by the formula: (HMe 2 SiO) 2 SiPh 2 are uniformly mixed, and then 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum A crosslinkable organopolysiloxane composition having a viscosity of 2500 mPa · s at 25 ° C. was prepared by mixing an amount of 20 ppm by weight with respect to the present composition.
　この組成物は、１５０℃に加熱すると２５０秒で硬化が完了し、２５℃でタイプＤデュロメータ硬さ５０の可とう性を有する硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 250 seconds, and a cured product having flexibility of type D durometer hardness 50 at 25 ° C. was obtained. There was no surface tack, and the hardness did not change even after heating.
［実施例１２］
　平均単位式：
（Ｍｅ２ＶｉＳｉＯ１／２）０．０５（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．２５（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６０重量部、式：
（ＶｉＭｅ２ＳｉＯ１／２）０．４（Ｐｈ２ＳｉＯ）０．３（ＰｈＳｉＯ３／２）０．３で表される粘度が２５℃で２０００ｍＰａ・ｓの分岐状メチルビニルフェニルポリシロキサン１６重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２４重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で２０ｐｐｍとなる量を混合して２５℃の粘度が２０００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 12]
Average unit formula:
(Me 2 ViSiO 1/2 ) 0.05 (MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.25 (PhSiO 3/2 ) 0.45 60 parts by weight of siloxane, formula:
(ViMe 2 SiO 1/2 ) 0.4 (Ph 2 SiO) 0.3 (PhSiO 3/2 ) Branched methyl vinyl phenyl polysiloxane having a viscosity represented by 0.3 of 2000 mPa · s at 25 ° C. 16 weight And 24 parts by weight of trisiloxane represented by the formula: (HMe 2 SiO) 2 SiPh 2 are uniformly mixed, and then 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum A crosslinkable organopolysiloxane composition having a viscosity of 2000 mPa · s at 25 ° C. was prepared by mixing an amount of 20 ppm by weight with respect to the present composition.
　この組成物は、１５０℃に加熱すると１５０秒で硬化が完了し、２５℃でタイプＤデュロメータ硬さ４５の可とう性を有する硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 150 seconds, and a cured product having flexibility of type D durometer hardness 45 at 25 ° C. was obtained. There was no surface tack, and the hardness did not change even after heating.
［実施例１３］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６０重量部、式：
（ＶｉＭｅ２ＳｉＯ１／２）０．３（Ｐｈ２ＳｉＯ）０．３（ＰｈＳｉＯ３／２）０．４で表される粘度が２５℃で８０００ｍＰａ・ｓの分岐状メチルビニルフェニルポリシロキサン１６重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２４重量部を均一に混合した後、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を本組成物に対して白金量が重量単位で５ｐｐｍとなる量を混合して２５℃の粘度が１２０００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Example 13]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 60 parts by weight of branched methylvinylphenyl polysiloxane represented by 0.45 , formula:
(ViMe 2 SiO 1/2 ) 0.3 (Ph 2 SiO) 0.3 (PhSiO 3/2 ) Branched methyl vinyl phenyl polysiloxane having a viscosity represented by 0.4 of 8000 mPa · s at 25 ° C. 16 weight And 24 parts by weight of trisiloxane represented by the formula: (HMe 2 SiO) 2 SiPh 2 are uniformly mixed, and then 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum A crosslinkable organopolysiloxane composition having a viscosity at 25 ° C. of 12000 mPa · s was prepared by mixing an amount of 5 ppm by weight with respect to the present composition.
　この組成物は、１５０℃に加熱すると３００秒で硬化が完了し、２５℃でタイプＤデュロメータ硬さ６０の可とう性を有する硬化物を得た。表面タックもなくその後の加熱でも硬さ変化は起こらなかった。 When this composition was heated to 150 ° C., curing was completed in 300 seconds, and a cured product having flexibility of type D durometer hardness 60 at 25 ° C. was obtained. There was no surface tack, and the hardness did not change even after heating.
［比較例１］
　平均単位式：
（ＭｅＶｉＳｉＯ２／２）０．２５（Ｐｈ２ＳｉＯ２／２）０．３（ＰｈＳｉＯ３／２）０．４５で表される分岐状メチルビニルフェニルポリシロキサン６３重量部、式：
ＶｉＭｅ２ＳｉＯ（ＰｈＭｅＳｉＯ）３８ＳｉＭｅ２Ｖｉで示される直鎖状オルガノポリシロキサン（一般式（１）で表されるシロキサン単位を有さない）１７重量部、および式：（ＨＭｅ２ＳｉＯ）２ＳｉＰｈ２で表されるトリシロキサン２０重量部を均一に混合した後、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を組成物に対して白金量が重量単位で２５ｐｐｍとなる量を混合して２５℃の粘度が２５００ｍＰａ・ｓである架橋性オルガノポリシロキサン組成物を調製した。 [Comparative Example 1]
Average unit formula:
(MeViSiO 2/2 ) 0.25 (Ph 2 SiO 2/2 ) 0.3 (PhSiO 3/2 ) 63 parts by weight of branched methylvinylphenylpolysiloxane represented by 0.45 , formula:
ViMe 2 SiO (PhMeSiO) 38 SiMe 2 Vi linear organopolysiloxane represented by Vi (not having a siloxane unit represented by the general formula (1)) 17 parts by weight, and the formula: (HMe 2 SiO) 2 SiPh After uniformly mixing 20 parts by weight of the trisiloxane represented by 2 , platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is added to the composition in the amount of platinum by weight. An amount of 25 ppm was mixed to prepare a crosslinkable organopolysiloxane composition having a viscosity of 2500 mPa · s at 25 ° C.
　この組成物は１５０℃に加熱すると８０秒で硬化が完了し、２５℃でタイプＡデュロメータ硬さ５２のゴム状の硬化物を得た。硬化物は表面タックがあり、その後、１５０℃での加熱を継続すると１時間後には２５℃でタイプＡデュロメータ硬さ５７となった。 When this composition was heated to 150 ° C., curing was completed in 80 seconds, and a rubber-like cured product having a type A durometer hardness of 52 was obtained at 25 ° C. The cured product had a surface tack, and when heating at 150 ° C. was continued thereafter, a Type A durometer hardness of 57 was obtained at 25 ° C. after 1 hour.
　本発明の架橋性オルガノポリシロキサン組成物は、架橋が速く、硬化物の表面タックがなく、十分の可とう性があるために応力が緩和される材料であって、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る。特に、高屈折率で光透過率が高いので光学用途のレンズ材料や、発光ダイオードなどの半導体素子のポッティング剤、コーティング剤、保護材、封止材などの用途に好適である。 The crosslinkable organopolysiloxane composition of the present invention is a material that is fast in cross-linking, has no surface tack of a cured product, and has sufficient flexibility to relieve stress. , Potting agents, protective coating agents, and underfill agents. In particular, since it has a high refractive index and a high light transmittance, it is suitable for lens materials for optical applications, potting agents for semiconductor elements such as light emitting diodes, coating agents, protective materials, and sealing materials.

Claims (6)

  1. 　（Ａ）平均単位式：
    （Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ（Ｒ２Ｏ１／２）ｅ（式中Ｒ１は炭素数１～１４の一価炭化水素基で、少なくとも１個はアリール基、また、少なくとも１個は炭素数２～６のアルケニル基であり、Ｒ２は水素原子または炭素数１～６のアルキル基であり、ａ、ｂ、ｃ、ｄ、およびｅは、０≦ａ≦０．１、０．２≦ｂ≦０．９、０．１≦ｃ≦０．６、０≦ｄ≦０．２、０≦ｅ≦０．１、かつａ＋ｂ＋ｃ＋ｄ＋ｅ＝１を満たす数である。）で示されるアリール基を含有するアルケニル官能性分岐状オルガノポリシロキサン、
    （Ｂ）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し、下記一般式（１）で表されるシロキサン単位を一分子中に少なくとも３個有する、アリール基を含有するアルケニル官能性分岐状オルガノポリシロキサン｛（Ａ）成分と（Ｂ）成分の比が１／１００～１００／１｝、
    Ｒ３ ３ＳｉＯ１／２　　　一般式（１）（式中、Ｒ３は置換又は非置換の一価炭化水素基である。）
    （Ｃ）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し、ケイ素原子結合有機基の１２～７０モル％がアリール基であるオルガノポリシロキサン｛（Ａ）成分中と（Ｂ）成分中のアルケニル基の合計に対する本成分中のケイ素原子結合水素原子のモル比が０．５～２となる量｝、および
    （Ｄ）ヒドロシリル化反応用触媒｛（Ａ）成分と（Ｂ）成分のアルケニル基と（Ｃ）成分のケイ素原子結合水素原子とのヒドロシリル化反応を促進するに十分の量｝を少なくとも含み、
    　アルケニル官能性直鎖状オルガノポリシロキサンを含まない架橋性オルガノポリシロキサン組成物。     (A) Average unit formula:
    (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (R 2 O 1/2 ) e (where R 1 the monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one aryl group also, at least one is an alkenyl group having 2 to 6 carbon atoms, R 2 is a hydrogen atom or a number of 1 to 6 carbon atoms An alkyl group, a, b, c, d, and e are 0 ≦ a ≦ 0.1, 0.2 ≦ b ≦ 0.9, 0.1 ≦ c ≦ 0.6, and 0 ≦ d ≦ 0. ., 2, 0 ≦ e ≦ 0.1, and a number satisfying a + b + c + d + e = 1.)
    (B) an aryl group having at least two alkenyl groups and at least one aryl group in one molecule, and having at least three siloxane units represented by the following general formula (1) in one molecule; Containing alkenyl functional branched organopolysiloxane {ratio of (A) component to (B) component is 1/100 to 100/1},
    R 3 3 SiO 1/2 general formula (1) (wherein R 3 is a substituted or unsubstituted monovalent hydrocarbon group)
    (C) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule and 12 to 70 mol% of silicon-bonded organic groups being aryl groups {in component (A) and component (B) In an amount such that the molar ratio of silicon-bonded hydrogen atoms in this component to the total of alkenyl groups in the component is 0.5 to 2}, and (D) hydrosilylation catalyst {components (A) and (B) An amount sufficient to promote the hydrosilylation reaction between the alkenyl group and the silicon-bonded hydrogen atom of component (C)},
    A crosslinkable organopolysiloxane composition free of alkenyl-functional linear organopolysiloxane.
  2. 　前記（Ｂ）成分が、平均単位式：
    （Ｒ４ ３ＳｉＯ１／２）ｆ（Ｒ４ ２ＳｉＯ２／２）ｇ（Ｒ４ＳｉＯ３／２）ｈ（ＳｉＯ４／２）ｉ（式中、Ｒ４は炭素数１～１４の一価炭化水素基で、少なくとも２個は炭素数２～６のアルケニル基であり、少なくとも１個はアリール基であり、ｆ、ｇ、ｈ、ｉは、０＜ｆ≦０．８、０≦ｇ≦０．９６、０＜（ｈ＋ｉ）、０．５≦ｆ／（ｈ＋ｉ）≦４、ｆ＋ｇ＋ｈ＋ｉ＝１を満たす数である。）で示されるアリール基を含有するアルケニル官能性分岐状オルガノポリシロキサンである請求項１記載の架橋性オルガノポリシロキサン組成物。     The component (B) is an average unit formula:
    (R 4 3 SiO 1/2) f (R 4 2 SiO 2/2) g (R 4 SiO 3/2) h one (SiO 4/2) i (wherein, R 4 having a carbon number of 1 to 14 A valent hydrocarbon group, at least two are alkenyl groups having 2 to 6 carbon atoms, at least one is an aryl group, and f, g, h, i are 0 <f ≦ 0.8, 0 ≦ g ≦ 0.96, 0 <(h + i), 0.5 ≦ f / (h + i) ≦ 4, and f + g + h + i = 1.) An alkenyl-functional branched organopolysiloxane containing an aryl group represented by The crosslinkable organopolysiloxane composition according to claim 1.
  3. 　前記（Ｂ）成分が、式：Ｒ５Ｒ６ ２ＳｉＯ（Ｒ６ ２ＳｉＯ）ｎＳｉＲ５Ｒ６ ２（Ｒ５は炭素数２～６のアルケニル基、Ｒ６は炭素数１～１４の一価炭化水素基で、少なくとも１個はアリール基であり、ｎは０以上２００以下）で示されるアリール基を含有するアルケニル官能性直鎖状オルガノポリシロキサンと、
    式：（ＨＲ７ ２ＳｉＯ）ｊＳｉＲ７ （４－ｊ）（Ｒ７は炭素数１～１４の一価炭化水素基であり、ｊは３ないし４で示される整数。）で示されるケイ素原子結合水素原子を含有するシロキサンオリゴマーを、ヒドロシリル化反応してなる、生成物一分子中にアルケニル基を少なくとも３個有し、ケイ素原子結合水素原子が無い、アリール基を含有するアルケニル官能性分岐状オルガノポリシロキサンである請求項１記載の架橋性オルガノポリシロキサン組成物。     The component (B) is a compound of the formula: R 5 R 6 2 SiO (R 6 2 SiO) n SiR 5 R 6 2 (R 5 is an alkenyl group having 2 to 6 carbon atoms, and R 6 is one having 1 to 14 carbon atoms. An alkenyl functional linear organopolysiloxane containing an aryl group represented by a valent hydrocarbon group, wherein at least one is an aryl group, and n is 0 or more and 200 or less,
    A silicon atom represented by the formula: (HR 7 2 SiO) j SiR 7 (4-j) (R 7 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, j is an integer represented by 3 to 4). A branched alkenyl functional group containing an aryl group containing at least three alkenyl groups in one molecule of the product and having no silicon-bonded hydrogen atoms, obtained by hydrosilylation of a siloxane oligomer containing a bonded hydrogen atom The crosslinkable organopolysiloxane composition according to claim 1, which is an organopolysiloxane.
  4. 　前記（Ｂ）成分が、２５℃において粘度が２０Ｐａ・ｓ以下の流動性を有する請求項１～３のいずれか一項に記載の架橋性オルガノポリシロキサン組成物。 The crosslinkable organopolysiloxane composition according to any one of claims 1 to 3, wherein the component (B) has a fluidity of a viscosity of 20 Pa · s or less at 25 ° C.
  5. 　前記架橋性オルガノポリシロキサン組成物は加熱により完全硬化した場合にＪＩＳ　Ｋ　６２５３で規定されるタイプＤデュロメータ硬さが４５以上となる、請求項１～４のいずれか一項に記載の架橋性オルガノポリシロキサン組成物。 The crosslinkable organopolysiloxane composition according to any one of claims 1 to 4, wherein when the crosslinkable organopolysiloxane composition is completely cured by heating, the type D durometer hardness defined in JIS K 6253 is 45 or more. Polysiloxane composition.
  6. 　請求項１～５のいずれか１項に記載の架橋性オルガノポリシロキサン組成物を硬化してなる硬化物。 A cured product obtained by curing the crosslinkable organopolysiloxane composition according to any one of claims 1 to 5.
PCT/JP2016/074899 2015-09-11 2016-08-26 Crosslinkable organopolysiloxane composition and cured object obtained therefrom WO2017043328A1 (en)

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* Cited by examiner, † Cited by third party
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CN116134093A (en) * 2020-06-30 2023-05-16 陶氏东丽株式会社 Curable silicone composition and cured product thereof
WO2024000245A1 (en) * 2022-06-29 2024-01-04 Dow Toray Co., Ltd. Uv curable organopolysiloxane composition and application thereof

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JP2011225715A (en) * 2010-04-20 2011-11-10 Shin-Etsu Chemical Co Ltd Curable organopolysiloxane composition
JP2012082300A (en) * 2010-10-08 2012-04-26 Shin-Etsu Chemical Co Ltd Addition-curable silicone composition, and semiconductor device in which semiconductor element is covered with cured product of the composition
WO2015119227A1 (en) * 2014-02-04 2015-08-13 東レ・ダウコーニング株式会社 Curable silicone composition, cured object thereof, and optical semiconductor device

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JP2011225715A (en) * 2010-04-20 2011-11-10 Shin-Etsu Chemical Co Ltd Curable organopolysiloxane composition
JP2012082300A (en) * 2010-10-08 2012-04-26 Shin-Etsu Chemical Co Ltd Addition-curable silicone composition, and semiconductor device in which semiconductor element is covered with cured product of the composition
WO2015119227A1 (en) * 2014-02-04 2015-08-13 東レ・ダウコーニング株式会社 Curable silicone composition, cured object thereof, and optical semiconductor device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116134093A (en) * 2020-06-30 2023-05-16 陶氏东丽株式会社 Curable silicone composition and cured product thereof
WO2024000245A1 (en) * 2022-06-29 2024-01-04 Dow Toray Co., Ltd. Uv curable organopolysiloxane composition and application thereof

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