Hydrosilylation-curable silicone compositions

Abstract

It is an object of the present invention to provide hydrosilylation-curable silicone compositions that exhibit good storage stability and that can be cured to form cured products that do not suffer from any surface wrinkling. [Solution] The present invention provides a hydrosilylation-curable silicone composition comprising a maleate compound and a hydrosilylation inhibitor other than a maleate compound, wherein the maleate compound is contained in an amount of 50 to 6,000 ppm by mass of the composition, and the hydrosilylation inhibitor is contained in an amount of 200 to 20,000 ppm by mass of the composition. The hydrosilylation-curable silicone composition exhibits good storage stability and can be cured to form a cured product that is completely free of surface wrinkling.

Description

[Technical Field]

[0001] The present invention relates to hydrosilylation-curable silicone compositions. [Background technology]

[0002] Hydrosilylation-curable silicone compositions form cured products with excellent properties such as weather resistance and heat resistance, and they cure rapidly, especially by heating, without producing by-products during curing. Therefore, such compositions are used to seal, coat, or bond optical conductor elements in optical semiconductor devices. It is well known that at least one hydrosilylation inhibitor is added to adjust the curability and storage stability of the composition. However, lowering the curing temperature and enabling a shorter curing time causes significant deterioration in the storage stability of the composition, and low-temperature curing promotes the formation of wrinkles on the surface of the cured product. To solve these problems, several curable silicone compositions have been proposed.

[0003] Examples of such curable silicone compositions include a curable silicone composition comprising an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, a hydrosilylation catalyst, and an amide compound (see Patent Document 1); a curable silicone composition comprising an organopolysiloxane having at least two alkenyl groups per molecule, an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, a platinum group metal catalyst, and a dihydrodisilane compound (see Patent Document 2); and a curable silicone composition comprising an organopolysiloxane having at least one silicon-bonded alkenyl group per molecule, an organohydrogenpolysiloxane having at least one silicon-bonded hydrogen atom at a molecular chain terminal and at least two silicon-bonded hydrogen atoms at non-molecular chain terminals per molecule, and a hydrosilylation catalyst (see Patent Document 3).

[0004] However, it is difficult to match good curability and prevent wrinkling of the surface of the cured product by curing at relatively low temperatures. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 08-183908 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-26716 [Patent Document 3] US Patent Application Publication No. 2005 / 0272893A1 Summary of the Invention [Problem to be solved by the invention]

[0006] It is an object of the present invention to provide hydrosilylation-curable silicone compositions that exhibit good storage stability and that can be cured to form cured products that do not suffer from any surface wrinkling. [Means for solving the problem]

[0007] The hydrosilylation-curable silicone composition of the present invention is characterized by comprising a maleate ester compound and a hydrosilylation inhibitor other than a maleate ester compound, wherein the content of the maleate ester compound is in an amount of 50 to 6,000 ppm, and the content of the hydrosilylation inhibitor is in an amount of 200 to 20,000 ppm, each expressed by mass of the composition.

[0008] The hydrosilylation-curable silicone composition of the present invention preferably comprises: (A) an organopolysiloxane having at least two alkenyl groups per molecule; (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule (in an amount such that 0.1 to 10.0 moles of silicon-bonded hydrogen atoms are provided for each mole of alkenyl groups in component (A); (C) a hydrosilylation catalyst (in an amount sufficient to promote cure of the composition); (D) maleic acid ester compounds (in an amount of 50 to 6,000 ppm by mass of the composition); and (E) A hydrosilylation inhibitor other than maleate ester (in an amount of 200 to 20,000 ppm by mass of the composition).

[0009] The hydrosilylation-curable silicone composition of the present invention may also include (F) an adhesion promoter (in an amount of 0.01 to 50 parts by weight per 100 parts by weight of components (A) to (E)).

[0010] The hydrosilylation-curable silicone composition of the present invention may also contain (G) a cerium-containing organopolysiloxane (in an amount such that the amount of cerium atoms in this component is 10 to 2,000 ppm by mass of the composition).

[0011] The hydrosilylation-curable silicone composition of the present invention is preferably a sealing, coating, or adhesive for optical semiconductor elements. [Effects of the Invention]

[0012] The hydrosilylation-curable silicone compositions of the present invention exhibit good storage stability and can be cured even at low temperatures, resulting in cured products that are completely free from surface wrinkling. DETAILED DESCRIPTION OF THE INVENTION

[0013] The hydrosilylation-curable silicone composition of the present invention comprises a maleate ester compound and a hydrosilylation inhibitor other than a maleate ester compound, wherein the content of the maleate ester compound is 50 to 6,000 ppm, and the content of the hydrosilylation inhibitor is 200 to 20,000 ppm, respectively, by mass unit relative to the composition.

[0014] The curable silicone composition of the present invention preferably comprises: (A) an organopolysiloxane having at least two alkenyl groups per molecule; (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule (in an amount such that 0.1 to 10.0 moles of silicon-bonded hydrogen atoms are provided per mole of alkenyl groups in component (A); (C) a hydrosilylation catalyst (in an amount sufficient to promote cure of the composition); (D) maleic acid ester compounds (in an amount of 50 to 6,000 ppm by mass of the composition); and (E) a hydrosilylation inhibitor other than a maleate ester compound (in an amount of 200 to 20,000 ppm by mass of the composition) Includes:

[0015] Component (A) is an organopolysiloxane having at least two alkenyl groups per molecule. Examples of the alkenyl groups include alkenyl groups having 2 to 12 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl. Vinyl groups are preferred. Examples of silicon-bonded groups other than alkenyl groups in component (A) include alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups having 6 to 20 carbon atoms, such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups having 7 to 20 carbon atoms, such as benzyl, phenethyl, and phenylpropyl; and groups in which some or all of the hydrogen atoms have been replaced by halogen atoms, such as fluorine, chlorine, and bromine. Small amounts of silicon atoms in component (A) may be bonded to hydroxyl or alkoxy groups, such as methoxy and ethoxy, as long as the objectives of the present invention are not impaired.

[0016] The molecular structure of component (A) is not particularly limited, and examples thereof include linear, partially branched linear, cyclic, and three-dimensional network structures. Component (A) may be one type of organopolysiloxane having such a molecular structure, or a mixture of two or more types of organopolysiloxane having such a molecular structure.

[0017] The state of component (A) at 25° C. is not particularly limited, and examples thereof include liquid and solid. When component (A) is a liquid at 25° C., the viscosity at 25° C. is preferably in the range of 1 to 1,000,000 mPa·sec, and particularly preferably in the range of 10 to 1,000,000 mPa·sec.

[0018] Examples of such component (A) include dimethylpolysiloxane having both molecular ends capped with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymer having both molecular ends capped with dimethylvinylsiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymer having both molecular ends capped with dimethylvinylsiloxy groups, methylphenylpolysiloxane having both molecular ends capped with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymer having both molecular ends capped with trimethylsiloxy groups, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer having both molecular ends capped with trimethylsiloxy groups, (CH3)3SiO 1 / 2 Units: (CH3)2(CH2=CH)SiO 1 / 2 Units, and C6H5SiO 3 / 2 Copolymer containing units, (CH3)2(CH2=CH)SiO 1 / 2 Units and C6H5SiO 3 / 2 Copolymer containing units, (CH3)3SiO 1 / 2 Units: (CH3)2(CH2=CH)SiO 1 / 2 units, and SiO 4 / 2 Copolymer containing units, (CH3)2(CH2=CH)SiO 1 / 2 Units and SiO 4 / 2 Included are copolymers containing units, as well as organopolysiloxanes as follows: Note that in the formula, Me, Vi, and Ph represent methyl, vinyl, and phenyl groups, respectively, and x and x' are integers from 1 to 100. ViMe2SiO(Me2SiO) x SiMe2Vi ViPhMeSiO(MeSiO) x SiMePhVi ViPh2SiO(Me2SiO) x SiPh2Vi ViMe2SiO(Me2SiO) x (Ph2SiO) x’ SiMe2Vi ViPhMeSiO(MeSiO) x (Ph2SiO)x’ SiPhMeVi ViPh2SiO(Me2SiO) x (Ph2SiO) x’ SiPh2Vi ViMe2SiO(MePhSiO) x SiMe2Vi MePhViSiO(MePhSiO) x SiMePhVi Ph2ViSiO(MePhSiO) x SiPh2Vi ViMe2SiO(Ph2SiO) x (PhMeSiO) x’ SiMe2Vi ViPhMeSiO(Ph2SiO) x (PhMeSiO) x’ SiPhMeVi ViPh2SiO(Ph2SiO) x (PhMeSiO) x’ SiPh2Vi

[0019] Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule. Examples of the molecular structure of component (B) include linear, partially branched linear, branched, cyclic, and dendritic structures, with linear, partially branched linear, and dendritic structures being preferred. The bonding positions of the silicon-bonded hydrogen atoms in component (B) are not limited, and examples include the terminal and / or side chains of the molecular chain. Examples of silicon-bonded groups other than hydrogen atoms in component (B) include alkyl groups such as methyl, ethyl, and propyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenethyl; and halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl. Methyl and phenyl groups are preferred. There are no particular limitations on the viscosity of component (B) at 25°C, but it is preferably in the range of 1 to 10,000 mPa·sec, and particularly preferably in the range of 1 to 1,000 mPa·sec.

[0020] Examples of such organohydrogenpolysiloxanes for component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, 1-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-diglycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-glycidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, and methylhydrogenpolysiloxanes having both molecular ends blocked with trimethylsiloxy groups. silane, dimethylsiloxane-methylhydrogensiloxane copolymer having both molecular ends capped with trimethylsiloxy groups, dimethylpolysiloxane having both molecular ends capped with dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer having both molecular ends capped with dimethylhydrogensiloxane groups, methylhydrogensiloxane-diphenylsiloxane copolymer having both molecular ends capped with trimethylsiloxy groups, methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer having both molecular ends capped with trimethylsiloxy groups, hydrolysis-condensation products of trimethoxysilane, (CH3)2HSiO 1 / 2 Units and SiO 4 / 2 Copolymer containing units, (CH3)2HSiO 1 / 2 Units, SiO 4 / 2 Units, and (C6H5)SiO 3 / 2 Examples include copolymers containing units, and the following organohydrogenpolysiloxanes: In the following formula, Me, Vi, Ph, and NapH represent a methyl group, a vinyl group, a phenyl group, and a naphthyl group, respectively, y and y' are integers of 1 to 100, and c, d, e, and f are positive numbers, with the proviso that the sum of c, d, e, and f in the molecule is 1. HMe2SiO(Ph2SiO) y SiMe2H HMePhSiO(PhSiO) ySiMePhH HMeNaphSiO(Ph2SiO) y SiMeNaphH HMePhSiO(Ph2SiO) y (MePhSiO) y’ SiMePhH HMePhSiO(Ph2SiO) y (Me2SiO) y’ SiMePhH (HMe2SiO 1 / 2 ) c (PhSiO 3 / 2 ) d (HMePhSiO 1 / 2 ) c (PhSiO 3 / 2 ) d (HMePhSiO 1 / 2 ) c (NaphSiO 3 / 2 ) d (HMe2SiO 1 / 2 ) c (NaphSiO 3 / 2 ) d (HMePhSiO 1 / 2 ) c (HMe2SiO 1 / 2 ) d (PhSiO 3 / 2 ) e (HMe2SiO 1 / 2 ) c (Ph2SiO 2 / 2 ) d (PhSiO 3 / 2 ) e (HMePhSiO 1 / 2 ) c (Ph2SiO 2 / 2 ) d (PhSiO 3 / 2 ) e (HMe2SiO 1 / 2 ) c (Ph2SiO 2 / 2 ) d (NaphSiO 3 / 2 ) e (HMePhSiO 1 / 2 ) c (Ph2SiO 2 / 2 ) d (NaphSiO 3 / 2 ) e (HMePhSiO 1 / 2 ) c (HMe2SiO 1 / 2 ) d (NaphSiO 3 / 2 ) e (HMePhSiO 1 / 2 ) c (HMe2SiO 1 / 2 ) d (Ph2SiO 2 / 2 ) e (NaphSiO 3 / 2 ) f (HMePhSiO 1 / 2 ) c (HMe2SiO 1 / 2 ) d (Ph2SiO 2 / 2 ) e (PhSiO 3 / 2 ) f

[0021] The content of component (B) is such that the silicon-bonded hydrogen atoms in component (B) are in the range of 0.1 to 10.0 moles, preferably 0.5 to 5 moles, per mole of alkenyl groups in component (A). When the content of component (B) is at or below the upper limit of the aforementioned range, the mechanical properties of the resulting cured product are good. In contrast, when the content of component (B) is at or above the lower limit of the range, the curability of the resulting composition is good.

[0022] Component (C) is a hydrosilylation catalyst used to accelerate the curing of the composition. Examples of component (C) include platinum group element catalysts and platinum group element compound catalysts, and specific examples include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, and combinations of at least two types thereof. In particular, platinum-based catalysts are preferred because they can dramatically accelerate the curing of the composition. Examples of these platinum catalysts include finely powdered platinum; platinum black; chloroplatinic acid, alcohol-modified chloroplatinic acid; chloroplatinic acid / diolefin complex; platinum / olefin complex; platinum / carbonyl complex, such as platinum bis(acetoacetate) and platinum bis(acetylacetonate); chloroplatinic acid / alkenylsiloxane complex, such as platinum acid / divinyltetramethyldisiloxane complex and chloroplatinic acid / tetravinyltetramethylcyclotetrasiloxane complex; platinum / alkenylsiloxane complex, such as platinum / divinyltetramethyldisiloxane complex and platinum / tetravinyltetramethylcyclotetrasiloxane complex; chloroplatinic acid and acetylene alcohol complex; and the mixture of two or more of them.In particular, platinum-alkenylsiloxane complex is preferred because it can accelerate the curing of the present composition.

[0023] Examples of alkenylsiloxanes used in platinum-alkenylsiloxane complexes include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers in which some of the methyl groups of these alkenylsiloxanes have been replaced with ethyl groups, phenyl groups, or similar, and alkenylsiloxane oligomers in which the vinyl groups of these alkenylsiloxanes have been replaced with allyl groups, hexenyl groups, or similar. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the resulting platinum-alkenylsiloxane complex has good stability.

[0024] To improve the stability of the platinum-alkenylsiloxane complexes, it is preferable to dissolve these platinum-alkenylsiloxane complexes in an alkenylsiloxane oligomer, such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, or 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, or an organosiloxane oligomer, such as a dimethylsiloxane oligomer, and it is particularly preferable to dissolve the complexes in an alkenylsiloxane oligomer.

[0025] The content of component (C) is an amount that promotes curing of the composition. Specifically, the content is preferably such that the content of catalytic metal atoms in component (C) is in the range of 0.01 to 500 ppm, 0.01 to 100 ppm, or 0.1 to 50 ppm by mass of the composition. This is because, when the content of component (C) is equal to or greater than the lower limit of the aforementioned range, the curability of the resulting composition is good, while when the content of component (C) is equal to or less than the upper limit of the aforementioned range, discoloration of the resulting cured product is suppressed.

[0026] Component (D) is a maleic acid ester compound. Examples of component (D) include diallyl maleate, dimethyl maleate, bis(2-methoxy-1-methylethyl) maleate, mono-octyl maleate, mono-iso-octyl maleate, mono-allyl maleate, mono-methyl maleate, and 2-methoxy-1-methylethyl maleate.

[0027] The content of component (D) in the composition is in the range of 50 to 6,000 ppm by mass, preferably 100 to 6,000 ppm, or 150 to 6,000 ppm, because, when the content of component (D) is equal to or greater than the lower limit of the aforementioned range, the occurrence of surface wrinkles can be sufficiently prevented, whereas, when the content of component (D) is equal to or less than the upper limit of the aforementioned range, the curability of the resulting composition is not reduced, and the physical properties of the resulting cured product are not reduced.

[0028] Component (E) is a hydrosilylation inhibitor other than maleic ester compounds, which is used to extend the useful life at room temperature and improve storage stability. Examples of component (E) include alkyne alcohols such as 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; alkenyl group-containing low molecular weight siloxanes such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; alkynoxysilanes such as dimethylbis(3-methyl-1-butyn-3-oxy)silane and methylvinylbis(3-methyl-1-butyn-3-oxy)silane, and triallyl isocyanurate compounds.

[0029] The content of component (E) in the composition is in the range of 200 to 20,000 ppm by mass, preferably 200 to 15,000 ppm, or 250 to 15,000 ppm. This is because, when the content of component (E) is equal to or greater than the lower limit of the aforementioned range, the storage stability of the composition can be sufficiently imparted, whereas, when the content of component (E) is equal to or less than the upper limit of the aforementioned range, the curability of the resulting composition is not reduced, and the physical properties of the resulting cured product are not reduced.

[0030] Additionally, the composition may also contain (F) an adhesion promoter to further improve adhesion to substrates that the composition contacts during curing. Component (F) is preferably an organosilicon compound having one or more silicon-bonded alkoxy groups per molecule. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy groups, with methoxy or ethoxy groups being particularly preferred. Examples of silicon-bonded groups other than alkoxy groups in component (F) include the same substituted or unsubstituted monovalent hydrocarbon groups as those described above, such as alkyl, alkenyl, aryl, aralkyl, and halogenated alkyl groups; glycidoxyalkyl groups, such as 3-glycidoxypropyl and 4-glycidoxybutyl; epoxycyclohexylalkyl groups, such as 2-(3,4-epoxycyclohexyl)ethyl and 3-(3,4-epoxycyclohexyl)propyl; epoxyalkyl groups, such as 4-epoxybutyl and 8-epoxyoctyl; acrylic group-containing monovalent organic groups, such as 3-methacryloxypropyl; isocyanate groups; isocyanurate groups; and hydrogen atoms. Component (F) preferably contains a group capable of reacting with an aliphatic unsaturated hydrocarbon group or a silicon-bonded hydrogen atom in the present composition. Specifically, component (F) preferably contains a silicon-bonded aliphatic unsaturated hydrocarbon group or a silicon-bonded hydrogen atom.

[0031] The content of component (F) is not limited, but is preferably in the range of 0.01 to 50 parts by weight, 0.01 to 30 parts by weight, 0.01 to 10 parts by weight, 0.01 to 5 parts by weight, or 0.1 to 3 parts by weight per 100 parts by weight of the composition. When the content of component (F) is equal to or greater than the lower limit of the aforementioned range, the resulting composition can be imparted with sufficient adhesion. In contrast, when the content of component (F) is equal to or less than the lower limit of the range, the curability of the resulting composition is unlikely to be inhibited, and discoloration of the resulting cured product, etc., can be suppressed.

[0032] The composition may also contain (G) a cerium-containing organopolysiloxane to inhibit cracking due to heat aging in the cured product obtained by curing the composition. Such component (G) is prepared, for example, by reacting cerium chloride or a cerium salt of a carboxylic acid with an alkali metal salt of a silanol-containing organopolysiloxane.

[0033] Examples of cerium salts of the above-listed carboxylic acids include cerium 2-ethylhexanoate, cerium naphthenate, cerium oleate, cerium laurate, and cerium stearate.

[0034] Examples of the alkali metal salts of the above-described silanol-containing organopolysiloxanes include potassium salts of diorganopolysiloxanes terminally terminated with silanol groups, sodium salts of diorganopolysiloxanes terminally terminated with silanol groups, potassium salts of diorganopolysiloxanes terminally terminated with silanol groups and triorganosiloxy groups at the other molecular end, and sodium salts of diorganopolysiloxanes terminally terminated with silanol groups and triorganosiloxy groups at the other molecular end. Examples of groups bonded to silicon atoms in the organopolysiloxane include alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups having 6 to 20 carbon atoms, such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups having 7 to 20 carbon atoms, such as benzyl, phenethyl, and phenylpropyl; and groups in which some or all of the hydrogen atoms in these groups have been replaced with halogen atoms, such as fluorine, chlorine, or bromine atoms.

[0035] The reaction described above can be carried out at room temperature or by heating in an alcohol, such as methanol, ethanol, isopropanol, or butanol; an aromatic hydrocarbon, such as toluene or xylene; an aliphatic hydrocarbon, such as hexane or heptane; and an organic solvent, such as mineral spirits, ligroin, or petroleum ether. It is preferable to distill off the organic solvent or low-boiling components, or, if necessary, filter any precipitate from the resulting reaction product. To accelerate the reaction, dialkylformamide, hexaalkylphosphamide, or the like may be added. The cerium atom content in the cerium-containing organopolysiloxane thus prepared is preferably within the range of 0.1 to 5% by weight.

[0036] The content of component (G) in the present composition is such that the cerium atoms are in the range of 10 to 2,000 ppm by mass, preferably 10 to 1,500 ppm, more preferably 10 to 1,000 ppm, even more preferably 10 to 500 ppm, and particularly preferably 10 to 200 ppm, because when the content of component (G) is equal to or greater than the lower limit of the range described above, the heat resistance of the resulting composition can be improved, and when the content is equal to or less than the upper limit of the range described above, the change in emission chromaticity can be reduced when used in optical semiconductor devices.

[0037] The present composition may contain a phosphor to obtain light having a desired wavelength by modifying the wavelength of light emitted from a light-emitting device encapsulated or coated with a cured product of the present composition. Examples of such phosphors include yellow, red, green, and blue light-emitting phosphors, such as oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, and oxysulfide phosphors, which are widely used in light-emitting diodes (LEDs). Examples of oxide phosphors include yttrium, aluminum, and garnet-type YAG phosphors containing cerium ions, green to yellow light-emitting phosphors; cerium, aluminum, and garnet-type TAG phosphors containing cerium ions, yellow light-emitting phosphors; and silicate phosphors containing cerium or europium ions, green to yellow light-emitting phosphors. Examples of oxynitride phosphors include silicon, aluminum, oxygen, and nitrogen-type SiAlON phosphors containing europium ions, red to green light-emitting phosphors. Examples of nitride-based phosphors include calcium, strontium, aluminum, silicon, and nitrogen-type CASN europium ion-containing red light-emitting phosphors. Examples of sulfide phosphors include ZnS copper or aluminum ion-containing green light-emitting phosphors. Examples of oxysulfide phosphors include Y2O2S europium ion-containing red light-emitting phosphors. These phosphors may be used as a single type or as a mixture of two or more types. In the present composition, the content of the phosphor is in the range of 0.1 to 70 mass %, preferably 1 to 20 mass %, based on the total amount of component (A) and component (B).

[0038] Furthermore, the composition may contain inorganic fillers such as silica, glass, alumina, zinc oxide, or the like; organic resin fine powders of polymethacrylate resin, or the like; heat-resistant agents, dyes, pigments, flame retardants, solvents, or the like as optional ingredients, provided that the purpose of the present invention is not impaired.

[0039] The composition can be cured either at room temperature or under heat, but it is preferred to heat the composition to achieve rapid curing. The heating temperature is preferably in the range of 50 to 200°C. [Example]

[0040] The hydrosilylation-curable silicone composition of the present invention is described in detail below using examples and comparative examples. The hydrosilylation-curable silicone composition was evaluated as follows.

[0041] <Storage Stability of Hydrosilylation-Curable Silicone Composition> The storage stability of the hydrosilylation-curable silicone compositions was evaluated based on the heat generation peak temperature (°C) measured at a heating rate of 10°C / min using a differential scanning calorimeter (DSC7000; manufactured by SII Nanotechnology).

[0042] <Curability of Hydrosilylation-Curable Silicone Composition> The curability of the hydrosilylation-curable silicone composition was evaluated using a rheometer MDR 2000 (manufactured by Alpha Technologies, Ltd.). The curing temperature was 150°C. For the measurement, the time (minutes) required to obtain a 1% torque value was designated as Ts1, and the time (minutes) required to obtain a 90% torque value was designated as Ts2. 90 As shown.

[0043] <Surface wrinkles of the cured product> 5 g of the hydrosilylation-curable silicone composition was poured into a 60 mm diameter aluminum Petri dish and cured by heating at 150°C for 1 hour. metaplasia The appearance of the cured product was visually observed as follows: N: No wrinkles were observed. Y: Wrinkles were observed.

[0044] Example Examples 1 to 4 and Examples 8 to 14 and comparative examples 1 to 8 and Comparative Examples 12 to 16 > The following components were uniformly mixed according to the compositions (parts by mass) shown in Tables 1 to 5. Examples 1 to 4 and Examples 8 to 14 and comparative examples 1 to 8 and Comparative Examples 12 to 16 A hydrosilylation-curable silicone composition of the formula (All examples in Table 3 are for reference only.) In the formula, "Me," "Vi," "Ph," and "Ep" represent methyl, vinyl, phenyl, and 3-glycidoxypropyl groups, respectively. Furthermore, in Tables 1 to 5, "SiH / Vi" represents the moles of silicon-bonded hydrogen atoms in component (B) per mole of vinyl groups in component (A) in the hydrosilylation-curable silicone composition.

[0045] The following components were used as component (A): Component (a-1): An organopolysiloxane having two or more vinyl groups per molecule and represented by the following average unit formula: (Me2ViSiO 1 / 2 ) 0.25 (PhSiO 3 / 2 ) 0.75 Component (a-2): An organopolysiloxane represented by the following average formula: Me2ViSiO(Me2SiO) 200 (Ph2SiO) 50 SiMe2Vi Component (a-3): An organopolysiloxane having two or more vinyl groups per molecule and represented by the following average unit formula: (Me2ViSiO 1 / 2 ) 0.13 (MeSiO 1 / 2 ) 0.14 (MeSiO 3 / 2 ) 0.53 (PhSiO 3 / 2 ) 0.22 Component (a-4): 30% by mass of an organopolysiloxane having two or more vinyl groups per molecule and represented by the following average unit formula: (MeSiO 1 / 2 ) 0.47 (Me2ViSiO 1 / 2 ) 0.05 (SiO 4 / 2 )0.48 and a mixture of 70% by mass of dimethylpolysiloxane terminated at both molecular ends with dimethylvinylsiloxy groups (vinyl group content = 0.23% by mass). Component (a-5): An organopolysiloxane having two or more vinyl groups per molecule and represented by the following average unit formula: (Me2ViSiO 1 / 2 ) 0.20 (PhSiO 3 / 2 ) 0.80 Component (a-6): An organopolysiloxane represented by the following average formula: Me2ViSiO(MePhSiO) 25 SiMe2Vi The following component was used as component (H): Component (a-7): Organopolysiloxane represented by the following formula: (Me2ViSiO)4Si

[0046] The following components were used as component (B): Component (b-1): Organohydrogenpolysiloxane represented by the following formula: HMe2SiO(Ph2SiO)SiMe2H Component (b-2): Organohydrogenpolysiloxane represented by the following formula: (MeHSiO 1 / 2 ) 0.60 (PhSiO 3 / 2 ) 0.40 Component (b-3): Organohydrogenpolysiloxane represented by the following formula: Me3SiO(MeHSiO) 40 SiMe3

[0047] The following components were used as component (C): Component (c-1): 1,3-divinyltetramethyldisiloxane solution of platinum 1,3-divinyltetramethyldisiloxane complex (platinum metal content = approximately 4,000 ppm)

[0048] The following component was used as component (D): Ingredient (d-1): Diallyl maleate Ingredient (d-2): Bis(ethylhexyl) maleate

[0049] The following components were used as component (E): Component (e-1): 1-ethynylcyclohexan-1-ol Component (e-2): 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane

[0050] The following components were used as component (F): Component (f-1): Organopolysiloxane represented by the following average unit formula: (Me2ViSiO 1 / 2 ) 0.18 (MeEpSiO 2 / 2 ) 0.28 (PhSiO 3 / 2 ) 0.54

[0051] The following component was used as component (G): Component (g-1): Cerium-containing dimethylpolysiloxane having a cerium content of 1.4% by mass

[0052] The following ingredients were used as optional ingredients: Component (h-1): 100m 2 / g BET surface area of ​​silica filler

[0053] [Table 1]

[0054] [Table 2]

[0055] [Table 3]

[0056] [Table 4]

[0057] [Table 5] [Industrial Applicability]

[0058] The hydrosilylation-curable silicone compositions of the present invention are useful as sealants or adhesives for optical semiconductor devices, such as light-emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid-state imaging devices, emitters and receivers for photocouplers, or the like.

Claims

1. (A) an organopolysiloxane having at least two alkenyl groups per molecule and at least one aryl group per molecule, and having no epoxy groups; (A-1) a linear organopolysiloxane having at least two alkenyl groups per molecule and at least one aryl group per molecule, and (A-2) (CH ３ ) ３ SiO １／２ Units, (CH ３ ) ２ (CH ２ =CH)SiO １／２ Units, and C ６ H ５ SiO ３／２ copolymers comprising units, and (CH ３ ) ２ (CH ２ =CH)SiO １／２ Units and C ６ H ５ SiO ３／２ an organopolysiloxane selected from the group consisting of copolymers containing units an organopolysiloxane which is a mixture of (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule in an amount to provide 0.1 to 10.0 moles of silicon-bonded hydrogen atoms per mole of alkenyl groups in component (A); (C) a hydrosilylation catalyst (in an amount sufficient to promote cure of the composition); (D) a maleate compound (in an amount of 50 to 6,000 ppm by mass of the composition); and (E) a hydrosilylation inhibitor other than a maleate ester compound (in an amount of 200 to 20,000 ppm by mass of the composition); (D) the maleate compound is selected from the group consisting of diallyl maleate and bis(ethylhexyl) maleate, and (E) the hydrosilylation inhibitor is selected from the group consisting of 1-ethynylcyclohexan-1-ol and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Hydrosilylation-curable silicone compositions.

2. The linear organopolysiloxane of component (A-1) is represented by the following formula: ViMe ２ SiO(Me ２ SiO) ｘ (Ph ２ SiO) ｘ’ SiMe ２ Vi ViMe ２ SiO(MePhSiO) ｘ SiMe 2Vi (wherein x and x' each independently represent an integer of 1 to 100) 2. The hydrosilylation-curable silicone composition according to claim 1, wherein the compound is selected from the group consisting of methyl, ...

3. 2. The hydrosilylation-curable silicone composition of claim 1, wherein the organohydrogenpolysiloxane of component (B) has at least one aryl group per molecule.

4. Component (B) is (B-1) a linear organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms and at least one aryl group per molecule, and 2. The hydrosilylation-curable silicone composition of claim 1, comprising (B-2) a partially branched or network organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms and at least one aryl group per molecule.

5. 10. The hydrosilylation-curable silicone composition of claim 1, wherein the hydrosilylation inhibitor of component (E) comprises 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

6. 6. The hydrosilylation-curable silicone composition according to claim 1, further comprising (F) an adhesion promoter (in an amount of 0.01 to 50 parts by weight per 100 parts by weight of components (A) through (E)).

7. 6. The hydrosilylation-curable silicone composition of claim 1, further comprising (G) a cerium-containing organopolysiloxane, in an amount such that the amount of cerium atoms in this component is 10 to 2,000 ppm by mass of the composition.

8. The hydrosilylation-curable silicone composition according to any one of claims 1 to 5, which is a sealant, coating, or adhesive for an optical semiconductor element.

9. (A) an organopolysiloxane having at least two alkenyl groups per molecule and at least one aryl group per molecule, and having no epoxy groups; (A-1) a linear organopolysiloxane having at least two alkenyl groups per molecule and at least one aryl group per molecule, and (A-2) (CH ３ ) ３ SiO １／２ Units, (CH ３ ) ２ (CH ２ =CH)SiO １／２ Units, and C ６ H ５ SiO ３／２ copolymers comprising units, and (CH ３ ) ２ (CH ２ =CH)SiO １／２ Units and C ６ H ５ SiO ３／２ an organopolysiloxane selected from the group consisting of copolymers containing units an organopolysiloxane which is a mixture of (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms and at least one aryl group per molecule in an amount to provide 0.1 to 10.0 moles of silicon-bonded hydrogen atoms per mole of alkenyl groups in component (A); (C) a hydrosilylation catalyst (in an amount sufficient to promote cure of the composition); (D) a maleate compound (in an amount of 50 to 6,000 ppm by mass of the composition); and (E) a hydrosilylation inhibitor other than a maleate ester compound (in an amount of 200 to 20,000 ppm by mass of the composition); (D) the maleate compound is selected from the group consisting of diallyl maleate and bis(ethylhexyl) maleate, and (E) the hydrosilylation inhibitor is selected from the group consisting of 1-ethynylcyclohexan-1-ol and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. An optical semiconductor device comprising the cured product of a hydrosilylation-curable silicone composition.

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