WO2016038836A1 - Composition de silicone durcissable, objet durci obtenu à partir de celle-ci et dispositif optique à semi-conducteurs - Google Patents

Composition de silicone durcissable, objet durci obtenu à partir de celle-ci et dispositif optique à semi-conducteurs Download PDF

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WO2016038836A1
WO2016038836A1 PCT/JP2015/004355 JP2015004355W WO2016038836A1 WO 2016038836 A1 WO2016038836 A1 WO 2016038836A1 JP 2015004355 W JP2015004355 W JP 2015004355W WO 2016038836 A1 WO2016038836 A1 WO 2016038836A1
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group
mass
formula
composition
curable silicone
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Japanese (ja)
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亮介 山▲崎▼
数也 市川
宏明 吉田
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東レ・ダウコーニング株式会社
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Priority to KR1020177009581A priority Critical patent/KR20170052649A/ko
Priority to CN201580047531.9A priority patent/CN106661329B/zh
Priority to JP2016547680A priority patent/JP6590445B2/ja
Publication of WO2016038836A1 publication Critical patent/WO2016038836A1/fr

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Definitions

  • the present invention relates to a curable silicone composition, a cured product thereof, and an optical semiconductor device.
  • the optical semiconductor device is provided with a light reflecting material in order to efficiently reflect light emitted from the optical semiconductor element.
  • a light reflecting material examples include a hydrosilylation reactive silicone having a structure in which one of a vinyl group and an allyl group and a hydrogen atom are directly bonded to a silicon atom.
  • a curable silicone composition comprising a resin, a platinum-based catalyst, and a white pigment (see Patent Document 1), a vinyl group-containing organopolysiloxane having a weight average molecular weight (Mw) of 30,000 or more, and a silicon atom bond in one molecule
  • Curable silicone composition comprising organohydrogenpolysiloxane having at least two hydrogen atoms, white pigment, inorganic filler other than white pigment, platinum metal catalyst, and reaction control agent (see Patent Document 2), silicon atom bond Branched chain in which 30 to 80 mol% of all organic groups are phenyl groups and 5 to 20 mol% are alkenyl groups
  • Organopolysiloxane in the form of a molecule, organopolysiloxane having 10 or less silicon atoms, in which 30 to 60 mol% of all silicon-bonded organic groups are alkenyl groups, and having at least two silicon-bonded hydrogen atoms in one molecule
  • a curable silicone composition comprising an
  • the present invention has thixotropy, good handling workability, cured, low thermal expansion coefficient, high concealment ratio, high mechanical strength, and good adhesion to various substrates. It is an object of the present invention to provide a curable silicone composition that forms a cured product, a cured product that has a low coefficient of thermal expansion, a high concealment rate, a high mechanical strength, and an optical semiconductor device that is excellent in reliability.
  • the curable silicone composition of the present invention contains a titanium oxide powder having an average particle size of 0.05 to 10 ⁇ m and an inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 ⁇ m, and the content of the titanium oxide powder is A thermosetting silicone composition having a content of 50 to 90% by mass in the present composition and a content of the inorganic powder of 5 to 40% by mass in the present composition, wherein the titanium oxide powder and the inorganic powder But the general formula: R 1 (4-a) Si (OR 2 ) a Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3.
  • R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group
  • R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond
  • R 5 is an oxygen atom or a divalent hydrocarbon group.
  • a hydrogen group R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group
  • b is an integer of 1 to 3
  • p is an integer of 1 or more.
  • the cured product of the present invention is characterized by curing the above curable silicone composition.
  • the optical semiconductor device of the present invention is characterized by having a light reflecting material made of a cured product of the curable silicone composition.
  • the curable silicone composition of the present invention has thixotropy, good handling workability, is cured, has a low coefficient of thermal expansion, a high concealment rate, a high mechanical strength, and various substrates. It has the characteristic of forming a cured product with good adhesion to the substrate. Further, the cured product of the present invention is characterized by a low coefficient of thermal expansion, a high concealment rate, and a high mechanical strength. Furthermore, the optical semiconductor device of the present invention is characterized by excellent reliability.
  • the curable silicone composition of the present invention contains a titanium oxide powder having an average particle size of 0.05 to 10 ⁇ m and an inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 ⁇ m, and the content of the titanium oxide powder is It is 50 to 90% by mass in the present composition, and the content of the inorganic powder is 5 to 40% by mass in the present composition.
  • This titanium oxide powder is a white pigment for imparting light reflection performance to the cured product of the present composition.
  • examples of such titanium oxide powder include anatase-type titanium oxide powder and rutile-type titanium oxide powder, and rutile-type titanium oxide powder is preferable because the light reflection performance and hiding power of the cured product are high.
  • the average particle diameter of the titanium oxide is in the range of 0.05 to 10 ⁇ m, preferably in the range of 0.01 to 5 ⁇ m, or in the range of 0.01 to 3 ⁇ m.
  • This titanium oxide may have a surface that has been surface-treated with a silane coupling agent, silica, alumina, zirconia or the like in advance.
  • the content of the titanium oxide powder is in the range of 50 to 90% by mass in the present composition, preferably in the range of 50 to 85% by mass, in the range of 50 to 80% by mass, and 55 to 90% by mass. %, 55-85% by weight, or 55-80% by weight.
  • the content of the titanium oxide powder is not less than the lower limit of the above range, the resulting curable silicone composition has good thixotropy, and the concealability and strength of the obtained cured product.
  • operativity of the curable silicone composition obtained as it is below the upper limit of the said range is favorable.
  • the content of titanium oxide powder is 10 to 30% by mass with respect to the curable silicone composition.
  • the content of 50% by mass or more not only improves the concealability of the resulting cured product. Also, the mechanical strength can be improved. Moreover, in this composition, even if it does not mix
  • the inorganic powder other than titanium oxide is a component for reducing the linear expansion coefficient of the cured product and improving the dimensional stability when used in combination with the above titanium oxide powder.
  • examples of such inorganic powders include spherical silica, non-spherical silica, and glass fiber, and spherical silica is preferred because the viscosity increase of the resulting curable silicone composition is small.
  • examples of the spherical silica include dry silica, wet silica, fused silica, and deflagration silica, but fused silica is preferred because the filling property of the present composition is good.
  • the average particle size of the inorganic powder is in the range of 0.1 to 20 ⁇ m, and preferably 0.1 to 15 ⁇ m because of the ease of passing through the mesh and the ease of forming a thin film when using a coating process by screen printing.
  • 0.1 to 10 ⁇ m within a range of 0.1 to 10 ⁇ m, within a range of 0.2 to 20 ⁇ m, within a range of 0.2 to 15 ⁇ m, or within a range of 0.2 to 10 ⁇ m.
  • the content of the inorganic powder is in the range of 5 to 40% by mass in the present composition, preferably in the range of 5 to 35% by mass, or in the range of 5 to 30% by mass. This is because when the content of the inorganic powder is not less than the lower limit of the above range, the resulting cured product has a low coefficient of linear expansion and good dimensional stability, while it is not more than the upper limit of the above range. This is because the viscosity of the resulting curable silicone composition does not become too high and the handling workability is good.
  • the titanium oxide powder and the inorganic powder have the general formula: R 1 (4-a) Si (OR 2 ) a
  • R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms
  • R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group
  • a is an integer of 1 to 3.
  • R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group
  • R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond
  • R 5 is an oxygen atom or a divalent hydrocarbon group.
  • a hydrogen group R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group
  • b is an integer of 1 to 3
  • p is an integer of 1 or more.
  • R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms. This is because when R 1 has less than 6 carbon atoms, the effect of lowering the viscosity of the resulting curable silicone composition is poor. On the other hand, when the number of carbon atoms exceeds 20, the compatibility with the organopolysiloxane component decreases. Because it does.
  • R 1 monovalent hydrocarbon group includes hexyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups; benzyl group, phenylethyl group and other aralkyl groups; these alkyl groups and aralkyl groups. Examples thereof include groups in which part or all of the hydrogen atoms in the group are substituted with halogen atoms such as fluorine and chlorine, and alkyl groups having 6 to 20 carbon atoms are preferred.
  • R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group.
  • an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group;
  • Illustrative examples include alkenyl groups such as isopropylene group and isobutenyl group; acyl groups such as acetoxy group, preferably an alkyl group, and particularly a methyl group and an ethyl group.
  • a is an integer of 1 to 3, preferably 3.
  • organosilanes include the following compounds. C 6 H 13 Si (OCH 3 ) 3 C 8 H 17 Si (OC 2 H 5 ) 3 C 10 H 21 Si (OCH 3 ) 3 C 12 H 25 Si (OCH 3 ) 3 C 14 H 29 Si (OC 2 H 5 ) 3 C 6 H 5 —CH 2 CH 2 Si (OCH 3 ) 3
  • the amount of the organosilane blended is in the range of 0.1 to 10 parts by weight, preferably in the range of 0.1 to 5 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight of the present composition. In the range of 0.5 part by weight or in the range of 0.5 to 10 parts by weight. This is because the surface of titanium oxide and inorganic powder can be sufficiently treated when the compounding amount of organosilane is at least the lower limit of the above range, and on the other hand, when the amount is less than the upper limit of the above range, This is because the mechanical strength and adhesive strength can be improved.
  • R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, for example, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkenyl group, an aryl Group, aralkyl group and halogenated alkyl group.
  • the linear alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group.
  • Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, and 2-ethylhexyl group.
  • Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.
  • Examples of the alkenyl group include a vinyl group and an allyl group.
  • Examples of the aryl group include a phenyl group and a tolyl group.
  • Examples of the aralkyl group include 2-phenylethyl group and 2-methyl-2-phenylethyl group.
  • halogenated alkyl group examples include a 3,3,3-trifluoropropyl group, a 2- (nonafluorobutyl) ethyl group, and a 2- (heptadecafluorooctyl) ethyl group.
  • R 3 is preferably a methyl group or a vinyl group.
  • R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond, for example, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aryl group, Examples include aralkyl groups and halogenated alkyl groups.
  • Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group.
  • Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, and 2-ethylhexyl group.
  • Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.
  • Examples of the aryl group include a phenyl group and a tolyl group.
  • Examples of the aralkyl group include 2-phenylethyl group and 2-methyl-2-phenylethyl group.
  • Examples of the halogenated alkyl group include a 3,3,3-trifluoropropyl group, a 2- (nonafluorobutyl) ethyl group, and a 2- (heptadecafluorooctyl) ethyl group.
  • R 4 is preferably a methyl group or a phenyl group.
  • R 5 is an oxygen atom or a divalent hydrocarbon group.
  • the divalent hydrocarbon group for R 5 include alkylene groups such as ethylene group, propylene group, and butylene group; and alkylenearylene alkylene groups such as ethylenephenyleneethylene group and ethylenephenylenepropylene group.
  • R 6 represents an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group.
  • an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group;
  • Illustrative examples include alkenyl groups such as isopropylene group and isobutenyl group; acyl groups such as acetoxy group, preferably an alkyl group, and particularly a methyl group and an ethyl group.
  • b is an integer of 1 to 3, preferably 3.
  • p is an integer of 1 or more, preferably an integer in the range of 1 to 200, an integer in the range of 5 to 200, or
  • Examples of such an organosiloxane include the following compounds.
  • Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
  • the amount of the organosiloxane blended is in the range of 0.1 to 10 parts by weight, preferably in the range of 0.1 to 5 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight of the composition. In the range of 0.5 part by weight or in the range of 0.5 to 10 parts by weight. This is because the surface of titanium oxide and inorganic powder can be sufficiently treated when the amount of the organosiloxane is not less than the lower limit of the above range, and on the other hand, if the amount is less than the upper limit of the above range, This is because a decrease in hardness can be suppressed, an increase in linear expansion coefficient can be suppressed, and mechanical strength and adhesive strength can be improved.
  • the above organosilane or the above organosiloxane may be used alone or in combination. By using these together, it is possible to efficiently perform the surface treatment of the titanium oxide powder and the inorganic powder, and simultaneously impart high mechanical strength, low linear expansion coefficient, and high adhesive ability to the resulting cured product. it can.
  • the mass ratio of the organosilane to the organosiloxane is preferably in the range of 3: 7 to 7: 3, particularly 1: 1.
  • This composition is thermosetting, and its curing mechanism is not particularly limited. Examples thereof include hydrosilylation reactions, radical reactions with organic peroxides, and condensation reactions, and hydrosilylation reactions are preferred.
  • Examples of the hydrosilylation reaction-curable silicone composition include: (A) an organopolysiloxane having at least two alkenyl groups in one molecule; (B) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule ⁇ the amount of silicon-bonded hydrogen atoms in this component is 0.1 to 0.1 mol per 1 mole of alkenyl groups in component (A) Amount to be 10 moles ⁇ , (C) Titanium oxide powder having an average particle size of 0.05 to 10 ⁇ m (in the present composition, an amount of 50 to 90% by mass), (D) Inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 ⁇ m (amount of 5 to 40% by mass in the present composition), (E) (E-1) General formula: R 1 (4-a)
  • a hydrogen group R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, b is an integer of 1 to 3, and p is an integer of 1 or more.
  • Hydrosilylation catalyst (amount for promoting the hydrosilylation reaction of the composition) represented by the formula (0.1 to 10 parts by mass with respect to 100 parts by mass of the composition)
  • a curable silicone composition comprising at least
  • the organopolysiloxane of the component has at least two alkenyl groups in one molecule.
  • alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group.
  • the group bonded to the silicon atom other than the alkenyl group in the component (A) has 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like.
  • alkyl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group or a phenethyl group; a part of hydrogen atoms of these groups Or the group which substituted all with halogen atoms, such as a fluorine atom and a chlorine atom, is illustrated.
  • Component organopolysiloxane has at least two silicon-bonded hydrogen atoms in one molecule.
  • the group bonded to the silicon atom other than the hydrogen atom in the component (B) has 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group.
  • alkyl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group or a phenethyl group; a part of hydrogen atoms of these groups Or the group which substituted all with halogen atoms, such as a fluorine atom and a chlorine atom, is illustrated.
  • the component (A) is represented by the formula (A-1): -(R 7 R 8 SiO 2/2 ) m-
  • R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • alkyl group for R 7 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group.
  • R 8 is an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • m is an integer in the range of 5 to 50, preferably an integer in the range of 5 to 30. This is because when m is not less than the lower limit of the above range, the thermal expansion coefficient of the obtained cured product is remarkably reduced, and when it is not more than the upper limit of the above range, the mechanical strength of the obtained cured product is improved. It is.
  • the component (A-1) is a linear organopolysiloxane composed of only the above-mentioned linear siloxane block and having both molecular chain ends blocked.
  • Examples of the group at the end of the molecular chain include hydroxyl groups; alkoxy groups such as methoxy group, ethoxy group, and propoxy group; and organosiloxy groups such as trimethylsiloxy group, dimethylvinylsiloxy group, dimethylphenylsiloxy group, and methylphenylvinylsiloxy group. Is done.
  • the component (A-1) may be a block copolymer in which the linear siloxane block (X) and another siloxane block (Y) are linked.
  • a block copolymer As such a block copolymer, an XY copolymer in which X and Y are connected one by one, an XYX copolymer in which X is connected to both ends of Y, and X and Y are alternately connected z times repeatedly ( XY) z copolymers are exemplified.
  • the siloxane block (Y) has a general formula: -(R 7 c SiO (4-c) / 2 )- (Wherein R 7 is the same as above, and c is a number from 0.5 to 2). Or a polysiloxane composed of a repetition thereof.
  • the group at the end of the molecular chain of this block copolymer is exemplified by a hydroxyl group, an alkoxy group similar to the above, or an organosiloxy group similar to the above.
  • the organopolysiloxane is generally prepared by polymerizing a cyclic diorganosiloxane by a re-equilibration reaction in the presence of a base catalyst or an acid catalyst. In such a method, the linear siloxane block is retained. It is difficult to prepare a block copolymer. Therefore, as a method for preparing the block copolymer as described above, the polysiloxane having the linear siloxane block (X) and the siloxane or polysiloxane having another siloxane block (Y) are subjected to a condensation reaction. A method is illustrated.
  • the content of the component (A-1) is such that the content of the linear siloxane block is 20 to 60% by mass of the total of the organopolysiloxanes in the present composition, preferably 30 to 50% by mass. This is because when the content of the linear siloxane block is equal to or higher than the lower limit of the above range, the thermal expansion coefficient of the resulting cured product is remarkably lowered, whereas when the content is equal to or lower than the upper limit of the above range, the obtained curing is obtained. This is because the flexibility and mechanical strength of the object are improved.
  • (A) in addition to the component (A-1), (A-2) a linear or branched organopolysiloxane having at least two alkenyl groups in one molecule May be used in combination.
  • alkenyl group in the component (A-2) include alkenyl groups having 2 to 6 carbon atoms such as vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, and cyclohexenyl group.
  • the group bonded to the silicon atom other than the alkenyl group in the component (A-2) includes an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a phenyl group, a tolyl group, and a xylyl group.
  • Aryl groups having 6 to 12 carbon atoms such as benzyl groups, phenethyl groups and other aralkyl groups having 7 to 12 carbon atoms; halogenated alkyl groups such as 3-chloropropyl groups and 3,3,3-trifluoropropyl groups; Illustrated.
  • molecular chain both ends dimethylvinylsiloxy group-capped dimethylpolysiloxane
  • Examples include dimethylsiloxane / methylphenylsiloxane copolymers blocked with dimethylvinylsiloxy groups blocked at both molecular chains, and dimethylsiloxane / methylvinylsiloxane random copolymers blocked with trimethylsiloxy groups blocked at both molecular chains.
  • the branched chain organopolysiloxane (A-2) includes a siloxane unit represented by the formula: SiO 4/2 and a siloxane unit represented by the general formula: R 7 2 R 8 SiO 1/2. And those composed of siloxane units represented by the general formula: R 7 3 SiO 1/2 .
  • R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and examples thereof are the same groups as described above.
  • R 8 is an alkenyl group having 2 to 10 carbon atoms, and examples thereof are the same groups as described above.
  • the total of the siloxane units represented by 2 is preferably in the range of 0.5 to 1.5.
  • the organopolysiloxane may have a very small amount of hydroxyl groups, alkoxy groups, etc. bonded to silicon atoms in the molecule.
  • the content of the component (A-2) is not particularly limited, but the alkenyl group in this component is at most 10 mol% with respect to the total of the alkenyl group in component (A-1) and the alkenyl group in this component. It is preferable that the amount is as follows. This is because the thermal expansion coefficient of the resulting cured product is significantly reduced when the content of this component is not more than the upper limit of the above range.
  • R 9 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and examples thereof include the same groups as R 7 .
  • n is an integer in the range of 10 to 100, preferably an integer in the range of 20 to 80. This is because when n is not less than the lower limit of the above range, the coefficient of thermal expansion of the obtained cured product is remarkably reduced, while when it is not more than the upper limit of the above range, the mechanical strength of the obtained cured product is improved. It is.
  • an organopolysiloxane composed only of the above-mentioned linear siloxane block and blocked at both ends of the molecular chain is exemplified.
  • the group at the end of this molecular chain is a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group; an organosiloxy group such as a trimethylsiloxy group, a dimethylhydrogensiloxy group, a dimethylphenylsiloxy group, or a methylphenylhydrogensiloxy group Is exemplified.
  • the component (B) may be a block copolymer in which the linear siloxane block (X ′) and another siloxane block (Y ′) are linked.
  • a block copolymer an X′Y copolymer in which X ′ and Y are linked one by one, an X′YX ′ copolymer in which X ′ is linked to both ends of Y, and X ′ and Y are alternated And (X′Y) z copolymer linked repeatedly z times.
  • Examples of the siloxane block (Y) are the same as those described above.
  • the group at the end of the molecular chain of this block copolymer is exemplified by a hydroxyl group, an alkoxy group similar to the above, or an organosiloxy group similar to the above.
  • the content of component (B) is such that the silicon-bonded hydrogen atoms in this component are within the range of 0.1 to 10 mol per mol of alkenyl groups in component (A), preferably , An amount in the range of 0.5 to 10 mol, an amount in the range of 0.5 to 5 mol, or an amount in the range of 0.7 to 2 mol.
  • the content of the component (B) is not less than the lower limit of the above range, the thermal expansion coefficient of the resulting cured product is remarkably reduced, whereas when it is not more than the upper limit of the above range, the resulting cured product is a machine. This is because the mechanical strength is improved.
  • Tianium oxide powder of component (C) and inorganic powder of component (D) are as described above. Further, the organosilane and organosiloxane of the component (E) are as described above.
  • the component (C) and the component (D) are mixed with part or all of the component (A), Next, a method of mixing the component (E) with this and heating as necessary, mixing the component (C) with a part of the component (A), and then mixing a part of the component (E) with this Then, the component (D) was mixed with part of the component (A) that was heated as necessary, and then part of the component (E) was mixed with this and heated as necessary.
  • the method of mixing things is illustrated. Moreover, you may mix
  • the component (F) is a hydrosilylation reaction catalyst for promoting the curing reaction of the composition.
  • the component (F) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
  • the component (F) is preferably a platinum-based catalyst because curing of the composition can be remarkably accelerated.
  • the platinum catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex.
  • alkenylsiloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, and the like.
  • the content of the component (F) is not particularly limited as long as it is an amount sufficient to promote the hydrosilylation reaction of the present composition.
  • the metal atom in the present component is in mass units relative to the present composition. In an amount in the range of 0.01 to 500 ppm, an amount in the range of 0.01 to 100 ppm, or an amount in the range of 0.01 to 50 ppm.
  • the content of the component (F) is not less than the lower limit of the above range, the resulting composition is cured well.
  • the content is not more than the upper limit of the above range, the resulting cured product is colored. It is difficult.
  • the composition may contain (G) a reaction inhibitor in order to appropriately control the curing rate of the composition.
  • a reaction inhibitor in order to appropriately control the curing rate of the composition.
  • Examples of such component (G) include 1-ethynylcyclohexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyne- Alkyne alcohols such as 2-ol; Enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole.
  • the content of the component (G) is not limited, but is preferably in the range of 1 to 5,000 ppm by
  • the composition may contain (H) an adhesion promoter in order to further improve the adhesion to the substrate that is in contact with the curing process.
  • a trialkoxysiloxy group for example, trimethoxysiloxy group, triethoxysiloxy group
  • a trialkoxysilylalkyl group for example, trimethoxysilylethyl group, triethoxysilylethyl group
  • a hydrosilyl group or Organosilane having an alkenyl group for example, vinyl group, allyl group
  • Organosilane having a roxyalkyl group for example, 3-methacryloxypropyl group
  • the viscosity at 25 ° C. at a shear rate of 1 s ⁇ 1 is preferably 1000 Pa ⁇ s or less, and the viscosity at 25 ° C. at a shear rate of 10 s ⁇ 1 is preferably 100 Pa ⁇ s or less. This is because when the viscosity is as described above, it is easy to cope with various production processes when a cured product is formed. Further, since the liquid does not easily drip at the time of use, the value of the thixo index determined by the following formula is preferably 5.0 or more.
  • the present composition may be mixed with a diluent such as an organic solvent or silicone oil to adjust the viscosity.
  • a diluent such as an organic solvent or silicone oil to adjust the viscosity.
  • This diluent preferably has a boiling point within the range of 150 to 250 ° C. because it is easily volatilized in the curing or post-cure process of the present composition and hardly remains in the cured product.
  • examples of such diluents include isoparaffinic organic solvents such as IP solvent manufactured by Idemitsu Kosan Co., Ltd., glycol ether organic solvents such as diethylene glycol monomethyl ether, or OS-20 manufactured by Toray Dow Corning Co., Ltd. Silicone solvents are exemplified.
  • the content of this diluent is not particularly limited, but it is easily volatilized in the curing or post-curing process of the present composition and hardly remains in the cured product. Therefore, 0.1 to 10 parts per 100 parts by mass of the present composition. It is preferably within the range of parts by mass.
  • the cured product of the present invention is obtained by curing the above curable silicone composition.
  • the linear expansion coefficient of the cured product of the present invention is not particularly limited, but the average linear expansion coefficient at 25 to 200 ° C. is preferably 100 ppm / ° C. or less, and more preferably 50 ppm / ° C. or less.
  • JIS K 7375: 2008 “Plastic total light transmittance and total light reflectance calculation method” when it is a 100 ⁇ m film cured product
  • the total light reflectance in is preferably 90% or more.
  • the shape of the cured product of the present invention is not particularly limited, but may be a plate or film formed on the support. Since the thermal expansion coefficient of the cured product of the present invention is extremely low, it is suitable as a coating film or film for coating the support.
  • a method for forming such a cured product of the present invention a method of forming a film-like or plate-like cured product on a support by a molding process of the above curable silicone composition, or the above curable silicone composition The method of forming a film-like or plate-like cured product on a support by an application step is mentioned.
  • imide resin bismaleimide / triazine resin
  • glass fiber-containing epoxy resin paper phenol resin, bakelite, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacrylonitrile resin, polycarbonate resin, fluororesin, polyimide resin, polyphenylene Sulfide resin, aramid resin, polyether ether resin, polyether imide resin, liquid crystal polymer, polyether sulfone resin, cycloolefin resin, silicone rubber, silicone resin and other resin supports; aluminum foil, copper foil, nickel foil, Or metal supports, such as aluminum nitride foil, are illustrated.
  • Examples of methods for forming a cured product on the support include a molding process and a coating process.
  • Examples of the molding process include press molding and compression molding using a mold.
  • Examples of the coating process include screen printing and bar coater. , Roll coater, reverse coater, gravure coater, air knife coater, spray coater, curtain coater are exemplified, and in particular, when coating on a thin film, a known coating method such as a high-precision offset coater or a multi-stage roll coater is used. be able to.
  • the cured product of the present invention is preferably formed on the support in the form of a plate or film by the method as described above. Since the hardened
  • COB chip-on-board type
  • the optical semiconductor device of the present invention has a light reflecting material made of a cured product of the above composition. Such an optical semiconductor device of the present invention will be described in detail with reference to FIGS.
  • FIG. 1 shows a cross-sectional view of a chip-on-board (COB) type optical semiconductor device which is an example of the optical semiconductor device of the present invention.
  • COB chip-on-board
  • an optical semiconductor element 1 is mounted on a COB substrate 2 by die bonding, and the optical semiconductor element 1 and circuits 3 and 4 are electrically connected by a bonding wire 5.
  • a light reflecting material 6 is formed around the optical semiconductor element 1 on the substrate 2 so as to efficiently reflect light emitted from the optical semiconductor element 1.
  • FIG. 2 shows a sectional view of another chip-on-board (COB) type optical semiconductor device which is an example of the optical semiconductor device of the present invention.
  • COB chip-on-board
  • the optical semiconductor element 1 is electrically connected to the circuits 3 and 4 on the COB substrate 2 by bonding pads.
  • a light reflecting material 6 is formed around the optical semiconductor element 1 on the substrate 2 so as to efficiently reflect light emitted from the optical semiconductor element 1.
  • the substrate 2 may be a metal substrate such as aluminum or copper, and the circuits 3 and 4 are formed on the surface of the metal substrate via an insulating layer (not shown). Is formed.
  • a non-metallic substrate is used as the substrate 2, it is not necessary to form an insulating layer.
  • Such non-metallic substrates include glass epoxy substrates, polybutylene terephthalate (PBT) substrates, polyimide substrates, polyester substrates, aluminum nitride substrates, boron nitride substrates, silicon nitride substrates, alumina ceramic substrates, glass substrates, flexible glass substrates. Is illustrated.
  • a hybrid substrate made of an aluminum substrate or a copper substrate having an insulating resin layer, a printed wiring silicon substrate, a silicon carbide substrate, or a sapphire substrate can be used as the substrate 2.
  • the circuits 3 and 4 are made of at least one metal selected from the group consisting of silver, copper, and aluminum having high electrical conductivity, or an alloy containing at least one selected from the group consisting of silver, copper, and aluminum. Used. Further, it is preferable that a light reflecting material 6 is formed on the substrate 2 so as to expose a portion on which the optical semiconductor element 1 is mounted.
  • the optical semiconductor element 1 and the light reflecting material 6 are sealed with the sealing material 7, but only the optical semiconductor element 1 may be sealed with the sealing material 7 in a dome shape.
  • FIG. 1 and FIG. 2 only one optical semiconductor element 1 is shown on the substrate 2, but a plurality of optical semiconductor elements 1 may be mounted on the substrate 2.
  • a viscosity is a value in each share rate in 25 degreeC.
  • Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
  • the hardness, bending strength, linear expansion coefficient, adhesion to metal, and total light reflectance of the cured product were measured as follows.
  • the curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product.
  • the hardness of the cured product was measured with a type D durometer specified in JIS K 7215-1986 “Method for testing the durometer hardness of plastics”.
  • Total light reflectance of cured product The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product having a thickness of 100 ⁇ m. The total light reflectance of this cured product was measured by the method defined in JIS K 7375: 2008 “Plastic Total Light Transmittance and Total Light Reflectance Determination Method”.
  • Example 1 formula: - (MeViSiO 2/2) 20 - 4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula: Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, titanium oxide having an average primary particle size of 0.2 ⁇ m (SX-3103 manufactured by Sakai Chemical Industry), and an average particle size of 15 ⁇ m 21.8 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then heated to 150 ° C. under reduced pressure.
  • a silicone base was prepared by
  • a curable silicone composition (I) is prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (the amount of platinum atoms with respect to the present composition is 3.5 ppm by mass). ) was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition.
  • the curable silicone composition and the properties of the cured product are shown in Table 1.
  • Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3 After putting 3 parts by mass of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the following formula, and mixing at room temperature with 3 parts by mass of dimethylpolysiloxane blocked with a trimethoxysiloxy group at the other end, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
  • a silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
  • Silicone composition (VII) was prepared.
  • content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition.
  • the curable silicone composition and the properties of the cured product are shown in Table 1.
  • Example 8 formula: - (MeViSiO 2/2) 20 - 5.8 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula: Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi 5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 72 parts by mass of titanium oxide having an average primary particle size of 0.24 ⁇ m (Taipaque R-630 manufactured by Ishihara Sangyo), an average particle size of 15 ⁇ m Of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron), 6 parts by mass, 1 part by mass of n-decyltrimethoxysilane, and a viscosity of 125 mPa ⁇
  • Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3 After putting 3 parts by mass of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the following formula, and mixing at room temperature with 3 parts by mass of dimethylpolysiloxane blocked with a trimethoxysiloxy group at the other end, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
  • a curable silicone composition (XI) was prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (with respect to the present composition, an amount in which platinum atoms are 3.5 ppm by mass). ) was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
  • a curable silicone composition (XV) is prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (amount in which platinum atoms are 3 ppm by mass with respect to the present composition). Prepared. In addition, content of said linear methylvinylsiloxane block is 34.7 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
  • Example 10 to 12 Inside the support of either PET film, aluminum plate, or copper plate, a spacer with a thickness of 100 ⁇ m is installed so that a space of 5 cm ⁇ 5 cm can be taken, and the curability prepared above within the range surrounded by the spacer 0.8 g of the silicone composition was injected. Next, a release film is placed on the curable silicone composition and heated at 150 ° C. and a press pressure of 5 kg for 15 minutes to produce an integrally molded product of the light reflecting material comprising the cured product and the support. did. The appearance of the cured product was visually observed, and the results are shown in Table 3.
  • Examples 13 to 15, Comparative Examples 13 to 15 Using a film coater (PI-1210) manufactured by Tester Sangyo Co., Ltd., the curable silicone composition prepared above was applied to any one of an aluminum plate, a copper plate, a PET film, and a glass plate with a gap size of 100 ⁇ m. And applied. The state of application was visually observed. Then, it heated in 150 degreeC oven for 1 hour, and produced the integral molded product of the light reflection material which consists of hardened
  • PI-1210 manufactured by Tester Sangyo Co., Ltd.
  • the adhesiveness to the support is good and the cured product does not have cracks or the like. I understood.
  • the curable silicone composition of the present invention has thixotropy, dripping hardly occurs between the coating process and heat curing, and no change in shape was observed.
  • the curable silicone composition of the present invention has a low coefficient of thermal expansion of a cured product obtained by curing, and has high light reflectivity in a thin film. Therefore, the curable silicone composition is suitable as a composite light reflecting material to be used integrally with other members. is there.

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Abstract

Cette invention concerne une composition de silicone thermodurcissable qui comprend une poudre d'oxyde de titane ayant un diamètre de particule moyen de 0,05 à 10 µm et une poudre inorganique qui n'est pas de l'oxyde de titane et a un diamètre de particule moyen de 0,1 à 20 µm, la teneur en poudre d'oxyde de titane étant de 50 à 90 % en poids par rapport à la composition et la teneur en poudre inorganique de 5 à 40 % en poids par rapport à la composition, la composition selon l'invention étant caractérisée en ce que les surfaces de la poudre d'oxyde de titane et de la poudre inorganique ont été traitées avec un organosilane spécifique et/ou un organosiloxane spécifique. La composition de silicone durcissable est thixotrope, douée d'une maniabilité et applicabilité satisfaisantes, et durcit de façon à former un objet durci ayant un faible coefficient de dilatation thermique, un haut pouvoir couvrant, une résistance mécanique élevée, et une adhérence satisfaisante à divers substrats.
PCT/JP2015/004355 2014-09-10 2015-08-28 Composition de silicone durcissable, objet durci obtenu à partir de celle-ci et dispositif optique à semi-conducteurs WO2016038836A1 (fr)

Priority Applications (3)

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KR20190039962A (ko) 2016-08-08 2019-04-16 다우 코닝 도레이 캄파니 리미티드 경화성 입상 실리콘 조성물, 이것으로 이루어지는 광반사재 및 이의 제조 방법
WO2018030287A1 (fr) 2016-08-08 2018-02-15 東レ・ダウコーニング株式会社 Composition de silicone particulaire durcissable, élément semi-conducteur comprenant la composition de silicone particulaire durcissable et procédé de moulage pour élément semi-conducteur comprenant la composition de silicone particulaire durcissable
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WO2018043270A1 (fr) * 2016-09-01 2018-03-08 東レ・ダウコーニング株式会社 Composition d'organopolysiloxane durcissable, et composition d'agent protecteur ou d'agent adhésif pour composants électriques/électroniques
KR20190075047A (ko) * 2016-09-01 2019-06-28 다우 도레이 캄파니 리미티드 경화성 오가노폴리실록산 조성물 및 전기·전자 부품의 보호제 또는 접착제 조성물
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CN110088206B (zh) * 2016-09-01 2021-08-20 陶氏东丽株式会社 固化性有机聚硅氧烷组合物以及电气电子零部件的保护剂或粘合剂组合物
US11555119B2 (en) 2017-06-19 2023-01-17 Dow Toray Co., Ltd. Curable granular silicone composition, semiconductor member comprising same, and forming method thereof
EP3684078A4 (fr) * 2017-09-11 2020-11-04 FUJIFILM Corporation Composition de sonde à ondes acoustiques, sonde à ondes acoustiques en résine de silicone, sonde à ondes acoustiques, sonde ultrasonique, appareil de mesure d'ondes acoustiques, appareil de diagnostique à ultrasons, appareil de mesure d'ondes photoacoustiques, et endoscope à ultrasons
WO2019181713A1 (fr) * 2018-03-23 2019-09-26 信越化学工業株式会社 Composition de silicone
JPWO2019181713A1 (ja) * 2018-03-23 2021-02-25 信越化学工業株式会社 シリコーン組成物
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KR20210108990A (ko) 2018-12-27 2021-09-03 다우 도레이 캄파니 리미티드 경화성 실리콘 조성물, 그의 경화물 및 그의 제조 방법
CN113396188A (zh) * 2018-12-27 2021-09-14 陶氏东丽株式会社 传递成型用固化性有机硅组合物、其固化物及其制造方法
CN113396188B (zh) * 2018-12-27 2023-01-17 陶氏东丽株式会社 传递成型用固化性有机硅组合物、其固化物及其制造方法
JP7103974B2 (ja) 2019-02-25 2022-07-20 信越化学工業株式会社 付加硬化型シリコーン組成物、光反射材用シリコーン硬化物、光反射材及び光半導体装置
JP2020132824A (ja) * 2019-02-25 2020-08-31 信越化学工業株式会社 付加硬化型シリコーン組成物、光反射材用シリコーン硬化物、光反射材及び光半導体装置
CN111607231B (zh) * 2019-02-25 2022-04-22 信越化学工业株式会社 加成固化型硅酮组合物、光反射材料用硅酮固化物、光反射材料及光半导体装置
CN111607231A (zh) * 2019-02-25 2020-09-01 信越化学工业株式会社 加成固化型硅酮组合物、光反射材料用硅酮固化物、光反射材料及光半导体装置
WO2020241368A1 (fr) * 2019-05-31 2020-12-03 ダウ・東レ株式会社 Composition d'organopolysiloxane durcissable, et élément optique formé à partir dudit produit durci
US11845869B2 (en) 2019-06-21 2023-12-19 Dow Silicones Corporation Method for producing thixotropic curable silicone composition
WO2022038888A1 (fr) * 2020-08-21 2022-02-24 ダウ・東レ株式会社 Composition d'organopolysiloxane durcissable, élément thermoconducteur et structure de dissipation de chaleur
WO2023164018A1 (fr) * 2022-02-24 2023-08-31 Dow Silicones Corporation Composition de silicone durcissable et produit durci à base de celle-ci
WO2023164019A1 (fr) * 2022-02-24 2023-08-31 Dow Silicones Corporation Composition de silicone durcissable

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