TWI690553B - Hardening polysiloxane composition, hardened product thereof, method of forming hardened product, and optical semiconductor device - Google Patents

Abstract

The curable polysiloxane composition of the present invention is characterized in that it contains titanium oxide powder with an average particle diameter of 0.05 to 10 μm and inorganic powder other than titanium oxide with an average particle diameter of 0.1 to 20 μm, and the content of the above titanium oxide powder It is 50 to 90% by mass of the composition, the content of the inorganic powder is 5 to 40% by mass of the thermosetting polysiloxane composition in the composition, and the titanium oxide powder and the inorganic powder are obtained by Surface treatment of specific organosilanes and/or specific organosiloxanes. The curable polysiloxane composition has thixotropy, good operability, and is hardened to form a hardened product with low thermal expansion rate, high concealment rate, high mechanical strength, and good adhesion to various substrates .

Description

Hardening polysiloxane composition, hardened product thereof, method of forming hardened product, and optical semiconductor device

The present invention relates to a curable polysiloxane composition, a cured product thereof, and an optical semiconductor device.

In the optical semiconductor device, in order to efficiently reflect the light emitted from the optical semiconductor element, a light reflecting material is provided. Examples of the hardening polysiloxane composition for forming the light reflecting material include a hydrosilation reaction having a structure in which any one of a vinyl group and an allyl group is directly bonded to a silicon atom with a hydrogen atom Polysiloxane resin, platinum catalyst, and white pigment hardening polysiloxane composition (refer to Patent Document 1); including vinyl-containing organic polysiloxane with a weight average molecular weight (Mw) of 30,000 or more, Organic hydrogen polysiloxane with at least two hydrogen atoms bonded to silicon atoms in one molecule, white pigment, inorganic filler other than white pigment, platinum metal catalyst, and hardening polysiloxane of reaction control agent Composition (refer to Patent Document 2); a branched-chain organic polysiloxane containing 30 to 80 mol% of all organic groups bonded to silicon atoms is phenyl and 5 to 20 mol% is alkenyl, 30 to 60 mole% of all organic groups bonded to silicon atoms are alkenyl groups and organic polysiloxanes with silicon atoms of 10 or less, in a molecule having at least 2 hydrogen atoms bonded to silicon atoms and with 20 to 70 mol% of all organic groups bonded to silicon atoms are organic polysiloxanes with phenyl groups, white pigments Material, non-spherical silica or glass fiber, spherical silica, and a hardening polysilicone composition for hydrosilylation catalyst (refer to Patent Document 3).

In recent years, when the light reflecting material is used on the substrate in the form of a thin film in the optical semiconductor device, it is required that the crack caused by the difference in thermal expansion rate between the light reflecting material and the substrate is less likely to occur, Peel off. In addition to this, the light-reflecting material requires not only sufficient light-reflecting performance, but also sufficient concealing performance that does not transmit light even if it is a thin film.

However, if a large amount of white pigment is blended into the curable polysiloxane composition in order to make the light reflection performance excellent and improve the film's shielding performance, the operation workability of the obtained composition will be reduced. The issue of reduced continuity.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-021394

[Patent Document 2] Japanese Patent Laid-Open No. 2011-140550

[Patent Document 3] Japanese Patent Laid-Open No. 2013-076050

The object of the present invention is to provide a thixotropy, good operability, and hardening to form a hardened product with low thermal expansion rate, high concealment rate, high mechanical strength, and good adhesion to various substrates Hardening polysiloxane composition; hardening product with low thermal expansion rate, high concealment rate, high mechanical strength; and optical semiconductor device with excellent reliability.

The curable polysiloxane composition of the present invention is characterized in that it contains titanium oxide powder with an average particle diameter of 0.05 to 10 μm and inorganic powder other than titanium oxide with an average particle diameter of 0.1 to 20 μm, and the content of the above titanium oxide powder It is 50 to 90% by mass of the composition, the content of the inorganic powder is 5 to 40% by mass of the thermosetting polysiloxane composition in the composition, and the titanium oxide powder and the inorganic powder are obtained by General formula: R ¹ _(4-a) Si(OR ² ) _a

(In the formula, 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 1 to 3. Integer)

The organosilane and/or formula represented by:

(In the formula, R ³ is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R ⁴ is the same kind or a different kind of monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, R ⁵ is an oxygen atom or a divalent hydrocarbon group, R ⁶ is an alkyl, alkoxyalkyl, alkenyl, or acetyl group, b is an integer of 1 to 3, and p is an integer of 1 or more)

The organosiloxane indicated is surface-treated.

Moreover, the cured product of the present invention is characterized in that it is obtained by curing the curable polysiloxane composition.

Furthermore, the optical semiconductor device of the present invention is characterized by having a light reflecting material containing the cured product of the curable polysiloxane composition.

The curable polysiloxane composition of the present invention has the following characteristics: it has thixotropy, good operability, and is hardened to form a low thermal expansion rate, a high concealment rate, a high mechanical strength, and further Followed by a hardened product with good properties. In addition, the hardened product of the present invention has the characteristics of low thermal expansion rate, high concealment rate, and high mechanical strength. Furthermore, this The optical semiconductor device of the invention is characterized by excellent reliability.

1: Optical semiconductor element

2: substrate

3: Circuit

4: Circuit

5: Bonding wire

6: Light reflecting material

7: Sealing material

1 is a cross-sectional view of a chip on board (COB, Chip on Board) type optical semiconductor device as an example of the optical semiconductor device of the present invention.

2 is a cross-sectional view of another chip on board (COB) type optical semiconductor device as an example of the optical semiconductor device of the present invention.

First, the curable polysiloxane composition of the present invention will be described.

The curable polysiloxane composition of the present invention contains titanium oxide powder having an average particle diameter of 0.05 to 10 μm and inorganic powder other than titanium oxide having an average particle diameter of 0.1 to 20 μm, and the content of the above titanium oxide powder is in the composition 50 to 90% by mass, the content of the above inorganic powder is 5 to 40% by mass in the composition.

The titanium oxide powder is a white pigment used to impart light reflection properties to the hardened product of the composition. Examples of such titanium oxide powder include anatase-type titanium oxide powder and rutile-type titanium oxide powder. In terms of high light reflection performance and concealing power of the hardened product, rutile-type titanium oxide powder is preferred. . The average particle diameter of the titanium oxide is in the range of 0.05 to 10 μm, preferably in the range of 0.01 to 5 μm, or in the range of 0.01 to 3 μm. The titanium oxide may be prepared by surface-treating the surface with a silane coupling agent, silica, alumina, zirconia, or the like in advance.

The content of the titanium oxide powder is within the range of 50 to 90% by mass in the composition, preferably within the range of 50 to 85% by mass, within the range of 50 to 80% by mass, within the range of 55 to 90% by mass , Within the range of 55 to 85% by mass, or within the range of 55 to 80% by mass. The reason is that, in the present composition, if the content of titanium oxide powder is more than the lower limit of the above range, the thixotropy of the obtained curable polysiloxane composition is good, and the concealment or The strength is good. On the other hand, if it is equal to or lower than the upper limit of the above range, the workability of the obtained curable polysiloxane composition is good. Generally, titanium oxide powder The content is 10 to 30% by mass relative to the curable polysiloxane composition. However, in the present invention, by containing 50% by mass or more, not only can the concealment of the obtained hardened product be improved, but also the mechanical strength can be improved. In addition, even if a thixotropy-imparting component such as fumed silica is not prepared in the present composition, it is possible to impart appropriate thixotropy to the composition.

Inorganic powders other than titanium oxide are used to reduce the linear expansion rate of the hardened product and improve the dimensional stability by using together with the above titanium oxide powder. Examples of such inorganic powders include spherical silica, non-spherical silica, or glass fiber, but in view of the small increase in viscosity of the obtained hardenable polysiloxane composition, spherical is preferred Silicon dioxide. Examples of spherical silicas include dry silica, wet silica, molten silica, and explosive silica. However, in terms of good filling properties of the composition, it is preferably molten Silicon dioxide. The average particle diameter of the inorganic powder is in the range of 0.1 to 20 μm. In view of the ease of passing through the screen or the ease of film formation when using the coating step using screen printing, it is preferably 0.1 to Within the range of 15 μm, within the range of 0.1-10 μm, within the range of 0.2-20 μm, within the range of 0.2-15 μm, or within the range of 0.2-10 μm.

The content of the inorganic powder is in the range of 5 to 40% by mass in the composition, preferably in the range of 5 to 35% by mass, or in the range of 5 to 30% by mass. The reason is that if the content of the inorganic powder is more than the lower limit of the above range, the linear expansion rate of the obtained hardened product is low, and the dimensional stability is good. On the other hand, if it is below the upper limit of the above range, the obtained The viscosity of the hardenable silicone composition does not become too high, and the workability is good.

The composition is characterized in that the titanium oxide powder and the inorganic powder have the general formula: R ¹ _(4-a) Si(OR ² ) _a

(In the formula, 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 1 to 3. Integer)

The organosilane and/or formula represented by:

(In the formula, R ³ is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R ⁴ is the same kind or a different kind of monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, R ⁵ is an oxygen atom or a divalent hydrocarbon group, R ⁶ is an alkyl, alkoxyalkyl, alkenyl, or acetyl group, b is an integer of 1 to 3, and p is an integer of 1 or more)

The organosiloxane indicated is surface-treated.

In the above-mentioned organosilane, in the formula, R ¹ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms. The reason is that when the carbon number of R ¹ is less than 6, the effect of reducing the viscosity of the obtained hardenable polysiloxane composition is lacking. On the other hand, if the carbon number exceeds 20, The compatibility of the alkane component decreases. As the monovalent hydrocarbon group of R ¹ , there can be exemplified: alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; aralkyl groups such as benzyl and phenylethyl ; Part or all of the hydrogen atoms in the alkyl or aralkyl groups are substituted with halogen atoms such as fluorine and chlorine, preferably C 6-20 alkyl groups;

In the formula, R ² is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group. Specifically, it can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like having 1 to 6 carbon atoms; methoxymethyl, ethoxymethyl, methoxyethyl Alkoxy groups such as alkoxyalkyl; alkenyl groups such as isopropyl and isobutenyl; and acetyl groups such as acetyloxy, preferably alkyl, especially methyl and ethyl. In addition, in the formula, a is an integer of 1 to 3, preferably 3.

As such an organosilane, the following compounds can be exemplified.

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 compounding amount of the organosilane is within a range of 0.1 to 10 parts by mass relative to 100 parts by mass of the composition, preferably within a range of 0.1 to 5 parts by mass, within a range of 0.5 to 5 parts by mass, or 0.5 to Within 10 parts by mass. The reason is that if the blending amount of the organosilane is above the lower limit of the above range, the surface of titanium oxide and inorganic powder can be sufficiently treated. On the other hand, if it is below the upper limit of the above range, it can be Increase the mechanical strength or adhesion of the hardened material obtained.

On the other hand, in the above-mentioned organosiloxane, in the formula, R ³ is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and examples include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups. , Alkenyl, aryl, aralkyl, halogenated alkyl. Examples of linear alkyl groups include methyl, ethyl, propyl, hexyl, and octyl. Examples of branched alkyl groups include isopropyl, isobutyl, tertiary butyl, and 2-ethylhexyl. Examples of cyclic alkyl groups include cyclopentyl and cyclohexyl. Examples of the alkenyl group include vinyl and allyl groups. Examples of the aryl group include phenyl and tolyl. Examples of aralkyl groups include 2-phenylethyl and 2-methyl-2-phenylethyl. Examples of halogenated alkyl groups include 3,3,3-trifluoropropyl, 2-(nonafluorobutyl)ethyl, and 2-(heptadecafluorooctyl)ethyl. R ^{3 is} preferably methyl or vinyl.

Furthermore, in the formula, R ⁴ is a monovalent hydrocarbon group having no aliphatic unsaturated bond of the same kind or different kinds, for example, linear alkyl, branched alkyl, cyclic alkyl, aryl, aromatic Alkyl, halogenated alkyl. Examples of linear alkyl groups include methyl, ethyl, propyl, hexyl, and octyl. Examples of branched alkyl groups include isopropyl, isobutyl, tertiary butyl, and 2-ethylhexyl. Examples of cyclic alkyl groups include cyclopentyl and cyclohexyl. Examples of the aryl group include phenyl and tolyl. Examples of aralkyl groups include 2-phenylethyl and 2-methyl-2-phenylethyl. Examples of halogenated alkyl groups include 3,3,3-trifluoropropyl, 2-(nonafluorobutyl)ethyl, and 2-(heptadecafluorooctyl)ethyl. R ^{4 is} preferably methyl or phenyl.

In the formula, R ⁵ is an oxygen atom or a divalent hydrocarbon group. As the divalent hydrocarbon group of R ⁵ , there can be exemplified: alkylene groups such as ethylidene, propylidene, butylidene; ethylidene, phenylidene, ethylidene, propylidene, etc. .

In the formula, R ⁶ is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group. Specifically, it can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like having 1 to 6 carbon atoms; methoxymethyl, ethoxymethyl, methoxyethyl Alkoxy groups such as alkoxyalkyl; alkenyl groups such as isopropyl and isobutenyl; and acetyl groups such as acetyloxy, preferably alkyl, especially methyl and ethyl. In the formula, b is an integer of 1 to 3, preferably 3. In the formula, 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 an integer in the range of 5 to 150.

As such an organosiloxane, the following compounds can be exemplified. In addition, in the formula, Me, Ph, and Vi represent methyl, phenyl, and vinyl, respectively.

Me ₃ SiO(Me ₂ SiO) ₁₅ Si(OMe) ₃

Me ₃ SiO(Me ₂ SiO) ₂₃ Si(OMe) ₃

Me ₃ SiO(Me ₂ SiO) ₁₁₀ Si(OMe) ₃

ViMe ₂ SiO(Me ₂ SiO) ₂₉ Si(OMe) ₃

ViMe ₂ SiO(Me ₂ SiO) ₁₀ Si(OMe) ₃

ViMe ₂ SiO(Me ₂ SiO) ₅ Si(OMe) ₃

Me ₃ SiO(MePhSiO) ₁₀ Si(OMe) ₃

The compounding amount of the organosiloxane is within a range of 0.1 to 10 parts by mass relative to 100 parts by mass of the composition, preferably within a range of 0.1 to 5 parts by mass, within a range of 0.5 to 5 parts by mass, or 0.5 to 10 parts by mass. The reason is that if the amount of organosiloxane is more than the lower limit of the above range, the surface of titanium oxide and inorganic powder can be fully Surface treatment, on the other hand, is because if it is below the upper limit of the above range, it is possible to suppress a decrease in the hardness of the obtained hardened product, or to suppress an increase in the coefficient of linear expansion, or to increase the mechanical strength or adhesion.

In the present composition, the above-mentioned organosilane or the above-mentioned organosiloxane may be used alone, or may be used in combination. By using these in combination, the surface treatment of the above-mentioned titanium oxide powder and inorganic powder can be performed efficiently, and the obtained hardened product can be simultaneously given higher mechanical strength, lower linear expansion ratio, and higher adhesion ability. The quality of the above-mentioned organosilane and the above-mentioned organosiloxane is preferably in the range of 3:7 to 7:3, and particularly preferably 1:1.

The composition is thermosetting, and its hardening mechanism is not particularly limited. For example, it can be exemplified by hydrosilylation reaction, radical reaction using organic peroxide, and condensation reaction, preferably hydrosilylation reaction. As the hydrosilation reaction curable polysiloxane composition, for example, a curable polysiloxane composition containing at least the following components is preferred: (A) an organic polysiloxane having at least 2 alkenyl groups in one molecule, ( B) An organic polysiloxane containing at least 2 hydrogen atoms bonded to silicon atoms in one molecule {1 mole of alkenyl groups in (A) component, hydrogen atoms bonded to silicon atoms in this component Become 0.1 to 10 moles), (C) Titanium oxide powder with an average particle diameter of 0.05 to 10 μm (in this composition, an amount of 50 to 90% by mass), (D) with an average particle diameter of 0.1 to 20 μm Inorganic powder other than titanium oxide (in this composition, it is 5 to 40% by mass), (E) (E-1) General formula: R ¹ _(4-a) Si(OR ² ) _a

(In the formula, 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 1 to 3. Integer)

The represented organosilane (0.1 to 10 parts by mass relative to 100 parts by mass of the composition) and/or (E-2) general formula:

(In the formula, R ³ is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R ⁴ is the same kind or a different kind of monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, R ⁵ is an oxygen atom or a divalent hydrocarbon group, R ⁶ is an alkyl, alkoxyalkyl, alkenyl, or acetyl group, b is an integer of 1 to 3, and p is an integer of 1 or more)

The indicated organic silicone (0.1 to 10 parts by mass relative to 100 parts by mass of the composition), and (F) a catalyst for hydrosilylation reaction (amount to promote the hydrosilylation reaction of the composition).

(A) The component organic polysiloxane has at least 2 alkenyl groups in one molecule. Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, and hexenyl. As the group bonded to the silicon atom other than the alkenyl group in the component (A), there can be exemplified: methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, etc. ~6 alkyl groups; aryl groups with 6 to 12 carbon atoms such as phenyl, tolyl and xylyl; aralkyl groups with 7 to 12 carbon atoms such as benzyl and phenethyl; hydrogen of these groups A part or all of the atoms are replaced with halogen atoms such as fluorine atoms and chlorine atoms.

(B) The component organic polysiloxane has at least 2 hydrogen atoms bonded to silicon atoms in one molecule. As the group bonded to the silicon atom other than the hydrogen atom in the component (B), there can be exemplified: methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, etc. ~6 alkyl groups; aryl groups with 6 to 12 carbon atoms such as phenyl, tolyl and xylyl; aralkyl groups with 7 to 12 carbon atoms such as benzyl and phenethyl; hydrogen of these groups A part or all of the atoms are replaced with halogen atoms such as fluorine atoms and chlorine atoms.

In the present composition, in terms of significantly reducing the thermal expansion rate of the obtained hardened product, it is preferable that the component (A) has at least the general formula (A-1): -(R ⁷ R ⁸ SiO _{2 /2} ) _m-

The linear polysiloxane compound represented by the linear silicone block, (B) component has at least the general formula (B-1): -(R ⁹ HSiO _2/2 ) _n-

The linear polysiloxanes represented by the linear silicone block.

In the component (A-1), in the formula, R ⁷ is an alkyl group having 1 to 6 carbon atoms or a phenyl group. Examples of the alkyl group for R ⁷ include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, and cyclohexyl. In the formula, R ⁸ is an alkenyl group having 2 to 10 carbon atoms, and examples thereof include vinyl, allyl, butenyl, pentenyl, and hexenyl.

In addition, in the formula, m is an integer in the range of 5-50, preferably an integer in the range of 5-30. The reason for this is that if m is above the lower limit of the above range, the thermal expansion coefficient of the obtained cured product is significantly reduced, and on the other hand, if it is below the upper limit of the above range, the mechanical strength of the obtained cured product is improved.

(A-1) The component can be exemplified by a chain-shaped organic polysiloxane containing only the above-mentioned linear siloxane block and having both molecular chain ends blocked. As the terminal group of the molecular chain, there can be exemplified: hydroxy; alkoxy such as methoxy, ethoxy, propoxy; trimethylsiloxy, dimethylvinylsiloxy, dimethylphenyl Organic silane alkoxy such as silane alkoxy, methylphenyl vinyl silane alkoxy. In addition, the component (A-1) may be a block copolymer formed by connecting the linear siloxane block (X) and another siloxane block (Y). As such a block copolymer, an XY copolymer formed by connecting one of X and Y, an XYX copolymer having X connected to both ends of Y, and X and Y are alternately repeated z times and connected (XY)z copolymer. As this siloxane block (Y), the general formula can be exemplified: -(R ⁷ _c SiO _(4-c)/2 )-

(In the formula, R ⁷ is the same as above, c is a number of 0.5~2)

The represented silicone or polysiloxane containing the repeating block unit. In addition, as the group of the molecular chain terminal of the block copolymer, a hydroxyl group, the same alkoxy group as described above, or the same organosilane alkoxy group as described above can be exemplified.

Organopolysiloxane is usually prepared by polymerizing cyclic diorganosiloxane in the presence of an alkali catalyst or an acid catalyst by rebalancing reaction, but it is difficult to prepare by this method. Block copolymer of linear siloxane block. Therefore, as a method of preparing the block copolymer as described above, polysiloxanes having the above-mentioned linear siloxane block (X) and silicon having other siloxane blocks (Y) can be exemplified. A method of condensation reaction of oxane or polysiloxane.

In the present composition, the content of the component (A-1) is such that the content of the linear siloxane block becomes 20 to 60% by mass of the total organic polysiloxane in the composition, preferably In order to become 30-50% by mass. The reason is that if the content of the linear siloxane block is above the lower limit of the above range, the thermal expansion coefficient of the obtained hardened product is significantly reduced, and on the other hand, if it is below the upper limit of the above range, the obtained The softness and mechanical strength of the hardened product are improved.

In this composition, as the component (A), in addition to the component (A-1), (A-2) a linear or branched organic polymer having at least 2 alkenyl groups in one molecule may be used in combination. Siloxane. Examples of the alkenyl group in the component (A-2) include alkenyl groups having 2 to 6 carbon atoms such as vinyl, allyl, isopropenyl, butenyl, hexenyl, and cyclohexenyl. In addition, as the group bonded to the silicon atom other than the alkenyl group in the (A-2) component, an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, and propyl; phenyl, tolyl, Aryl groups with a carbon number of 6-12 such as xylyl; aralkyl groups with a carbon number of 7-12 such as benzyl and phenethyl; halogenated alkyl groups such as 3-chloropropyl, 3,3,3-trifluoropropyl .

The linear organic polysiloxane as the component (A-2) can be exemplified by dimethyl polysiloxane terminated at both ends of the molecular chain with dimethylvinylsiloxy groups, and at both ends of the molecular chain. Dimethyl vinyl siloxane end capped dimethyl siloxane-methyl vinyl siloxane random Copolymer, dimethylsiloxane-methylphenylsiloxane copolymer terminated with dimethylvinylsiloxy groups at both ends of the molecular chain, trimethylsiloxy group terminated at both ends of the molecular chain Random copolymer of dimethylsiloxane-methylvinylsiloxane.

In addition, examples of the branched-chain organic polysiloxane of the component (A-2) include a siloxane unit represented by the formula: SiO _4/2 , and a general formula: R ⁷ ₂ R ⁸ SiO _1/2 The represented siloxane unit and the general formula: the siloxane unit represented by R ⁷ ₃ SiO _1/2 . In the formula, R ⁷ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and the same groups as described above can be exemplified. In addition, R ⁸ is an alkenyl group having 2 to 10 carbon atoms, and the same groups as described above can be exemplified. In this organic polysiloxane, with respect to one formula: the formula of the siloxane unit represented by SiO _4/2 : the formula and formula of the siloxane unit represented by R ⁷ ₂ R ⁸ SiO _1/2 : The total amount of siloxane units represented by R ⁷ ₃ SiO _1/2 is preferably in the range of 0.5 to 1.5. Furthermore, in the organic polysiloxane, a very small amount of hydroxyl groups, alkoxy groups, etc. can be bonded to the silicon atoms in the molecule.

(A-2) The content of the component is not particularly limited, but it is preferably at most 10 mole% relative to the total of the alkenyl group in the (A-1) component and the alkenyl group in the component The amount. The reason for this is that if the content of this component is equal to or lower than the upper limit of the above range, the thermal expansion rate of the obtained hardened product is significantly reduced.

In addition, in the component (B-1), in the formula, R ⁹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and the same group as the above R ⁷ can be exemplified. In addition, in the formula, n is an integer in the range of 10 to 100, preferably an integer in the range of 20 to 80. The reason is that if n is above the lower limit of the above range, the thermal expansion coefficient of the obtained cured product is significantly reduced, while if it is below the upper limit of the above range, the mechanical strength of the obtained cured product is improved.

As the component (B-1), there can be exemplified an organic polysiloxane containing only the above-mentioned linear siloxane block and having both ends of the molecular chain blocked. As the group at the end of the molecular chain, there can be exemplified: hydroxy; alkoxy such as methoxy, ethoxy, and propoxy; trimethylsilyloxy, dimethylhydrosilyloxy, dimethylphenylsilane Oxygen, methylphenylhydrosilyloxy and other organosiloxy groups. In addition, the component (B) may also be the linear silicone block (X′) and another silicone Block copolymer formed by linking alkane blocks (Y'). As such a block copolymer, an X′Y copolymer formed by connecting X′ and Y each, an X′YX′ copolymer having X′ connected to both ends of Y, X′, Y The (X'Y)z copolymer is formed by repeating it alternately z times. As this siloxane block (Y), the same as described above can be exemplified. In addition, as the group of the molecular chain terminal of the block copolymer, a hydroxyl group, the same alkoxy group as described above, or the same organosilane alkoxy group as described above can be exemplified.

(B) The content of the component is relative to 1 mole of the alkenyl group in the (A) component, and the hydrogen atom bonded to the silicon atom in this component is in the range of 0.1 to 10 moles, preferably 0.5 The amount within the range of ~10 moles becomes the amount within the range of 0.5-5 moles, or the amount within the range of 0.7-2 moles. The reason is that if the content of the component (B) is above the lower limit of the above range, the thermal expansion coefficient of the obtained cured product is significantly reduced, and on the other hand, if it is below the upper limit of the above range, the mechanical properties of the obtained cured product Strength increased.

The titanium oxide powder of component (C) and the inorganic powder of component (D) are as described above. In addition, the organosilane and organosiloxane of the component (E) are also as described above.

In the present composition, in the case of performing in-situ treatment on the surface treatment of the component (C) and the component (D), the following method can be exemplified: mixing in part or all of the component (A) ( C) The component and (D) component, and then, the method of mixing the (E) component and heating if necessary; the (C) component will be mixed in a part of the (A) component, and then (E) will be mixed in it One part of the component, and if necessary, heated, mixed with the (D) component in the (A) part, and then mixed with the (E) component, and if necessary, heated and mixed method. Moreover, (E)component, (C)component, and (D)component can also be mix|blended only in this composition.

(F) The component is a catalyst for hydrosilylation reaction for promoting the hardening reaction of the composition. Examples of the component (F) include platinum catalysts, rhodium catalysts, and palladium catalysts. In terms of significantly promoting the hardening of the composition, the component (F) is preferably a platinum-based catalyst. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, and platinum-alkenyl Silicone complex, platinum-olefin complex, platinum-carbonyl complex. As this alkenylsiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilaxane, 1,3,5,7-tetramethyl-1,3 can be exemplified ,5,7-tetravinylcyclotetrasiloxane, one part of the methyl group of the alkenyl siloxane is replaced with ethyl, phenyl and other alkenyl siloxane, the alkenyl siloxane The vinyl group is replaced by an alkenyl siloxane such as allyl, hexenyl and the like.

In addition, in terms of improving the stability of the platinum-alkenyl siloxane complex, it is preferable to add 1,3-divinyl-1,1,3,3- to the complex Tetramethyldisilaxane, 1,3-diallyl-1,1,3,3-tetramethyldisilaxane, 1,3-divinyl-1,3-dimethyl-1 ,3-diphenyldisilaxane, 1,3-divinyl-1,1,3,3-tetraphenyldisilaxane, 1,3,5,7-tetramethyl-1,3 , 5,7-tetravinyl cyclotetrasiloxane and other alkenyl siloxanes or dimethyl siloxane oligomers and other organic siloxane oligomers.

(F) The content of the component is not particularly limited as long as it is sufficient to promote the hydrosilylation reaction of the present composition, and it is preferred that the metal atom in the present component is 0.01 in mass unit relative to the present composition The amount in the range of ~500ppm becomes the amount in the range of 0.01~100ppm, or the amount in the range of 0.01~50ppm. The reason for this is that if the content of the (F) component is more than the lower limit of the above range, the obtained composition is cured well. On the other hand, if it is less than the upper limit of the above range, the obtained cured product is less likely to be colored.

Moreover, in this composition, in order to control the hardening rate of this composition suitably, (G) reaction inhibitor may be contained. As such (G) component, 1-ethynylcyclohexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, Alkynes such as 2-phenyl-3-butyn-2-ol; alkynes such as 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne Compounds; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7 -Tetrahexenylcyclotetrasiloxane, benzotriazole. (G) The content of the component is not particularly limited, but it is preferably within a range of 1 to 5,000 ppm in terms of mass unit relative to the composition.

In addition, in the present composition, in order to further improve the adhesiveness to the substrate that is in contact during the hardening, (H) an adhesion promoter may be included. As the (H) component, there can be exemplified: having a trialkoxysilyloxy group (for example, trimethoxysiloxy group, triethoxysiloxy group) or a trialkoxysilylalkyl group (for example, trimethoxysilyl group) Ethyl, triethoxysilylethyl), organic silane with hydrosilyl or alkenyl (e.g. vinyl, allyl) or linear, branched or cyclic with a silicon atom number of about 4-20 Organic siloxane oligomers in the form of: having trialkoxysiloxy or trialkoxysilylalkyl and methacryloyloxyalkyl (such as 3-methacryloyloxypropyl) Organic silane or linear, branched or cyclic organic siloxane oligomers with 4 to 20 silicon atoms; with trialkoxysiloxy or trialkoxysilyl alkyl groups and bonding Epoxy-containing alkyl groups (eg 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-cyclo Oxycyclohexyl)propyl) organosilane or linear, branched or cyclic organosiloxane oligomers with a silicon atom number of about 4 to 20; aminoalkyltrialkoxysilane and bonding Epoxy-containing alkyl trialkoxysilane reactant, epoxy-containing ethyl polysilicate. Specifically, it can be exemplified by vinyl trimethoxy silane, allyl trimethoxy silane, allyl triethoxy silane, hydrogen triethoxy silane, 3-glycidoxy propyl trimethoxy silane , 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -The reactant of methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane and 3-aminopropyltriethoxysilane, the two ends of the molecular chain are hydroxylated Condensation reactant of blocked methyl vinyl siloxane oligomer with 3-glycidoxypropyl trimethoxy silane, methyl vinyl siloxane oligomer terminated at both ends of the molecular chain with hydroxyl groups Condensation reaction product with 3-methacryloxypropyltriethoxysilane, tris(3-trimethoxysilylpropyl) isocyanurate. The content of (H) component is not particularly limited, and it is preferably in the range of 0.1 to 10 parts by mass relative to 100 parts by mass of (A) component.

Since this composition is highly filled with titanium oxide, it exhibits a higher thixotropy that cannot be observed when using other inorganic fillers. The viscosity at 25°C under a shear rate of 1s ^-1 is preferably 1000 Pa. Below s, the viscosity at 25°C at a shear rate of 10 s ^-1 is preferably 100 Pa. s below. The reason is that if the viscosity is as described above, it is easy to cope with various production processes when forming a hardened product. In addition, in view of the difficulty of dripping during use, the value of the thixotropic index obtained by the following formula is preferably 5.0 or more.

In addition, in order to improve the coating workability of the composition, a diluent such as an organic solvent or silicone oil may be blended to adjust the viscosity. Regarding this diluent, it is preferable that the boiling point is in the range of 150 to 250°C in terms of being easily volatilized during the hardening or post-heat treatment step of the present composition and not easily remaining in the hardened material. Examples of such a diluent include isoparaffin-based organic solvents such as IP (Isoparaffin) solvents manufactured by Idemitsu Corporation, and glycol ether-based organic solvents such as diethylene glycol monomethyl ether, or Dow Corning Toray Co., Ltd. made OS-20 and other polysiloxane-based solvents. The content of the diluent is not particularly limited. In terms of being easily volatilized during the hardening or post-heat treatment step of the composition, and not easily remaining in the hardened material, it is preferably 0.1 to 100 parts by mass of the composition. Within 10 parts by mass.

Next, the hardened product of the present invention will be described in detail.

The cured product of the present invention is characterized in that it is obtained by curing the curable polysiloxane composition. The linear expansion rate of the cured product of the present invention is not particularly limited, and the average linear expansion rate at 25 to 200°C is preferably 100 ppm/°C or less, and more preferably 50 ppm/°C or less. In addition, regarding the cured product of the present invention, in terms of excellent film-like concealment performance, it is preferably JIS K 7375:2008 "Plastic full light rays" when it is made into a film-shaped cured product of 100 μm. The total light in the "transmission rate and total light reflectance" The reflectivity is over 90%.

The shape of the hardened product of the present invention is not particularly limited, and may be formed on the support in a plate shape or a film shape. Since the cured product of the present invention has a very low thermal expansion rate, it is suitable as a coating film or film for covering a support.

As a method for forming such a cured product of the present invention, a method of forming the above-mentioned curable polysiloxane composition on a support into a film-shaped or plate-shaped cured product by a molding step, or by a coating step A method for forming the above-mentioned curable polysiloxane composition into a film-shaped or plate-shaped cured product on a support.

As the support, there can be exemplified: amide imide resin, bis-cis-butadiene imide three-wire resin, glass fiber-containing epoxy resin, phenolic paper resin, bakelite, polyethylene terephthalate resin, poly Butyl terephthalate resin, polyacrylonitrile resin, polycarbonate resin, fluororesin, polyimide resin, polyphenylene sulfide resin, aromatic polyamide resin, polyether ether resin, polyether amide resin Resin support such as amine resin, liquid crystal polymer, polyether resin, cycloolefin resin, polysiloxane rubber, polysiloxane resin; metal support such as aluminum foil, copper foil, nickel foil, or aluminum nitride foil.

As a method of forming the hardened material on the support, a molding step and a coating step can be exemplified. As the molding step, pressure molding or compression molding using a mold can be exemplified. As the coating step, screen printing, stick type can be exemplified: Coating, roll coating, reverse coating, gravure coating, air knife coating, spray coating, curtain coating, especially when the coating is a thin film, high-precision lithographic coating can be used Known coating methods such as cloth and multi-stage roll coating.

The hardened product of the present invention is preferably formed in a plate shape or a film shape on the support by the method described above. Since the cured product of the present invention exhibits high light reflectivity, it can be used as a light reflecting material used in optical semiconductor devices. Especially when the material of the present invention is used in an optical semiconductor device, it is more suitable for an optical semiconductor device of a chip on board (COB) type.

Next, the optical semiconductor device of the present invention will be described in detail.

The optical semiconductor device of the present invention is characterized by having a light reflecting material containing the hardened product of the above composition. This optical semiconductor device of the present invention will be described in detail using FIGS. 1 and 2.

1 is a cross-sectional view of a chip-on-board (COB) type optical semiconductor device as an example of the optical semiconductor device of the present invention. In the COB type optical semiconductor device of FIG. 1, the optical semiconductor element 1 is mounted on the COB substrate 2 by die bonding, and the optical semiconductor element 1 and the circuits 3 and 4 are electrically connected by bonding wires 5. In addition, a light reflecting material 6 is formed around the optical semiconductor element 1 on the substrate 2 to efficiently reflect the light emitted from the optical semiconductor element 1.

2 is a cross-sectional view of another chip on board (COB) type optical semiconductor device as an example of the optical semiconductor device of the present invention. In the COB type optical semiconductor device of FIG. 2, the optical semiconductor element 1 and the circuits 3 and 4 on the COB substrate 2 are electrically connected by bonding pads. In addition, a light reflecting material 6 is formed around the optical semiconductor element 1 on the substrate 2 to efficiently reflect the light emitted from the optical semiconductor element 1.

In the optical semiconductor device of FIGS. 1 and 2, the substrate 2 may also be a metal substrate such as aluminum or copper, and circuits 3 and 4 are formed on the surface of the metal substrate via an insulating layer (not shown). In addition, when a non-metal substrate is used as the substrate 2, it is not necessary to form an insulating layer. Examples of such non-metal substrates include glass epoxy substrates, polybutylene terephthalate (PBT) substrates, polyimide substrates, polyester substrates, aluminum nitride substrates, and boron nitride substrates. Silicon nitride substrate, alumina ceramic substrate, glass substrate, flexible glass substrate. Furthermore, as the substrate 2, a mixed substrate including an aluminum substrate or a copper substrate having an insulating resin layer, or a printed wiring silicon substrate, a silicon carbide substrate, or a sapphire substrate can also be used.

The circuits 3 and 4 can use at least one metal selected from the group consisting of silver, copper, and aluminum with high conductivity, or an alloy containing at least one selected from the group consisting of silver, copper, and aluminum. . It is preferable to further mount the optical semiconductor element 1 on the substrate 2 The light reflecting material 6 is formed in such a way that it is exposed separately.

In FIGS. 1 and 2, the optical semiconductor element 1 and the light reflecting material 6 are sealed by a sealing material 7, but the sealing material 7 may be used to seal only the optical semiconductor element 1 into a dome shape. In addition, in FIGS. 1 and 2, although only one optical semiconductor element 1 is shown on the substrate 2, a plurality of optical semiconductor elements 1 may be mounted on the substrate 2.

[Example]

The hardening polysiloxane composition, hardened material, and optical semiconductor device of the present invention will be described in detail through examples. Furthermore, in the examples, the viscosity is the value at each shear rate at 25°C. In the formula, Me, Ph, and Vi represent methyl, phenyl, and vinyl, respectively.

In addition, the hardness, bending strength, linear expansion rate, adhesion to metal, and total light reflectance of the hardened product were measured as follows.

[Hardness of hardened material]

The curable polysiloxane composition was heated at 150°C for 2 hours to produce a cured product. The hardness of the hardened product is measured by a D-type hardness tester specified in JIS K 7215-1986 "Test Method for Hardness of Plastic Hardness Testers".

[Bending strength of hardened material]

The curable polysiloxane composition was heated at 150°C for 2 hours to produce a cured product. The flexural strength of the cured product was measured by the method specified in JIS K 6911-1995 "General Test Methods for Thermosetting Plastics".

[Linear expansion rate of hardened product]

The curable polysiloxane composition was heated at 150°C for 2 hours to produce a cured product. The linear expansion rate of the hardened product was measured by the method specified in JIS K 7197-1991 "Test method for linear expansion rate of plastics based on thermomechanical analysis".

[Total light reflectance of hardened object]

The curable polysiloxane composition was heated at 150°C for 2 hours to produce a thickness of 100 μm Hardened. The total light reflectance of the hardened product was measured by the method specified in JIS K 7375:2008 "Method for calculating plastic total light transmittance and total light reflectance".

[Adhesion of hardened material to metal]

On a 25 mm × 75 mm aluminum plate, apply about 100 mg of each of the curable polysiloxane composition to 5 places using a dispenser. Next, the composition was coated with a 6 mm square aluminum wafer with a thickness of 1 mm, and was pressure-bonded with a 1 kg plate, and in this state, it was cured by heating at 150° C. for 2 hours. Thereafter, it was cooled to room temperature, and the shear strength of the wafer was measured using a shear strength measuring device (bond strength tester SS-100KP manufactured by Nishin Shoji Co., Ltd.). In the same manner as above, the wafer shear strength of the copper plate wafer to the copper plate was also measured.

[Example 1]

Will have the formula: -(MeViSiO _2/2 ) _20-

The represented straight-chain methylvinylsiloxane block, and the molecular chain is terminated with hydroxyl groups at both ends of the methylvinylpolysiloxane 4.4 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 60 which has 4.1 parts by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and has an average primary particle diameter of 60 μm 21.8 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, and 4 parts by mass of n-octyl triethoxysilane were put into the Ross mixer In the process, after mixing at room temperature, the mixture is heated to 150°C under reduced pressure to perform kneading to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 4.7 parts by mass (relative to the The total of vinyl groups in the base vinyl polysiloxane and dimethyl polysiloxane is 1 mole, and the hydrogen atoms bonded to the silicon atoms in this component become 1.5 moles), and the viscosity is 20 mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm) and mixed to prepare a hardenable silicone composition (I). In addition, the content of the linear methyl vinyl siloxane block is 32.4% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Example 2]

Will have the formula: -(MeViSiO _2/2 ) _20-

The represented straight-chain methylvinylsiloxane block, and the molecular chain is terminated with hydroxyl groups at both ends of the methylvinylpolysiloxane 4.4 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 51.8, which has 4.1 parts by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and has an average primary particle diameter of 0.2 μm 30 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, and a viscosity of 24 mPa. Formula of s: Me ₂ ViSiO(Me ₂ SiO) ₂₉ S1(OMe) ₃

4 parts by mass of dimethyl polysiloxane represented by one end of the molecular chain end capped with dimethylvinylsiloxy, and the other end of the other molecular chain end capped with trimethoxysiloxy are fed to the Ross mixer In, after mixing at room temperature, under reduced pressure, heat to At 150 ℃, one side was mixed to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 4.7 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes an amount of 1.5 mol), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm) and mixed to prepare a hardenable silicone composition (II). In addition, the content of the linear methyl vinyl siloxane block is 32.4% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Example 3]

Will have the formula: -(MeViSiO _2/2 ) _20-

The linear methyl vinyl siloxane block represented, and the molecular chain is terminated with hydroxyl groups at both ends of the methyl vinyl polysiloxane 5.8 parts by mass, formula: Me ₂ ViSiO (Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (Tipaque R-630 manufactured by Ishihara Industries) 72 whose molecular chain ends are 5.9 parts by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups and whose average primary particle size is 0.24 μm 6 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, 1 part by mass of n-decyltrimethoxysilane, and a viscosity of 125 mPa. Formula of s: Me ₃ SiO(Me ₂ SiO) ₁₁₀ Si(OMe) ₃

3 parts by mass of dimethyl polysiloxane which is represented by a single end of the molecular chain end capped with trimethylsiloxy and one end of the other molecular chain end capped with trimethoxysiloxy are put into the Ross mixer, After mixing at room temperature, the mixture is heated to 150° C. under reduced pressure while being kneaded to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The represented linear methylhydrogen siloxane block, and the molecular chain ends are trimethylsiloxy terminated methylhydropolysiloxane 5.9 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes 1.4 moles), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm) and mixed to prepare a curable polysiloxane composition (III). In addition, the content of the linear methyl vinyl siloxane block is 34.4% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Example 4]

Will have the formula: -(MeViSiO _2/2 ) _6-

The linear methyl vinyl siloxane block shown, and the molecular chain is terminated with hydroxyl groups at both ends of the methyl vinyl polysiloxane 4.2 parts by mass, formula: Me ₂ ViSiO (Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 72 which has 4.0 parts by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and has an average primary particle size of 72 10 parts by mass, spherical silica (HS-202 manufactured by Nippon Steel Materials Co. Ltd., Micron Co.) with an average particle size of 15 μm, 3 parts by mass of n-octyl triethoxysilane, and a viscosity of 22 mPa . Formula of s: Me ₃ SiO(Me ₂ SiO) ₂₃ Si(OMe) ₃

1 part by mass of dimethyl polysiloxane which is represented by a single end of the molecular chain end capped with trimethylsiloxy and one end of the other molecular chain end capped with trimethoxysiloxy is put into the Ross mixer, After mixing at room temperature, the mixture is heated to 150° C. under reduced pressure while being kneaded to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _20-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain is terminated with trimethylsiloxy groups at both ends of the methylhydrogenpolysiloxane 4.5 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes an amount of 1.3 mol), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1.5 parts by mass of the condensation reactant and 1-ethynyl-1-cyclohexanol (a quantity of 300 ppm in terms of mass relative to the composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 5 ppm) and mixed to prepare a curable polysiloxane composition (IV). Furthermore, the above The content of the linear methyl vinyl siloxane block is 34.5% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Example 5]

Will have the formula: -(MeViSiO _2/2 ) _6-

The linear methyl vinyl siloxane block represented, and the molecular chain is terminated with hydroxyl groups at both ends of the methyl vinyl polysiloxane 4.4 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₄₆ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 65 which has 4.1 parts by mass of dimethylpolysiloxane end capped with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and has an average primary particle size of 0.2 μm 65 17 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, 2 parts by mass of n-octyltriethoxysilane, and a viscosity of 125 mPa . Formula of s: Me ₃ SiO(Me ₂ SiO) ₁₁₀ Si(OMe) ₃

2 parts by mass of dimethyl polysiloxane which is represented by a single end of the molecular chain end capped with trimethylsiloxy and one end of the other molecular chain end capped with trimethoxysiloxy are put into the Ross mixer, After mixing at room temperature, the mixture is heated to 150° C. under reduced pressure while being kneaded to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 4.7 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes an amount of 1.5 mol), viscosity 20mPa. The two ends of the molecular chain of s are terminated with hydroxyl groups The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer to 3-glycidoxypropyl trimethoxy silane is 1: 2 by mass, and 1- After ethynyl-1-cyclohexanol (relative to the composition, which is 200 ppm in mass units) is mixed, the 1,3-divinyl-1,1,3,3-tetramethyl platinum The 1,3-divinyl-1,1,3,3-tetramethyldisilazane solution of disiloxane (the amount of platinum atoms in the unit of mass becomes 3 ppm relative to the composition), and Preparation of a hardenable silicone composition (V). In addition, the content of the linear methyl vinyl siloxane block is 34.7% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Example 6]

Put 5 into the formula: -(MeViSiO _2/2 ) _6-

The linear methyl vinyl siloxane block represented by the formula and 5 formulas: -(MePhSiO) _6-

The represented straight-chain methylphenylsiloxane blocks are alternately connected, and both ends of the molecular chain are capped with trimethylsilyloxymethylvinylsiloxane-methylphenylsiloxane Block copolymer 5.8 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (Tipaque R-630 manufactured by Ishihara Industries) 70 with 5.9 parts by mass of dimethylpolysiloxane end capped with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and having an average primary particle size of 0.24 μm 8 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, 2 parts by mass of n-decyltrimethoxysilane, and a viscosity of 22 mPa. Formula of s: Me ₃ SiO(Me ₂ SiO) ₂₃ Si(OMe) ₃

Two parts by mass of dimethyl polysiloxane which is represented by a single end of the molecular chain end capped with trimethylsiloxy and one end of the other molecular chain end capped with trimethoxysiloxy After mixing at room temperature in a Sri Lankan mixer, the mixture was heated to 150°C under reduced pressure while kneading to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _20-

The represented linear methylhydrogen siloxane block, and the molecular chain ends are trimethylsiloxy terminated methylhydropolysiloxane 5.9 parts by mass (relative to the Total vinyl vinyl siloxane-methylphenyl siloxane block copolymer and the vinyl group in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxane Ear, the hydrogen atom bonded to the silicon atom in this composition becomes an amount of 1.5 mol), and the viscosity is 20 mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3 ppm) and mixed to prepare a curable polysiloxane composition (VI). In addition, the content of the linear methyl vinyl siloxane block is 34.4% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Example 7]

Will have the formula: -(MeViSiO _2/2 ) _20-

The represented straight-chain methylvinylsiloxane block, and the molecular chain is terminated with hydroxyl groups at both ends of the methylvinylpolysiloxane 4.4 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (manufactured by Sakai Chemical Industry) of 4.1 parts by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and having an average primary particle size of 0.2 μm SX-3103) 60 parts by mass, spherical silica (HS-202 manufactured by Nippon Steel Materials Co. Ltd., Micron Co.) with an average particle size of 15 μm 21.8 parts by mass, and n-octyl triethoxysilane 4 The mass parts were put into a Ross mixer, mixed at room temperature, and heated to 150°C under reduced pressure while kneading to prepare polysiloxy materials.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 4.7 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes an amount of 1.5 mol), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm), and finally, the isoparaffin-based solvent (IP solvent 1620 manufactured by Idemitsu Kosei Co., Ltd., boiling point = 162~202°C) is adjusted so that the solid content of the composition becomes 95% by mass. ) Mix to prepare a hardenable silicone composition (VII). In addition, the content of the linear methyl vinyl siloxane block is 32.4% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Example 8]

Will have the formula: -(MeViSiO _2/2 ) _20-

The linear methyl vinyl siloxane block represented, and the molecular chain is terminated with hydroxyl groups at both ends of the methyl vinyl polysiloxane 5.8 parts by mass, formula: Me ₂ ViSiO (Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (Tipaque R-630 manufactured by Ishihara Industries) 72 whose molecular chain ends are 5.9 parts by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups and whose average primary particle size is 0.24 μm 6 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, 1 part by mass of n-decyltrimethoxysilane, and a viscosity of 125 mPa. Formula of s: Me ₃ SiO(Me ₂ SiO) ₁₁₀ Si(OMe) ₃

3 parts by mass of dimethyl polysiloxane which is represented by a single end of the molecular chain end capped with trimethylsiloxy and one end of the other molecular chain end capped with trimethoxysiloxy are put into the Ross mixer, After mixing at room temperature, the mixture is heated to 150° C. under reduced pressure while being kneaded to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The represented linear methylhydrogen siloxane block, and the molecular chain ends are trimethylsiloxy terminated methylhydropolysiloxane 5.9 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes 1.4 moles), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit is 3.5ppm), and finally, the polysiloxane-based solvent (OS-20 manufactured by Dow Corning Toray Co., Ltd.) is adjusted so that the solid content of the composition becomes 95% by mass. (Boiling point = 152°C), and a hardenable silicone composition (VIII) is prepared. In addition, the content of the linear methyl vinyl siloxane block is 34.4% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Example 9]

Will have the formula: -(MeViSiO _2/2 ) _20-

The linear methyl vinyl siloxane block represented, and the molecular chain ends of the molecular chain are terminated with hydroxyl groups 7.2 parts by mass of methyl vinyl polysiloxane, the formula: Me ₂ ViSiO (Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 55.0 of the molecular chain represented by 16.6 parts by mass of dimethylpolysiloxane end capped with dimethylvinylsiloxy groups and having an average primary particle diameter of 0.2 μm 7 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, and a viscosity of 24 mPa. Formula of s: Me ₂ ViSiO(Me ₂ SiO) ₂₉ Si(OMe) ₃

4 parts by mass of dimethyl polysiloxane represented by one end of the molecular chain end capped with dimethylvinylsiloxy, and the other end of the other molecular chain end capped with trimethoxysiloxy are fed to the Ross mixer In the process, after mixing at room temperature, the mixture is heated to 150°C under reduced pressure while kneading to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The straight-chain methylhydrosiloxane block represented, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 8.2 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom Of The amount of hydrogen atoms becomes 1.5 mol) and the viscosity is 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 2 parts by mass of the condensation reactant and 1-ethynyl-1-cyclohexanol (200 ppm in mass units relative to the composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm) and mixed to prepare a hardenable silicone composition (IX). In addition, the content of the linear methyl vinyl siloxane block is 23.4% by mass of the total organic polysiloxane in the composition. Table 1 shows the characteristics of the curable polysiloxane composition and its cured product.

[Comparative Example 1]

Will have the formula: -(MeViSiO _2/2 ) _20-

The represented straight-chain methylvinylsiloxane block, and the molecular chain is terminated with hydroxyl groups at both ends of the methylvinylpolysiloxane 4.4 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 25 of the molecular chain shown at both ends of dimethylvinylsiloxy-terminated dimethylpolysiloxane 4.1 parts by mass and an average primary particle size of 0.2 μm 25 56.3 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, and 4 parts by mass of n-octyl triethoxysilane were put into the Ross mixer In the process, after mixing at room temperature, the mixture is heated to 150°C under reduced pressure while kneading to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 4.7 parts by mass (relative to the The total of vinyl groups in the base vinyl polysiloxane and dimethyl polysiloxane is 1 mole, and the hydrogen atoms bonded to the silicon atoms in this component become 1.5 moles), and the viscosity is 20 mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm), and a hardenable silicone composition (X) is prepared. In addition, the content of the linear methyl vinyl siloxane block is 32.4% by mass of the total organic polysiloxane in the composition. The curable polysiloxane composition, and The characteristics of its hardened product are shown in Table 2.

[Comparative Example 2]

Will have the formula: -(MeViSiO _2/2 ) _20-

The represented straight-chain methylvinylsiloxane block, and the molecular chain is terminated with hydroxyl groups at both ends of the methylvinylpolysiloxane 4.4 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Alumina (AES-12 manufactured by Sumitomo Chemical) 60 masses of dimethyl polysiloxane with dimethyl vinyl siloxane end capped at both ends of the indicated molecular chain at 4.1 mass parts and an average primary particle size of 0.44 μm Parts, 21.8 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, and 4 parts by mass of n-octyl triethoxysilane were put into the Ross mixer After mixing at room temperature, under reduced pressure, while heating to 150 ℃, while mixing, to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 4.7 parts by mass (relative to the The total of vinyl groups in the base vinyl polysiloxane and dimethyl polysiloxane is 1 mole, and the hydrogen atoms bonded to the silicon atoms in this component become 1.5 moles), and the viscosity is 20 mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm) and mixed to prepare a curable polysiloxane composition (XI). Furthermore, the content of the linear methyl vinyl siloxane block is in the composition 32.4% by mass of the total organic polysiloxane. Table 2 shows the characteristics of the curable polysiloxane composition and its cured product.

[Comparative Example 3]

Will have the formula: -(MeViSiO _2/2 ) _20-

The linear methyl vinyl siloxane block represented, and the molecular chain is terminated with hydroxyl groups at both ends of the methyl vinyl polysiloxane 5.8 parts by mass, formula: Me ₂ ViSiO (Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (Tipaque R-630 manufactured by Ishihara Industries) 78 with 5.9 parts by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and having an average primary particle size of 0.24 μm The mass fraction and viscosity are 24mPa. Formula of s: Me ₂ ViSiO(Me ₂ SiO) ₂₉ Si(OMe) ₃

4 parts by mass of dimethyl polysiloxane represented by one end of the molecular chain end capped with dimethylvinylsiloxy, and the other end of the other molecular chain end capped with trimethoxysiloxy are fed to the Ross mixer In the process, after mixing at room temperature, the mixture is heated to 150°C under reduced pressure while kneading to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The represented linear methylhydrogen siloxane block, and the molecular chain ends are trimethylsiloxy terminated methylhydropolysiloxane 5.9 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes 1.4 moles), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), 1,3-divinyl-1,1,3,3-tetramethyldisilazane of 1,3-divinyl-1,1,3,3-tetramethyldisilazane The alkane solution (the amount of platinum atoms in a mass unit of 3.5 ppm relative to the present composition) was mixed to prepare a hardenable polysiloxane composition (XII). In addition, the content of the linear methyl vinyl siloxane block is 34.4% by mass of the total organic polysiloxane in the composition. Table 2 shows the characteristics of the curable polysiloxane composition and its cured product.

[Comparative Example 4]

Will have the formula: -(MeViSiO _2/2 ) _20-

The represented straight-chain methylvinylsiloxane block, and the molecular chain is terminated with hydroxyl groups at both ends of the methylvinylpolysiloxane 7.6 parts by mass, formula: Me ₂ ViSiO (Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium dioxide (SX-3103 manufactured by Sakai Chemical Industry) 56 which has 7.7 parts by mass of dimethylpolysiloxane end capped with dimethylvinylsiloxy groups at both ends of the molecular chain and has an average primary particle diameter of 0.2 μm 56 4 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, and a viscosity of 24 mPa. Formula of s: Me ₃ SiO(Me ₂ SiO) ₁₁₀ Si(OMe) ₃

5.2 parts by mass of dimethyl polysiloxane represented by the molecular chain whose one end is capped with trimethylsiloxy and whose other molecular end is capped with trimethoxysiloxy are put into the Ross mixer, After mixing at room temperature, the mixture is heated to 150° C. under reduced pressure while being kneaded to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated linear methylhydrosiloxane block, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 7.7 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes 1.4 moles), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After 1.3 parts by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (relative to this composition, an amount of 200 ppm in mass units) were mixed, then 1,3-divinyl-1 of platinum ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm) and mixed to prepare a curable polysiloxane composition (XIII). In addition, the content of the linear methyl vinyl siloxane block is 34.4% by mass of the total organic polysiloxane in the composition. Table 2 shows the characteristics of the curable polysiloxane composition and its cured product.

[Comparative Example 5]

Will have the formula: -(MeViSiO _2/2 ) _6-

The linear methyl vinyl siloxane block shown, and the molecular chain is terminated with hydroxyl groups at both ends of the methyl vinyl polysiloxane 4.2 parts by mass, formula: Me ₂ ViSiO (Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 72 which has 4 parts by mass of dimethylpolysiloxane end capped with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and has an average primary particle diameter of 0.2 μm 72 10 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, and 4 parts by mass of methyltrimethoxysilane were put into the Rose mixer, After mixing at room temperature, the mixture is heated to 150° C. under reduced pressure while being kneaded to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _20-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain is terminated with trimethylsiloxy groups at both ends of the methylhydrogenpolysiloxane 4.5 parts by mass (relative to the The total of vinyl groups in the base vinyl polysiloxane and dimethyl polysiloxane is 1 mole, and the hydrogen atoms bonded to the silicon atoms in this component become 1.3 moles), and the viscosity is 20 mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1.5 parts by mass of the condensation reactant and 1-ethynyl-1-cyclohexanol (a quantity of 300 ppm in terms of mass relative to the composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 5 ppm) and mixed to prepare a curable polysiloxane composition (XIV). In addition, the content of the linear methyl vinyl siloxane block is 34.5% by mass of the total organic polysiloxane in the composition. Table 2 shows the characteristics of the curable polysiloxane composition and its cured product.

[Comparative Example 6]

Will have the formula: -(MeViSiO _2/2 ) _6-

The linear methyl vinyl siloxane block represented, and the molecular chain is terminated with hydroxyl groups at both ends of the methyl vinyl polysiloxane 4.4 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₄₆ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 65 which has 4.1 parts by mass of dimethylpolysiloxane end capped with dimethylvinylsiloxy groups at both ends of the indicated molecular chain and has an average primary particle size of 0.2 μm 65 17 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle size of 15 μm, 2 parts by mass of methyltrimethoxysilane, and phenyltrimethoxy 2 parts by mass of silane was put into the Rose mixer and mixed at room temperature. Under reduced pressure, it was heated to 150°C while being kneaded to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated straight-chain methylhydrogensiloxane block, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 4.7 parts by mass (relative to the The total of vinyl groups in the base vinyl polysiloxane and dimethyl polysiloxane is 1 mole, and the hydrogen atoms bonded to the silicon atoms in this component become 1.2 moles), and the viscosity is 20 mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 1 part by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm by mass unit relative to the present composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3 ppm) and mixed to prepare a curable polysiloxane composition (XV). In addition, the content of the linear methyl vinyl siloxane block is 34.7% by mass of the total organic polysiloxane in the composition. Table 2 shows the characteristics of the curable polysiloxane composition and its cured product.

[Comparative Example 7]

Put 3 formulas: -(MeViSiO _2/2 )-

The represented methyl vinyl siloxane and 6 formulas: -(Me ₂ SiO _2/2 )-

The indicated dimethylsiloxane is randomly connected, and both ends of the molecular chain are hydroxy-terminated dimethylsiloxane-methylvinylsiloxane random copolymer 8.5 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) 65 which has 5.9 parts by mass of dimethylpolysiloxane terminated at both ends of the molecular chain with dimethylvinylsiloxy groups and an average primary particle diameter of 65 Parts by mass and spherical silica with an average particle size of 15 μm (Nippon Steel HS-202 manufactured by Materials Co. Ltd., Micron Co.) 16.3 parts by mass was put into a Ross mixer, mixed at room temperature, and heated to 150°C under reduced pressure while kneading to prepare poly Silicone.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The indicated linear methylhydrogen siloxane block, and the molecular chain is terminated with trimethylsiloxy groups at both ends of the methylhydrogen polysiloxane 5.7 parts by mass (relative to the polysiloxy two The total of the methylsiloxane-methylvinylsiloxane random copolymer and the vinyl groups in the dimethylpolysiloxane is 1 mole. The hydrogen atom bonded to the silicon atom in this component becomes 2.6 moles. Ear volume), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After 1.1 parts by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm in mass unit relative to the composition) are mixed, platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm), and a hardenable polysiloxane composition (XVI) is prepared. In addition, the content of the linear methyl vinyl siloxane block is 15.1% by mass of the total organic polysiloxane in the composition. Table 2 shows the characteristics of the curable polysiloxane composition and its cured product.

[Comparative Example 8]

Will have the formula: -(MeViSiO _2/2 ) _20-

The represented straight-chain methylvinylsiloxane block, and the molecular chain is terminated with hydroxyl groups at both ends of the methylvinylpolysiloxane 3.7 parts by mass, formula: Me ₂ ViSiO (Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Titanium oxide (manufactured by Sakai Chemical Industry) of 5.9 parts by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both ends of the indicated molecular chain SX-3103) 65 parts by mass, and 16.3 parts by mass of spherical silica (Nippon Steel Materials Co. Ltd., HS-202 manufactured by Micron Co.) with an average particle diameter of 15 μm were put into a Ross mixer at room temperature After mixing, the mixture was heated to 150°C under reduced pressure while being kneaded to prepare polysiloxy.

Next, at room temperature, in the polysiloxy substance, three formulas: -(Me ₂ SiO _2/2 )-

The represented dimethyl siloxane and 7 formulas: -(MeHSiO _2/2 )-

The indicated methylhydrosiloxane is randomly connected, and both ends of the molecular chain are capped with trimethylsiloxy groups. The methylhydrosiloxane-dimethylsiloxane random copolymer is 8.1 parts by mass ( Relative to the total of 1 mole of methyl vinyl polysiloxane in polysiloxy and vinyl in dimethyl polysiloxane, the hydrogen atom bonded to the silicon atom in this component becomes 1.7 mole Amount), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After 1.1 parts by mass of the condensation reaction product and 1-ethynyl-1-cyclohexanol (200 ppm in mass unit relative to the composition) are mixed, platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm) and mixed to prepare a curable polysiloxane composition (XVII). In addition, the content of the linear methyl vinyl siloxane block is 20.6% by mass of the total organic polysiloxane in the composition. Table 2 shows the characteristics of the curable polysiloxane composition and its cured product.

[Comparative Example 9]

Will have the formula: -(MeViSiO _2/2 ) _20-

The linear methyl vinyl siloxane block represented, and the molecular chain is terminated with hydroxyl groups at both ends of the methyl vinyl polysiloxane 7.2 parts by mass, formula: Me ₂ ViSiO(Me ₂ SiO) ₁₆₀ SiMe ₂ Vi

Alumina (AES-12 manufactured by Sumitomo Chemical Co., Ltd.) with an average primary particle diameter of 0.44 μm and an average primary particle size of 0.46 μm by mass of dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both ends of the indicated molecular chain 55.0 mass Parts, spherical silica with an average particle size of 15 μm (HS-202 manufactured by Nippon Steel Materials Co. Ltd., Micron Co.) 7 parts by mass, and a viscosity of 24 mPa. Formula of s: Me ₂ ViSiO(Me ₂ SiO) ₂₉ Si(OMe) ₃

4 parts by mass of dimethyl polysiloxane represented by one end of the molecular chain end capped with dimethylvinylsiloxy, and the other end of the other molecular chain end capped with trimethoxysiloxy are fed to the Ross mixer In the process, after mixing at room temperature, the mixture is heated to 150°C under reduced pressure while kneading to prepare polysiloxy.

Secondly, at room temperature, in the polysiloxy substance, it will have the formula: -(MeHSiO _2/2 ) _50-

The straight-chain methylhydrosiloxane block represented, and the molecular chain ends are trimethylsiloxy-terminated methylhydropolysiloxane 8.2 parts by mass (relative to the The total number of vinyl groups in the vinyl vinyl polysiloxane and the vinyl groups in the dimethyl polysiloxane terminated at both ends of the molecular chain with dimethyl vinyl siloxy groups is that this component is bonded to the silicon atom The hydrogen atom becomes an amount of 1.5 mol), viscosity 20mPa. The mass ratio of dimethyl siloxane-methylvinyl siloxane copolymer oligomer terminated with hydroxyl groups at both ends of the molecular chain of s and 3-glycidoxypropyltrimethoxy silane is 1:2 After mixing 2 parts by mass of the condensation reactant and 1-ethynyl-1-cyclohexanol (200 ppm in mass units relative to the composition), platinum 1,3-divinyl-1 ,1,3,3-tetramethyldisilazane solution of 1,3-divinyl-1,1,3,3-tetramethyldisilazane (relative to this composition, platinum atoms are in mass The unit amount is 3.5 ppm) and mixed to prepare a curable polysiloxane composition (XVIII). In addition, the content of the linear methyl vinyl siloxane block is 23.4% by mass of the total organic polysiloxane in the composition. Table 2 shows the characteristics of the curable polysiloxane composition and its cured product.

From the results in Table 1 and Table 2, it can be seen that if the content of titanium oxide is large, the thixotropy of the curable polysiloxane composition increases, and the strength of the cured product increases. Moreover, it can be seen that by using a specific organic polysiloxane component, the linear expansion coefficient of the hardened product can be reduced, and further, by using a specific filler treatment agent, the viscosity of the hardened polysiloxane composition can be effectively reduced, Improve all physical properties of hardened material strength, linear expansion coefficient, adhesion to metal.

[Examples 10-12, Comparative Examples 10-12]

On the inside of any support of PET (Polyethylene Terephthalate) film, aluminum plate, or copper plate, a spacer with a thickness of 100 μm is provided in such a way as to form a space of 5 cm×5 cm. 0.8 g of the hardenable polysiloxane composition prepared above was injected into the enclosed area. Next, a mold release film is coated on the curable polysiloxane composition, and heated at 150° C. and a pressure of 5 kg for 15 minutes to produce a molded body of the light reflecting material containing the cured product and the support. The appearance of the hardened product was observed by visual observation, and the results are shown in Table 3.

[Examples 13-15, Comparative Examples 13-15]

Using a film coating machine (PI-1210) manufactured by TESTER SANGYO, on any support of aluminum plate, copper plate, PET film, or glass plate, apply the hardened polysiloxane prepared above with a gap size of 100 μm combination. The state of coating was observed by visual inspection. After that, it was heated in an oven at 150° C. for 1 hour to produce a one-body molded product containing the light reflecting material and the above-mentioned support of the hardened product. Observe the appearance of the hardened product by visual inspection and show the result 于表4。 In Table 4.

[Examples 16-18, Comparative Examples 16-18]

Using an automatic screen printing machine (DP-320) manufactured by Newlong Precision Industry Co., Ltd., using a PET film as a support, screen printing was performed on the hardenable polysiloxane composition prepared above. A screen plate made of SUS with a screen size #100 and a wire diameter of 40 μm was used. Observe the status of screen printing by visual inspection. After that, it was heated in an oven at 150° C. for 1 hour to produce a one-body molded product containing the light reflecting material and the above-mentioned support of the hardened product. The appearance of the hardened product was observed by visual observation, and the results are shown in Table 5.

It can be seen that even if any of the methods of press molding, film coating machine, and screen printing is used, if the curable polysiloxane composition of the present invention is used, the adhesion to the support is good, and the cured product does not occur Cracks, etc. In addition, since the curable polysiloxane composition of the present invention has thixotropy, it is unlikely to cause dripping from the application step to the thermal curing. And no change in shape was observed.

[Industry availability]

The hardening polysiloxane composition of the present invention has a low thermal expansion rate due to the hardened product obtained by hardening it, and the light reflectivity in the film is high, so it is suitable as a composite light reflecting material used as a unit with other components .

Claims (11)

A curable polysiloxane composition, characterized in that it contains titanium oxide powder with an average particle diameter of 0.05 to 10 μm and inorganic powder other than titanium oxide with an average particle diameter of 0.1 to 20 μm, and the content of the above titanium oxide powder is 50 to 90% by mass of the composition, the content of the inorganic powder is 5 to 40% by mass of the thermosetting polysiloxane composition in the composition, and the titanium oxide powder and the inorganic powder are obtained by Formula: R ¹ _a Si(OR ² ) _(4-a) (In the formula, R ¹ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R ² is an alkyl group or an alkoxyalkyl group Group, alkenyl group, or acetyl group, a is an integer of 1~3) organosilane and/or general formula:

(In the formula, R ³ is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R ⁴ is the same kind or a different kind of monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, R ⁵ is an oxygen atom or a divalent hydrocarbon 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). The curable polysiloxane composition as claimed in claim 1, wherein the curable polysiloxane composition is a hydrosilation-curable polysiloxane composition containing at least the following components: (A) has at least 2 alkenyl groups in one molecule Organic polysiloxane, (B) an organic polysiloxane with at least 2 hydrogen atoms bonded to silicon atoms in one molecule {compared to 1 mole of alkenyl in (A) component, in this component Hydrogen atoms bonded to silicon atoms become 0.1 to 10 moles), (C) Titanium oxide powder with an average particle diameter of 0.05 to 10 μm (in this composition, it becomes 50 to 90% by mass), (D ) Inorganic powder other than titanium oxide with an average particle size of 0.1 to 20 μm (in this composition, it becomes an amount of 5 to 40% by mass), (E) (E-1) General formula: R ¹ _(4-a) Si(OR ² ) _a (In the formula, 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 from 1 to 3) organosilane (0.1 to 10 parts by mass relative to 100 parts by mass of the composition) and/or (E-2) general formula:

(In the formula, R ³ is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R ⁴ is the same kind or a different kind of monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, R ⁵ is an oxygen atom or a divalent hydrocarbon group, R ⁶ is an organic siloxane represented by 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) (with respect to 100 parts by mass of the composition) 0.1 to 10 parts by mass), and (F) catalyst for hydrosilylation reaction (amount to promote hydrosilylation reaction of this composition). The hardening polysiloxane composition according to claim 2, wherein the component (A) has at least the general formula (A-1): -(R ⁷ R ⁸ SiO _2/2 ) _m -(where R ⁷ is carbon Alkyl or phenyl group with 1 to 6 atoms, R ⁸ is alkenyl group with 2 to 10 carbon atoms, m is an integer of 5 to 50) linear polysiloxane block organic polysiloxane Alkanes {wherein, the content of the above-mentioned linear polysiloxane blocks is 20 to 60% by mass of the total of organic polysiloxanes in the composition}, (B) component has at least (B-1) Formula: -(R ⁹ HSiO _2/2 ) _n -(In the formula, R ⁹ is an alkyl or phenyl group with 1 to 6 carbon atoms, n is an integer of 10 to 100) linear polysiloxane Alkane block organic polysiloxane. The curable polysiloxane composition according to claim 3, which further contains the alkenyl group in the component relative to the total of the alkenyl group in the component (A-1) and the alkenyl group in the component, is at most 10 mole% The amount (A-2) of an organic polysiloxane having at least 2 alkenyl groups in one molecule {with the exception of the (A-1) component} is used as the (A) component. The hardening polysiloxane composition according to any one of claims 1 to 4, wherein the value of the thixotropic index obtained by the following formula is 5.0 or more,

A hardened product obtained by hardening the hardenable silicone composition according to any one of claims 1 to 5. For the hardened product of claim 6, the average linear expansion rate at 25~200℃ is 100ppm/℃ or less. As in the hardened product of claim 6, the total light reflectance of the film-shaped hardened product of 100 μm is more than 90%. A method for forming a hardened product by forming a hardened polysiloxane composition according to any one of claims 1 to 5 on a support through a molding step. A method for forming a hardened product by forming a hardened polysiloxane composition as described in any one of claims 1 to 5 on a support by a coating step. An optical semiconductor device having a light reflecting material containing the hardened product according to any one of claims 6 to 8.

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