TW201510094A - Reactive silicone composition, reactive thermoplastic material, cured product, and optical semiconductor device - Google Patents

Abstract

Provided are: a reactive silicon composition which comprises at least (A) an organo polysiloxane having an alkenyl group, (B) an organo polysiloxane having an alkenyl group, (C) an organo polysiloxane having a silicon-bonded hydrogen atom, (D) a hydrosilylation reaction catalyst, (E) a white pigment, (F) spherical silica, nonspherical silica, or glass fiber, and (G) a carboxylic acid or metal salt thereof having ten or more carbon atoms and at least one carbon-carbon double bond per molecule; a reactive thermoplastic thereof, a cured product thereof and a photosemiconductor device having the cured product. The present invention provides: a reactive silicon composition which is capable of forming a reactive thermoplastic; a reactive thermoplastic which temporarily fluidizes when heated, then provides a cured product; a cured product which has small reduction in mechanical strength and less discoloration due to heat and light, a high optical reflectivity, and excellent mold releasability; and a photosemiconductor device which has a high luminous efficiency, less thermal degradation and photodegradation of a light reflection material, and excellent reliability.

Description

Reactive polyoxo composition, reactive thermoplastic, cured product, and optical semiconductor device

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

The curable polyelectrolytic composition which is hardened by a hydrogenation reaction is used as a protective agent or coating agent for an optical semiconductor element in an optical semiconductor device such as a photocoupler, a light-emitting diode, or a solid-state imaging device; It is used as a lens forming material, a light reflecting material, or the like. In the composition for use as a light-reflecting material, for example, a resin composition for mounting and encapsulating an optical semiconductor element includes a vinyl group and an allyl group, and a hydrogen atom is directly bonded to the ruthenium. A thermosetting addition-reactive polyfluorene resin having a structure on an atom, a platinum-based catalyst as a curing catalyst, and a white pigment may further contain a release agent (see Patent Document 1); addition-hardening polypene An oxy-resin composition comprising a vinyl group-containing organopolyoxane having a weight average molecular weight (Mw) of 30,000 or more, an organic hydrogenated polyoxyalkylene having at least two hydrogen atoms bonded to a ruthenium in one molecule, and white A pigment, an inorganic filler other than a white pigment, a platinum metal catalyst, and a reaction control agent may further contain a fatty acid ester, a glycerate, a zinc stearate or the like as an internal mold release agent, and the visible light average reflection after hardening The rate is 80% or more (refer to Patent Document 2).

When the compositions are transferred, formed or compressed, there is a mold filling The chargeability is lowered, or pores or burrs are easily generated, or the mold release property is poor, and there is also a problem that the hardening speed is slow and the workability of the forming operation is poor. Further, the cured product obtained by hardening the composition has an advantage of less discoloration caused by heat or light, but has a problem that the linear expansion ratio is increased or the mechanical strength at a high temperature is low, or the light reflectance is not Sufficient, the problem of a large decrease in mechanical strength caused by heat or light.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-021394

Patent Document 2: Japanese Patent Laid-Open Publication No. 2011-140550

It is an object of the present invention to provide a reactive polysiloxane composition, a reactive thermoplastic, a cured product, and an optical semiconductor device which can form a reactive thermoplastic, the reactive heat The plastic system is temporarily fluidized after heating to provide a cured product, which is caused by heat or light, which has less mechanical strength or less discoloration, higher light reflectance, and excellent mold release property. The device has high luminous efficiency, less thermal deterioration or photo-degradation of the light-reflecting material, and excellent reliability.

The reactive polyoxymethylene composition of the present invention is characterized by comprising at least: (A) an average unit formula: (R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d (R ² O _1/2 ) _e

(wherein R ¹ is the same or different phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, wherein 30 to 80 mol% of all R ¹ is a phenyl group; All of 10 to 20 mol% of R ¹ are alkenyl groups, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a, b, c, d and e respectively satisfy 0≦a≦0.30, 0≦. b≦0.70, 0.3≦c≦0.9, 0≦d≦0.20, 0≦e≦0.10, and a+b+c+d=1)

100 parts by mass of the organic polyoxane represented, (B) Formula: R ³ ₃ SiO(R ³ ₂ SiO) _m SiR ³ ₃

(wherein R ³ is the same or different phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, wherein 30 to 70 mol% of all R ³ is a phenyl group; At least one of all R ³ is an alkenyl group, and m is an integer from 10 to 100)

The organic polyoxane represented by 0 to 40 parts by mass, (C) having at least 2 hydrogen atoms bonded to a ruthenium atom in one molecule, and 20 to 70 mol% of all organic groups bonded to the ruthenium atom It is a total of 1 mole of the phenyl organopolyoxane {relative to the alkenyl group in the component (A) and the component (B), and the hydrogen atom bonded to the ruthenium atom in the component is 0.5 to 2 moles. (1) (D) 触 hydrogenation reaction catalyst {to promote the hydrogenation reaction of the alkenyl group in the (A) component and the (B) component with the hydrogen atom bonded to the ruthenium atom in the component (C) (E) White pigment {50 parts by mass or more based on 100 parts by mass of the components (A) to (D)}, (F) non-spherical cerium oxide, spherical cerium oxide or glass The fiber {100 parts by mass or more based on 100 parts by mass of the components (A) to (D)) and (G) a carboxyl group having 10 or more carbon atoms having at least one carbon-carbon double bond in one molecule. The acid or a metal salt thereof, and the total content of the component (E) and the component (F) is 400 parts by mass or less based on 100 parts by mass of the total of the components (A) to (D), and the content of the component (G) is relative to ( A) 100 parts by mass of the components ~(D) 0.01 to 8 parts by mass.

Further, the reactive thermoplastic of the present invention is characterized in that the hydrogenation reaction of the reactive polyoxosiloxane composition is carried out until the conversion ratio is 70 to 95%.

Further, the cured product of the present invention is characterized in that it is obtained by heating the above-mentioned reactive thermoplastic body to 100 ° C or more, and is solid at 300 ° C or has a viscosity of 1,000,000. Pa‧s or more, or characterized in that it is obtained by hardening the above reactive polyoxo composition.

Further, the optical semiconductor device of the present invention is characterized in that the light-reflecting material is formed of the cured product.

The reactive polyoxo compositions of the present invention are characterized by the formation of reactive thermoplastics. Further, the reactive thermoplastic of the present invention is characterized in that it is temporarily fluidized upon heating, and thereafter a cured product is provided. Further, the cured product of the present invention is characterized in that the mechanical strength due to heat or light is lowered or the discoloration is small, the light reflectance is high, and the mold release property is excellent. Further, the optical semiconductor device of the present invention is characterized in that the light-emitting efficiency is high, the thermal deterioration of the light-reflecting material or the light deterioration is small, and the reliability is excellent.

1‧‧‧Optical semiconductor components

2‧‧‧ lead frame

3‧‧‧ lead frame

4, 4'‧‧‧ bonding line

5‧‧‧Light reflective material

6‧‧‧ Sealing material

Fig. 1 is a cross-sectional view showing an LED as an example of the optical semiconductor device of the present invention.

First, the reactive polysiloxane composition of the present invention will be described in detail.

The component (A) is the main component of the present composition, and is an average unit formula: (R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _{4 /2} ) _d (R ² O _1/2 ) _e

The organic polyoxane represented.

In the formula, R ¹ is the same or different phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. The alkyl group of R ¹ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group. The alkenyl group of R ¹ may, for example, be a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group. Further, the content of the phenyl group in the range of ¹ 30 to 80 mole% of all R, ¹ is preferably in a range of 60 to 75 mole% of all R. The reason for this is that if the content of the phenyl group is at least the lower limit of the above range, the obtained thermoplastic thermoplastic body has good flow properties at room temperature and high temperature, and the mechanical strength of the obtained cured product is good. On the other hand, if it is below the upper limit of the above range, the hardness of the obtained cured product at a high temperature is good. Further, in the formula, the content of the alkenyl group in all of R ¹ is in the range of 10 to 20 mol%. The reason for this is that if the content of the alkenyl group is at least the lower limit of the above range, the hardness of the obtained cured product at room temperature is good, and if it is at most the upper limit of the above range, the obtained cured product is mechanically. Good strength.

Further, in the formula, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group of R ² may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group.

Further, in the formula, a represents the ratio of the proportion of the oxirane unit represented by the formula: R ¹ ₃ SiO _1/2 , and satisfies the number of 0≦a ≦ 0.30, preferably satisfies 0≦a ≦ 0.25. The number. The reason for this is that if a is at most the upper limit of the above range, the hardness of the obtained cured product at room temperature is good. Further, in the formula, b represents the ratio of the ratio of the oxoxane unit represented by the formula: R ¹ ₂ SiO _2/2 , and satisfies the number of 0≦b ≦ 0.70, in the case of forming a reactive thermoplastic body. Preferably, it satisfies the number of 0.10 ≦ b ≦ 0.70, and further preferably satisfies the number of 0.15 ≦ b ≦ 0.60. The reason for this is that if b is at least the lower limit of the above range, the obtained reactive thermoplastic body has good hardness at room temperature and high flow properties at a high temperature, and if it is at most the upper limit of the above range, The hardened material obtained has a good hardness at room temperature. Further, c is a number representing the ratio of the oxirane unit represented by the formula: R ¹ SiO _3/2 , and satisfies the number of 0.3≦c≦0.9, preferably 0.35≦c≦0.85, and more preferably Good to meet the number of 0.40 ≦ c ≦ 0.80. The reason for this is that if c is at least the lower limit of the above range, the obtained cured product has a good hardness at room temperature, and on the other hand, when it is at most the upper limit of the above range, the obtained cured product has good mechanical strength. Further, d is a number indicating the ratio of the oxirane unit represented by the formula: SiO _4/2 , and satisfies the number of 0 ≦ d ≦ 0.20, and preferably satisfies the number of 0 ≦ b ≦ 0.10. The reason for this is that if d is at most the upper limit of the above range, the mechanical strength of the obtained cured product is good. Further, e is a number indicating the ratio of the unit represented by the general formula: R ² O _1/2 and satisfies the number of 0≦e ≦ 0.10. The reason for this is that if e is at most the upper limit of the above range, the hardness of the obtained cured product at room temperature is good. Further, in the formula, the total of a, b, c, and d is 1.

The component (A) is usually a mixture having a molecular weight distribution and is a mixture of a plurality of organopolyoxanes. Further, the component (A) may be obtained by mixing the organic polysiloxanes prepared separately, but each of the organopolyoxanes in the above formula must satisfy 0≦a≦0.30, 0≦b≦0.70, 0.3≦c≦0.9, 0≦d≦0.20, 0≦e≦0.10.

The component (B) is an arbitrary component for adjusting the viscosity of the composition and adjusting the hardness and mechanical strength of the obtained cured product, and is of the formula: R ³ ₃ SiO(R ³ ₂ SiO) _m SiR ³ ₃

The organic polyoxane represented.

In the formula, R ³ is the same or different phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. The alkyl group of R ³ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group. The alkenyl group of R ³ may, for example, be a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group. Further, in the formula, the content of the phenyl group in all of R ³ is in the range of 30 to 70 mol%, preferably 40 to 60 mol%. The reason for this is that if the content of the phenyl group is at least the lower limit of the above range, the mechanical strength of the obtained cured product is good, and on the other hand, when the content is less than or equal to the upper limit of the above range, the hardness of the obtained cured product is good. Further, in the formula, at least one of R ³ is an alkenyl group. The reason for this is that if an alkenyl group is present, the component is introduced into the hardening reaction.

Further, in the formula, m is an integer in the range of 10 to 100, preferably an integer in the range of 10 to 50. The reason for this is that the mechanical strength of the obtained cured product is good when m is at least the lower limit of the above range, and the treatment workability of the obtained composition is good when the content is at most the upper limit of the above range.

In the present composition, the content of the component (B) is in the range of 0 to 40 parts by mass based on 100 parts by mass of the component (A), and is preferably in the range of 0 to 20 parts by mass. The reason for this is that if the content of the component (B) is at most the upper limit of the above range, the hardness of the obtained cured product is good.

The component (C) is a crosslinking agent of the composition, and has at least 2 and 矽原 in one molecule An organopolyoxane having a hydrogen atom of a sub-bond and a total of 20 to 70 mol% of the total organic groups bonded to the ruthenium atom is a phenyl group. The hydrogen atom bonded to the ruthenium atom in the component (C) is at least two in one molecule because the crosslinking for hardening is sufficient, and the hardness of the obtained cured product is good. Further, examples of the organic group bonded to the ruthenium atom in the component (C) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. An alkyl group; an aryl group such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group such as a benzyl group or a phenethyl group; or a monovalent hydrocarbon group having no aliphatic unsaturated bond, preferably a phenyl group or a carbon atom number of 1; ~6 alkyl. In the component (C), 20 to 70 mol% of all the organic groups bonded to the ruthenium atom are phenyl groups. The reason for this is that if the content of the phenyl group is at least the lower limit of the above range, the mechanical strength of the obtained cured product at a high temperature is good, and on the other hand, if it is at most the upper limit of the above range, the obtained cured product is mechanically obtained. Good strength.

As such a component (C), a general formula: (HR ⁴ ₂ SiO) ₂ SiR ⁴ ₂ can be exemplified.

The organic trioxane represented by the formula: R ⁵ ₃ SiO(R ⁵ ₂ SiO) _n SiR ⁵ ₃

The linear organopolyoxane represented by and the average unit formula: (R ⁵ SiO _3/2 ) _p (R ⁵ ₂ SiO _2/2 ) _q (R ⁵ ₃ SiO _1/2 ) _r (SiO _{4 /2} ) _s (R ⁶ O _1/2 ) _t

A branched organic polyoxane represented by the group.

In the formula, R ⁴ is the same or different phenyl group or an alkyl group having 1 to 6 carbon atoms. The alkyl group of R ⁴ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group. Further, the content of the phenyl group in all of R ⁴ is in the range of 30 to 70 mol%.

Further, in the formula, R ⁵ is the same or different hydrogen atom, a phenyl group or an alkyl group having 1 to 6 carbon atoms, wherein at least two R ⁵ are a hydrogen atom. The alkyl group of R ⁵ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group. Further, the content of the phenyl group in all R ⁵ except the hydrogen atom is in the range of 30 to 70 mol%.

Further, in the formula, R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group of R ⁶ may, for example, be a methyl group, an ethyl group, a butyl group, a pentyl group or a hexyl group.

Further, in the formula, n is an integer in the range of 5 to 1,000.

Further, in the formula, p is a positive number, q is 0 or a positive number, r is 0 or a positive number, s is 0 or a positive number, t is 0 or a positive number, and q/p is a number in the range of 0 to 10, r/ p is the number in the range of 0~5, s/(p+q+r+s) is the number in the range of 0~0.3, and t/(p+q+r+s) is in the range of 0~0.4. The number.

Among such (C) components, it is preferred that all of them are of the formula: (HR ⁴ ₂ SiO) ₂ SiR ⁴ ₂

When the organic trioxane is not formed, but the cured thermoplastic is not subjected to a reactive thermoplastic, it is preferred that at least 50% by mass of the component (C) is the above organic trioxane. Further, in order to adjust the hardness of the obtained cured product, other organic decane may be added as appropriate.

In the present composition, the content of the component (C) is 1 mole based on the total of the alkenyl groups in the component (A) and the component (B), and the hydrogen atom bonded to the ruthenium atom in the component is 0.5 to 2 The amount within the range of the molar is preferably in the range of 0.5 to 1.5 moles. The reason for this is that if the content of the component (C) is within the above range, the hardness of the obtained cured product is good.

The component (D) is a catalyst for hydrogenation reaction for promoting the hydrogenation reaction of an alkenyl group in the component (A) and the component (B) with a hydrogen atom bonded to a hydrogen atom bonded to a halogen atom in the component (C). The component (D) is exemplified by a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst. Since the curing of the composition can be remarkably promoted, a platinum-based catalyst is preferable. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenyl alkane complex, a platinum-olefin complex, and a platinum-carbonyl complex. Preferably, it is a platinum-alkenyl alkane complex. As the alkenyl alkane, 1,3-divinyl-1,1,3,3-tetramethyldioxane and 1,3,5,7-tetramethyl-1,3 can be exemplified. 5,7-tetravinylcyclotetraoxane, a methyl group of one of the alkenyl alkoxynes being substituted with an alkenyl oxirane such as an ethyl group or a phenyl group, or an ethylene group of the alkenyl oxoxane Substituted as alkene An alkenyl alkane such as propyl or hexenyl. In particular, since the platinum-alkenyl alkoxysilane complex has good stability, it is preferably 1,3-divinyl-1,1,3,3-tetramethyldioxane. Further, since the stability of the platinum-alkenyl alkoxysilane complex can be improved, it is preferred to add 1,3-divinyl-1,1,3,3-tetramethyl to the complex. Dioxane, 1,3-diallyl-1,1,3,3-tetramethyldioxane, 1,3-divinyl-1,3-dimethyl-1,3- Diphenyldioxane, 1,3-divinyl-1,1,3,3-tetraphenyldioxane, 1,3,5,7-tetramethyl-1,3,5, An organic oxirane oligomer such as an alkenyl methoxy oxane such as 7-tetravinylcyclotetraoxane or a dimethyl methoxy siloxane oligomer is more preferably an alkenyl decane.

In the present composition, the content of the component (D) is as long as it is a hydrogenation reaction for promoting the hydrogenation of the alkenyl group in the component (A) and the component (B) with the hydrogen atom bonded to the ruthenium atom in the component (C). The amount of the metal atom in the present component is preferably in the range of 0.01 to 500 ppm, and more preferably in the range of 0.01 to 100 ppm, based on the total amount of the composition. The amount inside is particularly preferably in the range of 0.01 to 50 ppm. The reason for this is that if the content of the component (D) is at least the lower limit of the above range, the obtained composition is cured well, and if it is at most the upper limit of the above range, the obtained cured product is less likely to be colored.

The component (E) is a white pigment for coloring the composition and the cured product thereof to white to increase the light reflectance. The (E) component may, for example, be a metal oxide such as titanium oxide, aluminum oxide, zinc oxide, zirconium oxide or magnesium oxide; and examples thereof include barium sulfate and zinc sulfide, and more preferably titanium oxide or zinc oxide.

The average particle diameter or shape of the component (E) is not limited, and the average particle diameter is preferably in the range of 0.05 to 10.0 μm, and particularly preferably in the range of 0.1 to 5.0 μm. The white pigment may be subjected to surface treatment using a decane coupling agent, cerium oxide, aluminum oxide or the like in order to improve compatibility and dispersibility with a resin or an inorganic filler.

In the present composition, the content of the component (E) is 50 parts by mass or more, preferably 60 parts by mass or more, based on 100 parts by mass of the total of the components (A) to (D). The reason is: if When the content of the component (E) is at least the above lower limit, the light reflectance of the obtained cured product is good.

The component (F) is used for improving the workability of the composition due to an increase in viscosity, reducing the linear expansion ratio of the cured product, and improving the dimensional stability of the spherical cerium oxide, non-spherical cerium oxide or glass fiber. . Examples of the spherical cerium oxide as the component (F) include dry cerium oxide, wet cerium oxide, molten cerium oxide, and detonation cerium oxide. Since the filling property to the composition is good, it is preferably melted. Yttrium oxide. The non-spherical cerium oxide as the component (F) may, for example, be a quartz powder or a glass beads, and is preferably a quartz powder. The glass fiber as the component (F) may, for example, be chopped glass fibers or ground glass fibers, and is preferably ground glass fibers.

The particle diameter of the spherical cerium oxide of the component (F) is not limited, and the average particle diameter is preferably in the range of 0.1 to 50 μm, particularly preferably in the range of 0.5 to 20 μm. The average particle diameter of the non-spherical cerium oxide of the component (F) is not limited, but is preferably in the range of 0.1 to 20 μm, and more preferably in the range of 0.5 to 10 μm. The shape of the glass fiber of the component (F) is not limited, and the fiber diameter is preferably in the range of 1 to 50 μm, particularly preferably in the range of 5 to 20 μm, and the fiber length is preferably in the range of 5 to 500 μm. Especially preferred is in the range of 10 to 300 μm.

In the present composition, the content of the component (F) is 100 parts by mass or more, preferably 120 parts by mass or more, based on 100 parts by mass of the total of the components (A) to (D). The reason for this is that if the content of the component (F) is at least the above lower limit, the obtained cured product has a low coefficient of linear expansion and good dimensional stability.

In the present composition, the total content of the component (E) and the component (F) is 400 parts by mass or less, preferably 350 parts by mass or less, based on 100 parts by mass of the total of the components (A) to (D). The reason for this is that when the total content of the component (E) and the component (F) is at most the above upper limit, the viscosity of the obtained composition is good.

(G) component is a component for improving the release property of the cured product from the mold when the optical semiconductor device is produced by transfer molding, injection molding or compression molding using the composition. Further, it is a carboxylic acid having at least one carbon-carbon double bond in one molecule and having a carbon number of 10 or more or a metal salt thereof. Examples of such a component (G) include oleic acid, linoleic acid, linoleic acid, zinc oleate, aluminum oleate, and calcium oleate. From the viewpoint of less deterioration due to oxidation over the years, oleic acid and a metal salt thereof are preferred.

The content of the component (G) is in the range of 0.01 to 8 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the total of the components (A) to (D). The reason for this is that if the content of the component (G) is at most the upper limit of the above range, the obtained cured product does not become too soft, and on the other hand, if it is at least the lower limit of the above range, the obtained cured product is The mold release property is good.

In the present composition, as an adhesion promoter for improving the adhesion to a substrate which is in contact with the middle of hardening, it is preferred to contain (H) an average unit formula: (R ⁷ ₃ SiO _1/2 ) _f (R) ⁷ ₂ SiO _2/2 ) _g (R ⁷ SiO _3/2 ) _h (SiO _4/2 ) _i (R ⁸ O _1/2 ) _j

The organic polyoxane represented.

In the formula, R ⁷ is the same or different phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an organic group having an epoxy group. The alkyl group of R ⁷ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group, a cyclopentyl group or a cycloheptyl group. The alkenyl group of R ⁷ may, for example, be a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group. The epoxy group-containing organic group of R ⁷ may, for example, be 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl or 3-( 3,4-epoxycyclohexyl)propyl. Further, in the formula, the content of the phenyl group in all of R ⁷ is in the range of 15 to 60 mol%, preferably 20 to 50 mol%. The reason for this is that if the content of the phenyl group is at least the lower limit of the above range, the cured material obtained has good adhesion and reflectance, and if it is at most the upper limit of the above range, the cured product obtained is followed. Good properties and heat resistance. In the formula, the content of the alkenyl group in all of R ⁷ is in the range of 3 to 30 mol%, preferably in the range of 5 to 20 mol%. The reason for this is that if the content of the alkenyl group is within the above range, the cured property of the obtained cured product is good. Further, the content of the epoxy group-containing organic group in all of R ⁷ is in the range of 5 to 30 mol%, preferably 10 to 20 mol%. The reason for this is that if the content of the epoxy group-containing organic group is at least the lower limit of the above range, the cured material obtained has good adhesion, and if it is at most the upper limit of the above range, good heat resistance can be obtained. Sex.

Further, in the formula, R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group of R ⁸ may, for example, be a methyl group, an ethyl group, a butyl group, a pentyl group or a hexyl group.

Further, in the formula, f is a number representing the ratio of the oxime unit represented by the formula: R ⁷ ₃ SiO _1/2 , and is a number satisfying 0≦f≦0.5, preferably satisfying 0≦f≦0.4. The number. The reason for this is that if f is at most the upper limit of the above range, the cured property of the obtained cured product is good. Further, in the formula, g represents the ratio of the ratio of the oxirane unit represented by the formula: R ⁷ ₂ SiO _2/2 , and satisfies the number of 0≦g≦0.9, preferably satisfies 0≦g≦0.8. The number. The reason for this is that if g is at most the upper limit of the above range, the cured property of the obtained cured product is good. Further, h is a number representing the ratio of the oxime unit represented by the formula: R ⁷ SiO _3/2 , and is a number satisfying 0 ≦ h ≦ 0.7, preferably a number satisfying 0 ≦ h ≦ 0.6. The reason for this is that if h is at most the upper limit of the above range, the cured property of the obtained cured product is good. Further, i is a number indicating the ratio of the oxime unit represented by the formula: SiO _4/2 , and satisfies the number of 0≦i≦0.3, and preferably satisfies the number of 0≦i≦0.2. The reason for this is that if i is equal to or less than the upper limit of the above range, the cured property of the obtained cured product is good. Further, j is a number indicating the ratio of the unit represented by the formula: R ⁸ O _1/2 and satisfies the number of 0≦j≦0.02. The reason for this is that if j is at most the upper limit of the above range, the composition can be made to have good time and storage stability. Furthermore, in the formula, the total of f, g, h, and i is 1.

In the present composition, the content of the component (H) is preferably in the range of 0.5 to 10.0 parts by mass based on 100 parts by mass of the total of the components (A) to (D), and more preferably 1.0 to 8.0. The amount within the range of parts by mass. The reason for this is that if the content of the component (H) is at most the upper limit of the above range, the heat resistance of the obtained cured product is good, and on the other hand, if it is at least the lower limit of the above range, the cured product is obtained. good.

In the present composition, the hardenability of the composition is not impaired, according to the extension at room temperature For the purpose of improving the adhesion of the sealing material for an optical semiconductor device to the cured product of the composition, it is preferable to contain two or more of the molecules (I) as the second crosslinking agent. An atomic bonded hydrogen atom and a phenyl group having an organic polyoxane content of less than 20 mol% relative to the total of the organic groups bonded to the ruthenium atom.

The hydrogen atom bonded to the ruthenium atom in the component (I) is two or more in one molecule, because the crosslinking for hardening is sufficient, and the hardness of the obtained cured product is good. Further, examples of the organic group bonded to the ruthenium atom in the component (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. An alkyl group; an aryl group such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group such as a benzyl group or a phenethyl group; or a monovalent hydrocarbon group having no aliphatic unsaturated bond, preferably a phenyl group or a carbon atom number of 1; ~6 alkyl. The content of the phenyl group in the component (I) relative to the total organic group bonded to the ruthenium atom is less than 20 mol%, preferably 10 mol% or less. Further, 90 mol% or more of all the organic groups bonded to the ruthenium atom in the component (I) is preferably a methyl group. The reason for this is that if the content of the phenyl group is less than the above upper limit and the content of the methyl group is at least the lower limit of the above range, the cured product obtained is excellent in adhesion to various substrates, and the sealing material for an optical semiconductor device is used. The cured material has good adhesion.

As such a component (I), a formula: (MeHSiO) _k can be exemplified

(wherein Me represents a methyl group and k is an integer from 4 to 8)

The organic polyoxane represented by the formula: Me ₃ SiO(MeHSiO) _x SiMe ₃

Me ₃ SiO(MeHSiO) _y (Me ₂ SiO) _z SiMe ₃

(wherein Me represents a methyl group, x is an integer of 5 or more, and y and z are each an integer of 5 or more, but y is the same as or above z)

The organic polyoxane represented.

In the present composition, the content of the component (I) is 1 mole based on the total of the alkenyl group in the component (A) and the component (B), and the hydrogen atom bonded to the ruthenium atom in the component is 0.001 to 0.20. The amount in the range of the molar is preferably in the range of 0.002 to 0.10 mol. The reason for this is that when the content of the component (I) is within the above range, the composition can be prolonged at a normal temperature, and the sealing material for an optical semiconductor device has good adhesion to the obtained cured product, and further The fluidity of the reactive thermoplastic obtained by the hydrazine hydrogenation reaction of the composition at a high temperature becomes good.

The composition may contain at least the component (A) to the component (G), and may contain, as other optional components, 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, and 3 , an alkynyl alcohol such as 5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol; 3-methyl-3-pentene-1-yne, 3,5 - alkyne compound such as dimethyl-3-hexene-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, 1,3 , 5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetraoxane, benzotriazole and other reaction inhibitors. The content of the reaction inhibitor is not limited, and is preferably in the range of 1 to 5,000 ppm by mass based on the total amount of the composition.

Further, in the present composition, an adhesion promoter other than the above component (H) may be contained. As such a further promoter, there may be mentioned a trialkoxyquinoloxy group (for example, a trimethoxynonyloxy group, a triethoxysulfonyloxy group) or a trialkoxyphosphonylalkyl group (for example, a trimethoxy group). An organic decane of a decylethyl group, a triethoxy sulfonylethyl group, and a hydroquinoneyl or alkenyl group (for example, a vinyl group, an allyl group), or a linear structure or a branch having a fluorene atom number of about 4 to 20 An organic siloxane oxide having a chain structure or a cyclic structure; having a trialkoxy decyloxy or trialkoxy decylalkyl group and a methacryloxyalkyl group (for example, 3-methyl propylene) An organic decane of methoxypropyl) or an organic oxane oligomer having a linear structure, a branched structure or a cyclic structure of about 4 to 20 fluorene; having a trialkoxy decyloxy group or A trialkoxyalkylalkyl group and an epoxy-bonded alkyl group (for example, 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)B Organo, 3-(3,4-epoxycyclohexyl)propyl) organodecane, or an organic oxane having a linear structure, a branched structure or a cyclic structure of about 4 to 20 fluorene atoms. Copolymer; aminoalkyl trialkoxy silane-bonded epoxy group and an alkyl trialkoxy silane-product of the reaction, ethyl comprising poly silicon epoxy groups, Specific examples thereof include vinyl trimethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, hydrogenated triethoxy decane, 3-glycidoxy propyl trimethoxy decane, and 3 - glycidoxypropyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methyl Reaction of propylene methoxy propyl triethoxy decane, 3-glycidoxy propyl triethoxy decane with 3-aminopropyl triethoxy decane, stanol-based blocked methyl methacrylate Condensation reaction of a base oxyalkylene oligomer with 3-glycidoxypropyltrimethoxydecane, a stanol-based blocked methylvinyloxirane oligomer and 3-methylpropenyloxypropane A condensation reaction product of a triethoxy decane, tris(3-trimethoxydecylpropyl)isocyanurate, or an acid anhydride.

Further, when the composition is not subjected to a reactive thermoplastic to form a cured product, the hardness of the obtained cured product may be adjusted to improve the handling workability of the composition, and may also contain a bond with a ruthenium atom. The organic polysiloxane of 30 to 60 mol% of all the organic groups is an organic polyoxyalkylene having an alkyl group having 2 to 6 carbon atoms and having 10 or less atoms. The alkenyl group in the organopolysiloxane can be exemplified by a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group. Further, the organic group to be bonded to the ruthenium atom other than the alkenyl group in the organopolysiloxane is not particularly limited, and a methyl group or a phenyl group is preferable, and a methyl group is preferable. Further, 30 to 60 mol% of all the organic groups bonded to the ruthenium atom are alkenyl groups having 2 to 6 carbon atoms. The reason for this is that the hardness of the cured product obtained is good if the content of the alkenyl group is at least the lower limit of the above range, and the mechanical strength of the obtained cured product is good if the content is less than or equal to the upper limit of the above range. Further, the number of germanium atoms is 10 or less because the viscosity of the composition is good if the number of germanium atoms is 10 or less.

As such an organic polyoxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane and tetrakis(dimethylvinyldecyloxy) can be exemplified. And decane, methyl tris(dimethylvinyl nonyloxy) decane and phenyl tris(dimethylvinyl decyloxy) decane.

The content of the organopolysiloxane is preferably in the range of 0 to 50 parts by mass based on 100 parts by mass of the component (A), and the present composition is used as a liquid reactive polyoxane combination. In the case of a substance, it is particularly preferable to be in the range of 5 to 40 parts by mass. The reason for this is that if the content of the organopolysiloxane is more than the lower limit of the above range, the viscosity of the composition is good. On the other hand, when the content is less than or equal to the upper limit of the above range, the mechanical strength of the obtained cured product is good.

Further, in the present composition, as long as the object of the present invention is not impaired, an inorganic filler other than spherical cerium oxide, non-spherical cerium oxide or glass fiber may be contained as the other optional component, and polymethacrylic acid may be contained. An organic resin fine powder such as an ester resin or a polysiloxane resin; an anticorrosive agent such as benzotriazole or carboxybenzotriazole, a heat resistant agent, a flame retardant imparting agent, a solvent, and the like.

The viscosity of the composition at 25 ° C is not particularly limited, but in the case of obtaining a reactive thermoplastic, it is preferably 10,000 Pa ‧ or less, and particularly preferably 10 to 5,000 Pa ‧ . The reason for this is that when the viscosity is at least the lower limit of the above range, the reactive thermoplastic body having a desired shape is easily formed. On the other hand, when the viscosity is at most the upper limit of the above range, the handling property of the obtained composition is good.

Further, in the case where the composition is used as a liquid reactive polyoxymethylene composition, the viscosity at 25 ° C is preferably in the range of 5 to 200 Pa‧s, more preferably 5 to 120 Pa‧ Within the range of s, it is especially within the range of 10~80Pa‧s. The reason for this is that when the viscosity is at least the lower limit of the above range, the occurrence of burrs is suppressed during molding, and when the viscosity is at most the upper limit of the above range, the handling property of the obtained composition is good.

Next, the reactive thermoplastic body of the present invention will be described in detail.

The reactive thermoplastic system of the present invention is obtained by subjecting the above-mentioned reactive polyanthracene hardened product to a hydrogenation reaction until the conversion ratio is 70% to 95%. The conversion rate of the hydrogenation of the hydrazine is a percentage of the total amount of the functional group which is subjected to the hydrogenation reaction, and the ratio of the actual reaction is expressed by a percentage. The confirmation method is not particularly limited, and for example, a differential scanning calorimeter (DSC) can be used. The reaction calorific value of the reactive polyfluorene composition and the obtained reactive thermoplastic was measured, and the conversion was simply calculated from the difference. The reaction is carried out by room temperature or heating The reaction is carried out, but in order to obtain a reactive thermoplastic body efficiently, it is preferred to carry out heating. The heating temperature is preferably in the range of 50 to 150 ° C, more preferably in the range of 80 to 130 ° C.

The reactive thermoplastic of the present invention is preferably a liquid having a solidity or a viscosity of 1,000,000 Pa ‧ or more at 25 ° C and a viscosity of 100,000 Pa ‧ s or less at 100 ° C.

Further, the reactive thermoplastic of the present invention is preferably a D-type durometer having a hardness of 30 or more at 25 ° C as defined in JIS K 7215-1986 "Plastic hardness test method for plastics".

Such a reactive thermoplastic system of the present invention is temporarily fluidized when heated to 100 ° C or higher, and thereafter subjected to a hydrazine hydrogenation reaction to provide a cured product.

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

The cured product of the present invention is obtained by heating the reactive thermoplastic body to obtain the remaining hydrogenation reaction, or heating the liquid reactive polyoxymethylene composition without passing through the reactive thermoplastic. The obtained hydrogenation reaction was carried out, and it was solid at 300 ° C or had a viscosity of 1,000,000 Pa ‧ or more. The hardness of the cured product is not particularly limited, but the hardness of the D-type durometer specified in JIS K 7215-1986 "Test method for hardness of plastics" is preferably 60 or more, more preferably 65 or more, and particularly preferably 70 or more. . The reason for this is that if the hardness is at least the above lower limit, the dimensional stability of the cured product is improved, and deformation of the cured product is less likely to occur.

Further, the reflectance of the cured product is not particularly limited, but the total light reflectance measured by the method specified in JIS K 7375:2008 "Plastic-total light transmittance and total light reflectance" is measured. Good is more than 75%, especially better than 80%.

In addition, the coefficient of linear expansion of the cured product is not particularly limited, but the coefficient of linear expansion measured by a method defined in JIS K 7197-1991 "Testing method for linear expansion ratio of plastic by thermomechanical analysis" is 25 The average value in the temperature range of ~200 ° C is preferably 200 ppm / ° C or less, and particularly preferably 150 ppm / ° C or less.

Further, the cured product of the present invention preferably has the above reactive thermoplastic or the above reactivity. The polyoxymethylene composition is hardened in a metal mold heated to 100 ° C or higher. Examples of the curing method in the case where the cured product is formed as a reflective material of an optical semiconductor device include compression molding, transfer molding, and injection molding.

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

The optical semiconductor device of the present invention is characterized in that the light-reflecting material is formed of the cured product. As such an optical semiconductor device, a light emitting diode (LED) can be exemplified. In the optical semiconductor device, the light reflecting material also functions as a frame material (packaging material) of the optical semiconductor device.

A cross-sectional view of a surface mount type LED as an example of the semiconductor device is shown in Fig. 1. In the LED shown in FIG. 1, the optical semiconductor element 1 is bonded to the lead frame 2 by a bonding material, and the optical semiconductor element 1 and the lead frame 2 are bonded by bonding wires 4, 4'. 3. A light-reflecting member 5 including the cured product is provided around the upper portion of the optical semiconductor element 1 except for the upper portion, and the optical semiconductor element 1 inside the light-reflecting member 5 is sealed by the sealing member 6.

As a method of manufacturing the surface mount type LED shown in Fig. 1, a method including the following steps can be exemplified: (1) The reactive thermoplastic body of the present invention is formed by transfer molding or compression molding to form a lead frame 2, 3; (1) bonding the optical semiconductor element 1 to the lead frame 2 by means of a die bonding material; (3) bonding the optical semiconductor element 1 and the lead frames 2, 3 by bonding wires 4, 4' And (4) sealing the optical semiconductor element 1 to the sealing material 6.

[Examples]

The curable polyfluorene oxide composition, the reactive thermoplastic, the cured product, and the optical semiconductor device of the present invention will be described in detail by way of examples. Further, Me, Ph, Vi and Ep in the formula represent a methyl group, a phenyl group, a vinyl group and a 3-glycidoxypropyl group, respectively.

Further, the hardness of the reactive thermoplastic body and the cured product was measured by a D-type hardness tester specified in JIS K 7215-1986 "Testing method for hardness of plastics".

Moreover, the bending strength of the cured product is by JIS K 6911-1995 "The thermosetting plastic one The method specified in the general test method is measured.

Further, the total light reflectance of the cured product is measured by a method defined in JIS K 7375:2008 "Plastic-total light transmittance and total light reflectance method".

In addition, the linear expansion ratio of the cured product is measured by the method specified in JIS K 7197-1991 "Testing method for linear expansion ratio of plastic by thermomechanical analysis" in the range of 25 to 200 °C.

In addition, the mold release property of the composition was measured by forming a single body of the lead frame 10 times at a molding temperature of 120 ° C and a molding time of 5 minutes using a transfer molding machine, and confirming the molded optical semiconductor device. The number of molding defects such as cracks and peeling from the lead frame was evaluated and evaluated.

Further, regarding the conversion ratio of the hydrazine hydrogenation reaction, the heat of reaction in each state was determined by a differential scanning calorimeter, and calculated based on the difference.

[Example 1]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

100 parts by mass of methyl vinyl phenyl polysiloxane, represented by the formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂

13.3 parts by mass of a dimethylvinyl nonyloxy terminal polymethylphenyl siloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

33.3 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminated polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the present component is 1.15 moles, and the 1,3-divinyl group of platinum- a solution of 1,1,3,3-tetramethyldioxane as a complex of 1,3-divinyl-1,1,3,3-tetramethyldioxane (relative to the present composition, Platinum metal in an amount of 5.0 ppm by mass), 1-ethynyl-1-cyclohexanol (relative to this group) a compound (in an amount of 300 ppm by mass), 0.1 parts by mass of oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 122 parts by mass of titanium oxide (SX-3103, manufactured by Nippon Chemical Industry Co., Ltd.) having an average primary particle diameter of 0.2 μm, and 220 parts by mass of crushed quartz powder (CRYSTALITE VX-52 manufactured by Ronson) having an average particle diameter of 5 μm was mixed to prepare a reactive polyoxymethylene composition having a viscosity of 390 Pa·s at 25 ° C.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that it was a solid which could not measure the viscosity at 25 ° C, a D-type durometer hardness of 65, and a viscosity of 590 Pa s at 100 ° C. The conversion of the hydrazine hydrogenation reaction was 88%.

When the obtained thermoplastic body was heated at 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour is a solid which cannot be measured at 300 ° C. The hardness of the D-type durometer at 25 ° C is 84, the bending strength is 17 MPa, and the total light reflectance is 94.2%. The linear expansion ratio of the object was 110 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, no molding defects were observed in the obtained molded product, and no burrs or voids were obtained. Good shape.

[Embodiment 2]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

48.4 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

51.6 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by an average unit formula: (Me ₂ ViSiO _1/2 ) _0.2 (MeEpSiO _2/2 ) _0.25 (PhSiO _3/2 ) _0.55 (HO _1/2 ) _0.005

1.5 parts by mass of the epoxy group-containing polyoxyalkylene represented by the formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂

12.9 parts by mass of dimethylvinyl nonyloxy terminal polymethylphenyl fluorene represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

29.0 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene, dimethylvinyl decane) The total of the hydroxyl group of the oxy-terminated polymethylphenyl siloxane and the epoxy group-containing polyoxyalkylene is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the composition is 0.94 moles, 1,3-divinyl-1,1,3,3-tetramethyldifluoride of platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex An oxane solution (in an amount of 5.0 ppm by mass of the platinum metal), 1-ethynyl-1-cyclohexanol (in an amount of 300 ppm by mass based on the composition), Oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.2 parts by mass, an average primary particle diameter of 0.2 μm of titanium oxide (SX-3103, manufactured by Seiko Chemical Industry Co., Ltd.), 118 parts by mass, and a spherical cerium oxide having an average particle diameter of 15 μm (Nippon Steel Co., Ltd.) 213 parts by mass of HS-202 manufactured by Materials Micron Co., Ltd. was mixed to prepare a curable polyoxynoxy composition having a viscosity of 130 Pa s at 25 °C.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 62, and the viscosity at 100 ° C was 4,700 Pa·s. . The conversion of the hydrazine hydrogenation reaction was 79%.

When the obtained thermoplastic body was heated to 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour is a solid which cannot be measured at 300 ° C. The hardness of the D-type durometer at 25 ° C is 86, the bending strength is 25 MPa, and the total light reflectance is 94.4%. The linear expansion ratio of the object was 100 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, no molding defects were observed in the obtained molded product, and no burrs or voids were obtained. Good shape.

[Example 3]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

48.4 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

51.6 parts by mass of methyl vinyl phenyl polyoxyalkylene represented, average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂

12.9 parts by mass of a dimethylvinyl nonyloxy terminal polymethylphenyl siloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

29.0 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminal polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the composition is 0.96 moles, and 1,3,5,7-tetra 0.5 parts by mass of a tetracyclopentane alkane (relative to the total of 1 m of the vinyl group of the above methyl vinyl phenyl polyoxy siloxane and dimethyl vinyl decyloxy terminal polymethyl phenyl oxane, In this component, the hydrogen atom bonded to the ruthenium atom is 0.0467 moles, and the platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex is 1 , a solution of 3-divinyl-1,1,3,3-tetramethyldioxane (with respect to the composition, the platinum metal is 5.0 ppm by mass unit), 1-ethynyl-1- Cyclohexanol (in an amount of 300 ppm by mass of the composition), 0.1 part by mass of linoleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and titanium oxide having an average primary particle diameter of 0.24 μm (Tipaque R-made by Ishihara Sangyo Co., Ltd.) 630) 118 parts by mass, and an average cutting length of 20 μm and an average fiber 3μm diameter of milled glass fibers (manufactured by Asahi Glass fibers of MF03JB1-20) 213 parts by mass were mixed to prepare a viscosity at 25 deg.] C under the reactive silicon 150Pa‧s of polyethylene oxide composition.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that it was a solid which could not measure viscosity at 25 ° C, a hardness of D hardness of 70, and a viscosity of 16,500 Pa s at 100 ° C. . The conversion of the hydrazine hydrogenation reaction was 87%.

When the obtained thermoplastic body is heated to 150 ° C, the flow is lost and the flow is lost. Motivation. The cured product obtained by heating at 150 ° C for 1 hour has no fluidity below 300 ° C, the hardness of the D-type durometer at 25 ° C is 85, the bending strength is 20 MPa, and the total light reflectance is 94.7%. The linear expansion ratio was 108 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, no molding defects were observed in the obtained molded product, and no burrs or voids were obtained. Good shape.

[Example 4]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

38.5 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

61.5 parts by mass of methylvinylphenyl polysiloxane, represented by the formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂

19.4 parts by mass of a dimethylvinyl nonyloxy terminal polymethylphenyl siloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

28.2 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminated polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the composition is 0.92 moles, and the 1,3-divinyl group of platinum- a solution of 1,1,3,3-tetramethyldioxane as a complex of 1,3-divinyl-1,1,3,3-tetramethyldioxane (relative to the present composition, Platinum metal is 5.0 ppm by mass), 1-ethynyl-1-cyclohexanol (300 ppm by mass based on the composition), linoleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.2 118 parts by mass of titanium oxide (SX-3103 manufactured by Seiko Chemical Industry Co., Ltd.) having an average primary particle diameter of 0.2 μm, and crushed quartz powder having an average particle diameter of 5 μm (Silsic SAB-500 manufactured by Shansen Tuben Mining Co., Ltd.) 213 Mix and prepare to prepare at 25 ° C A reactive polyoxymethylene composition having a viscosity of 360 Pa ‧ .

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 69, and the viscosity at 100 ° C was 7,600 Pa·s. . The conversion of the hydrazine hydrogenation reaction was 88%.

When the obtained thermoplastic body was heated at 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour has no fluidity below 300 ° C, the hardness of the D-type durometer at 25 ° C is 86, the bending strength is 19 MPa, and the total light reflectance is 94.5%. The linear expansion ratio was 113 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, no molding defects were observed in the obtained molded product, and no burrs or voids were obtained. Good shape.

[Example 5]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

38.5 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

61.5 parts by mass of methylvinylphenyl polysiloxane, represented by the formula: (Me ₂ ViSiO _1/2 ) _0.2 (MeEpSiO _2/2 ) _0.25 (PhSiO _3/2 ) _0.55 (HO _1/2 ) _0.005

1.5 parts by mass of the epoxy group-containing polyoxyalkylene represented by the formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂

25.6 parts by mass of dimethylvinyl nonyloxy terminal polymethylphenyl fluorene represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

28.2 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene, dimethylvinyl decane) 1 mil of the total of the oxy-terminated polymethylphenyl siloxane and the epoxy group-containing polyoxyalkylene, in this component The hydrogen atom bonded to the ruthenium atom is 0.89 moles, and the 1,3-divinyl-1,1,3,3-tetramethyldioxane complex of platinum is 1,3-two Vinyl-1,1,3,3-tetramethyldioxane solution (in terms of mass ratio of platinum metal to 5.0 ppm relative to the present composition), 1-ethynyl-1-cyclohexanol ( Titanium oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.2 parts by mass, and an average primary particle diameter of 0.2 μm (SX-3103, manufactured by Suga Chemical Industry Co., Ltd.) A mass fraction and 256 parts by mass of spherical cerium oxide (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) having an average particle diameter of 15 μm were mixed to prepare a reactive polycondensate having a viscosity of 147 Pa·s at 25 ° C. Oxygenated composition.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 76, and the viscosity at 100 ° C was 4,600 Pa ‧ . The conversion of the hydrazine hydrogenation reaction was 79%.

When the obtained thermoplastic body was heated to 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour has no fluidity below 300 ° C, the hardness of the D-type durometer at 25 ° C is 85, the bending strength is 20 MPa, and the total light reflectance is 94.3%. The linear expansion ratio was 101 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, no molding defects were observed in the obtained molded product, and no burrs or voids were obtained. Good shape.

[Embodiment 6]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

38.5 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

61.5 parts by mass of methylvinylphenyl polysiloxane, represented by the formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂

25.6 parts by mass of dimethylvinyl nonyloxy terminal polymethylphenyl fluorene represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

28.2 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminated polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in this composition is 0.9 moles, and 1,3,5,7-tetra 0.5 parts by mass of a tetracyclopentane alkane (relative to the total of 1 m of the vinyl group of the above methyl vinyl phenyl polyoxy siloxane and dimethyl vinyl decyloxy terminal polymethyl phenyl oxane, In this component, the hydrogen atom bonded to the ruthenium atom is 0.0439 mol), and the platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex is 1 , a solution of 3-divinyl-1,1,3,3-tetramethyldioxane (with respect to the composition, the platinum metal is 5.0 ppm by mass unit), 1-ethynyl-1- Cyclohexanol (in an amount of 300 ppm by mass in terms of the composition), 0.2 parts by mass of zinc oleate (manufactured by Kanto Chemical Co., Ltd.), and titanium oxide having an average primary particle diameter of 0.2 μm (SX3103, manufactured by Nippon Chemical Industry Co., Ltd.) 141 Parts by mass, and an average cutting length of 20 μm and an average fiber diameter of 3 μm 282 parts by mass of ground glass fiber (MF03JB1-20 manufactured by Asahi Glass) was mixed to prepare a curable polyoxynoxy composition having a viscosity of 290 Pa s at 25 °C.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 73, and the viscosity at 100 ° C was 7,100 Pa s. . The conversion of the hydrazine hydrogenation reaction was 85%.

When the obtained thermoplastic body was heated to 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour has no fluidity below 300 ° C, the hardness of the D-type durometer at 25 ° C is 85, the bending strength is 25 MPa, and the total light reflectance is 94.5%. The linear expansion ratio was 69 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, the obtained molded product was not confirmed. In the case of poor molding, a molded product having no burrs or voids can be obtained.

[Comparative Example 1]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

100 parts by mass of methyl vinyl phenyl polysiloxane, represented by the formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂

13.3 parts by mass of a dimethylvinyl nonyloxy terminal polymethylphenyl siloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

33.3 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminated polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the present component is 1.15 moles, and the 1,3-divinyl group of platinum- a solution of 1,1,3,3-tetramethyldioxane as a complex of 1,3-divinyl-1,1,3,3-tetramethyldioxane (relative to the present composition, a platinum metal in an amount of 5.0 ppm by mass), 1-ethynyl-1-cyclohexanol (in an amount of 300 ppm by mass based on the composition), and an average primary particle diameter of 0.2 μm. 220 parts by mass of crushed quartz powder (CRYSTALITE VX-52 manufactured by Ronson) of 122 parts by mass of SX-3103) manufactured by Seiko Chemical Industry Co., Ltd., and a viscosity of 410 Pa ‧ at 25 ° C was mixed. a reactive polyoxo composition of s.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that it was a solid which could not measure viscosity at 25 ° C, a D-type durometer hardness of 65, and a viscosity of 650 Pa s at 100 ° C. The conversion of the hydrazine hydrogenation reaction was 87%.

When the obtained thermoplastic body was heated at 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour is a solid which cannot be measured at 300 ° C. The hardness of the D-type durometer at 25 ° C is 85, the bending strength is 17 MPa, and the total light reflectance is 94.3%. The linear expansion ratio of the object was 110 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, molding failure was confirmed in the molded product five times out of ten times.

[Comparative Example 2]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

48.4 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

51.6 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by an average unit formula: (Me ₂ ViSiO _1/2 ) _0.2 (MeEpSiO _2/2 ) _0.25 (PhSiO _3/2 ) _0.55 (HO _1/2 ) _0.005

1.5 parts by mass of the epoxy group-containing polyoxyalkylene represented by the formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂

12.9 parts by mass of a dimethylvinyl nonyloxy terminal polymethylphenyl siloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

29.0 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene, dimethylvinyl decane) The total of the hydroxyl group of the oxy-terminated polymethylphenyl siloxane and the epoxy group-containing polyoxyalkylene is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the composition is 0.94 moles, 1,3-divinyl-1,1,3,3-tetramethyldifluoride of platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex An oxane solution (in an amount of 5.0 ppm by mass of the platinum metal), 1-ethynyl-1-cyclohexanol (in an amount of 300 ppm by mass based on the composition), 0.2 parts by mass of stearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 118 parts by mass of titanium oxide having an average primary particle diameter of 0.2 μm (SX-3103 manufactured by Seiko Chemical Industry Co., Ltd.), and spherical cerium oxide having an average particle diameter of 15 μm (New Day) 213 parts by mass of HS-202 manufactured by Iron Materials Micron Co., Ltd. was mixed to prepare a hardening polycondensate having a viscosity of 160 Pa‧s at 25 ° C Oxygen composition.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 63, and the viscosity at 100 ° C was 4,900 Pa ‧ . The conversion of the hydrazine hydrogenation reaction was 76%.

When the obtained thermoplastic body was heated to 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour is a solid which cannot be measured at 300 ° C. The hardness of the D-type durometer at 25 ° C is 87, the bending strength is 25 MPa, and the total light reflectance is 94.2%. The linear expansion ratio of the material was 97 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, molding failure was confirmed in the molded product three times out of ten times.

[Comparative Example 3]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

48.4 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

51.6 parts by mass of methyl vinyl phenyl polyoxyalkylene represented, average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂

12.9 parts by mass of a dimethylvinyl nonyloxy terminal polymethylphenyl siloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

29.0 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminal polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the composition is 0.96 moles, and 1,3,5,7-tetra 0.5 parts by mass of a tetracyclic alkane (relative to the above methyl vinyl phenyl polyoxyalkylene and dimethyl vinyl alkoxy end polymethylphenyl hydrazine) The total of the vinyl groups of the oxyalkylene is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the composition is 0.0467 moles, and the 1,3-divinyl-1,1,3,3-tetra of platinum a solution of a methyl dioxane complex 1,3-divinyl-1,1,3,3-tetramethyldioxane (with respect to the composition, the platinum metal is 5.0 ppm in mass units) An amount of 1-ethynyl-1-cyclohexanol (in an amount of 300 ppm by mass based on the composition), 0.2 parts by mass of calcium stearate (manufactured by Tokyo Chemical Industry Co., Ltd.), and an average primary particle diameter of 0.24 118 parts by mass of titanium oxide (Tipaque R-630 manufactured by Ishihara Sangyo Co., Ltd.) and 213 parts by mass of ground glass fiber (MF03JB1-20 manufactured by Asahi Glass) having an average cutting length of 20 μm and an average fiber diameter of 3 μm were mixed. A reactive polyoxymethylene composition having a viscosity of 190 Pa s at 25 ° C was prepared.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 71, and the viscosity at 100 ° C was 17,100 Pa ‧ . The conversion of the hydrazine hydrogenation reaction was 85%.

When the obtained thermoplastic body was heated to 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour has no fluidity below 300 ° C, the hardness of the D-type durometer at 25 ° C is 85, the flexural strength is 21 MPa, and the total light reflectance is 94.5%. The linear expansion ratio was 104 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, molding failure was confirmed in the molded article twice in 10 times.

[Comparative Example 4]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

38.5 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

61.5 parts by mass of methylvinylphenyl polysiloxane, represented by the formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂

19.4 parts by mass of a dimethylvinyl nonyloxy terminal polymethylphenyl siloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

28.2 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminated polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the composition is 0.92 moles, and the 1,3-divinyl group of platinum- a solution of 1,1,3,3-tetramethyldioxane as a complex of 1,3-divinyl-1,1,3,3-tetramethyldioxane (relative to the present composition, Platinum metal is 5.0 ppm by mass), 1-ethynyl-1-cyclohexanol (300 ppm by mass based on the composition), polyfluorene oxide (Toray Dow Corning SH) -200 (1000 cs)) 0.2 parts by mass of titanium oxide (SX-3103, manufactured by Seiko Chemical Industry Co., Ltd.) having an average primary particle diameter of 0.2 μm, and a crushed quartz powder having an average particle diameter of 5 μm (manufactured by Shansen Tuben Mining Co., Ltd.) Silsic SAB-500) 213 parts by mass was mixed to prepare a reactive polyoxymethylene composition having a viscosity of 340 Pa‧s at 25 °C.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 71, and the viscosity at 100 ° C was 16,000 Pa·s. . The conversion of the hydrazine hydrogenation reaction was 87%.

When the obtained thermoplastic body was heated at 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour has no fluidity below 300 ° C, the hardness of the D-type durometer at 25 ° C is 87, the bending strength is 20 MPa, and the total light reflectance is 94.3%. The linear expansion ratio was 117 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, molding failure was confirmed in the molded article six times out of ten times.

[Comparative Example 5]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

38.5 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

61.5 parts by mass of methylvinylphenyl polysiloxane, represented by the formula: (Me ₂ ViSiO _1/2 ) _0.2 (MeEpSiO _2/2 ) _0.25 (PhSiO _3/2 ) _0.55 (HO _1/2 ) _0.005

1.5 parts by mass of the epoxy group-containing polyoxyalkylene represented by the formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂

25.6 parts by mass of dimethylvinyl nonyloxy terminal polymethylphenyl fluorene represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

28.2 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene, dimethylvinyl decane) The total of the hydroxyl group of the oxy-terminated polymethylphenyl siloxane and the epoxy group-containing polyoxyalkylene is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the composition is 0.89 moles, 1,3-divinyl-1,1,3,3-tetramethyldifluoride of platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex An oxane solution (in an amount of 5.0 ppm by mass of the platinum metal), 1-ethynyl-1-cyclohexanol (in an amount of 300 ppm by mass based on the composition), Polyfluorene oil (manufactured by Toray Dow Corning SH-200 (10000cs)) 0.2 parts by mass, an average primary particle diameter of 0.2 μm of titanium oxide (SX-3103, manufactured by Seiko Chemical Industry Co., Ltd.), 128 parts by mass, and a ball having an average particle diameter of 15 μm 256 parts by mass of cerium oxide (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) was mixed to prepare a reactive polyoxymethylene composition having a viscosity of 164 Pa s at 25 °C.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 77, and the viscosity at 100 ° C was 5,100 Pa·s. . The conversion of the hydrazine hydrogenation reaction was 84%.

When the obtained thermoplastic body was heated to 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour has no fluidity below 300 ° C, the hardness of the D-type durometer at 25 ° C is 86, the bending strength is 20 MPa, and the total light reflectance is 94.4%. The linear expansion ratio was 98 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, molding failure was confirmed in the molded product five times out of ten times.

[Comparative Example 6]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

38.5 parts by mass of methyl vinyl phenyl polysiloxane, and the average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.01

61.5 parts by mass of methylvinylphenyl polysiloxane, represented by the formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂

25.6 parts by mass of dimethylvinyl nonyloxy terminal polymethylphenyl fluorene represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

28.2 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminated polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in this composition is 0.9 moles, and 1,3,5,7-tetra 0.5 parts by mass of a tetracyclopentane alkane (relative to the total of 1 m of the vinyl group of the above methyl vinyl phenyl polyoxy siloxane and dimethyl vinyl decyloxy terminal polymethyl phenyl oxane, In this component, the hydrogen atom bonded to the ruthenium atom is 0.0439 mol), and the platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex is 1 , a solution of 3-divinyl-1,1,3,3-tetramethyldioxane (with respect to the composition, the platinum metal is 5.0 ppm by mass unit), 1-ethynyl-1- Cyclohexanol (relative to this combination) Mn mass (300 parts by mass), oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.01 parts by mass, average primary particle diameter of 0.2 μm, titanium oxide (SX3103, manufactured by Nippon Chemical Industry Co., Ltd.), 141 parts by mass, and average cutting length 282 parts by mass of ground glass fiber (MF03JB1-20, manufactured by Asahi Glass) of 20 μm and an average fiber diameter of 3 μm was mixed to prepare a curable polyoxynoxy composition having a viscosity of 300 Pa·s at 25 ° C.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that the solid which could not be measured at 25 ° C, the hardness of the D-type durometer was 75, and the viscosity at 100 ° C was 7,300 Pa·s. . The conversion of the hydrazine hydrogenation reaction was 88%.

When the obtained thermoplastic body was heated to 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour has no fluidity below 300 ° C, the hardness of the D-type durometer at 25 ° C is 86, the flexural strength is 25 MPa, and the total light reflectance is 94.4%. The linear expansion ratio was 73 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, molding failure was confirmed in the molded product five times out of ten times.

[Comparative Example 7]

The average unit formula is: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.02

100 parts by mass of methyl vinyl phenyl polysiloxane, represented by the formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂

13.3 parts by mass of a dimethylvinyl nonyloxy terminal polymethylphenyl siloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

33.3 parts by mass of 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented (relative to the above methylvinylphenyl polyoxyalkylene and dimethylvinylnonane) The total of the vinyl groups of the oxy-terminal polymethylphenyl fluorene oxide is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the present component 1,3-divinyl-1,1,3 which is a 1.15 molar amount of platinum, a 1,3-divinyl-1,1,3,3-tetramethyldioxane complex of platinum , 3-tetramethyldioxane solution (in terms of mass ratio of platinum metal to 5.0 ppm relative to the present composition), 1-ethynyl-1-cyclohexanol (relative to the composition, by mass) 12 parts by mass of oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 12 parts by mass of oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.2 parts by mass of titanium oxide (SX-3103, manufactured by Seiko Chemical Industry Co., Ltd.) having an average primary particle diameter of 0.2 μm, and an average particle diameter of 5 μm. 220 parts by mass of crushed quartz powder (CRYSTALITE VX-52 manufactured by Ronson) was mixed to prepare a reactive polyoxyl composition having a viscosity of 130 Pa s at 25 °C.

The composition was heated at 120 ° C for 10 minutes, and as a result, it was found that it was a solid which could not measure viscosity at 25 ° C, a D-type durometer hardness of 51, and a viscosity of 120 Pa s at 100 ° C. The conversion of the hydrazine hydrogenation reaction was 86%.

When the obtained thermoplastic body was heated at 150 ° C, fluidity was lost and fluidity was lost. The cured product obtained by heating at 150 ° C for 1 hour is a solid which cannot be measured at 300 ° C. The hardness of the D-type durometer at 25 ° C is 72, the bending strength is 5 MPa, and the total light reflectance is 94.4%. The linear expansion of the material was 115 ppm/°C.

Further, in order to manufacture the optical semiconductor device shown in Fig. 1, the thermoplastic body was molded into a single body of the lead frame 10 times using a transfer molding machine, and as a result, no molding defects were observed in the obtained molded product, and no burrs or voids were obtained. Good shape. However, it is known that the molded article obtained is too soft.

[Industrial availability]

The reactive polyoxo composition of the present invention can obtain a reactive thermoplastic which is suitable for the formation of a cured product in a heated mold, which is obtained by heat or light. The mechanical strength is lowered or the discoloration is small, the light reflectance is high, and the mold release property is excellent, so that it is preferably used as a material for forming a white frame material of a light-emitting diode.

1‧‧‧Optical semiconductor components

2‧‧‧ lead frame

3‧‧‧ lead frame

4, 4'‧‧‧ bonding line

5‧‧‧Light reflective material

6‧‧‧ Sealing material

Claims (16)

A reactive polyoxynoxy composition comprising at least: (A) an average unit formula: (R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c ( SiO _4/2 ) _d (R ² O _1/2 ) _e (wherein R ¹ is the same or different phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, wherein , R & lt all 30 ¹ to 80 mole% of the phenyl, R & lt entire ¹ to 20 mole% of the 10 alkenyl group, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, of, a, b, c , d and e respectively satisfy 0≦a≦0.30, 0≦b≦0.70, 0.3≦c≦0.9, 0≦d≦0.20, 0≦e≦0.10, and a+b+c+d=1) 100 parts by mass of the organic polyoxane represented by the formula (B): R ³ ₃ SiO(R ³ ₂ SiO) _m SiR ³ ₃ (wherein R ³ is the same or different phenyl group, carbon number 1 ~ 6 carbon atoms or an alkyl group of an alkenyl group of 2 to 6, wherein all of R ³ is 30 to 70 mole% phenyl, all R ³ is at least one alkenyl group, m is an integer of 10 to 100 The organic polyoxane represented by 0 to 40 parts by mass, (C) having at least 2 hydrogen atoms bonded to a ruthenium atom in one molecule, and 20 to 70 moles of all organic groups bonded to the ruthenium atom % is a phenyl organopolyoxane {relative to (A) The total amount of alkenyl groups in the component (B) is 1 mole, and the hydrogen atom bonded to the ruthenium atom in the component is 0.5 to 2 moles}, (D) 触 hydrogenation reaction catalyst {for promotion A sufficient amount of the (A) component and the alkenyl group in the component (B) to the hydrogenation reaction of the hydrogen atom bonded to the halogen atom in the component (C), and (E) the white pigment {relative to (A) 100 parts by mass or more of the component (D) component is 50 parts by mass or more}, (F) non-spherical cerium oxide, spherical cerium oxide or glass fiber {compared to the total of (A) component to (D) component 100 parts by mass or more of 100 parts by mass or more, and (G) a carboxylic acid having 10 or more carbon atoms or a metal salt thereof having at least one carbon-carbon double bond in one molecule, and (E) component and (F) The total content of the components is 400 parts by mass or less based on 100 parts by mass of the total of the components (A) to (D), and the content of the component (G) is 0.01% by mass based on 100 parts by mass of the components (A) to (D). ~8 parts by mass. The reactive Paragraph 1 request poly silicon oxide composition, which further contains with respect to component (A) - the total component (D) of 100 parts by mass of 0.5 to 10.0 parts by mass of (H) the average unit formula: (R ⁷ ₃ SiO _1/2 ) _f (R ⁷ ₂ SiO _2/2 ) _g (R ⁷ SiO _3/2 ) _h (SiO _4/2 ) _i (R ⁸ O _1/2 ) _j (wherein R ⁷ is the same or a different phenyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an organic group having an epoxy group, wherein all 15 to 60 mol% of R ⁷ are a phenyl group, all 3 to 30 mol% of R ⁷ is an alkenyl group, 5 to 30 mol % is an epoxy group-containing organic group, R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and f, g, h, i and j are respectively satisfying 0≦f≦0.5, 0≦g≦0.9, 0≦h≦0.7, 0≦i≦0.3, 0≦j≦0.02, and f+g+h+i=1) The organic polyoxane represented. The reactive polyoxosiloxane composition of claim 1, which further contains 1 mole of the total of the alkenyl groups in the component (A) and the component (B), and the hydrogen atom bonded to the ruthenium atom in the component becomes 0.001 to 0.20 moles of (I) organic having at least 2 hydrogen atoms bonded to a ruthenium atom in one molecule and having a phenyl group having less than 20 mol% relative to all organic groups bonded to the ruthenium atom Polyoxane. The reactive polyoxosiloxane composition of claim 2, which further comprises (I) a content of at least 2 hydrogen atoms bonded to a ruthenium atom in one molecule and a phenyl group bonded to a ruthenium atom Less than 20 mol% of the organopolyoxane, the content of the component (I) is 1 mol in total with respect to the alkenyl group in the component (A) and the component (B), in the component The hydrogen atom bonded to the ruthenium atom is 0.001 to 0.20 moles. The reactive polyoxosiloxane composition according to any one of claims 1 to 4, which has a viscosity at 25 ° C of 10,000 Pa ‧ or less. A reactive thermoplastic body which is subjected to a hydrogenation reaction of a reactive polyoxosiloxane composition according to any one of claims 1 to 5 until the conversion ratio is 70 to 95%. The reactive thermoplastic of claim 6 which is solid at 25 ° C or has a viscosity of 1,000,000 Pa ‧ or more and is a liquid having a viscosity of 100,000 Pa ‧ s or less at 100 ° C. The reactive thermoplastic of claim 6 which has a D-type durometer hardness of 30 or more as defined by JIS K 7215 at 25 °C. The reactive thermoplastic of claim 7 has a D-type durometer hardness of 30 or more as defined by JIS K 7215 at 25 °C. The reactive thermoplastic according to any one of claims 6 to 9, which is heated to 100 ° C or higher to form a cured product which does not exhibit fluidity below 300 ° C. A cured product obtained by heating a reactive thermoplastic body according to any one of claims 6 to 10 to 100 ° C or higher, and having a solidity at 300 ° C or a viscosity of 1,000,000 Pa ‧ or more. A cured product obtained by hardening a reactive polyoxymethylene composition according to any one of claims 1 to 5. The cured product of claim 11 has a total light reflectance of 80% or more. The cured product of claim 12 has a total light reflectance of 80% or more. The cured product according to any one of claims 11 to 14, which has an average linear expansion ratio of 200 ppm/° C. or less in the range of 25 to 200 ° C. An optical semiconductor device obtained by forming a light-reflecting material from the cured product according to any one of claims 11 to 15.