JP2016534160A - One-component curable silicone composition and optical semiconductor device - Google Patents

Abstract

The present invention relates to (A) a branched organopolysiloxane having an alkenyl group and an aryl group, and (B) (i) a general formula: HR22SiO (R22SiO) mSiR22H, wherein R2 is the same or different, A monovalent hydrocarbon group having no saturated bond, provided that at least 15 mol% of R2 in one molecule is an aryl group; m is an integer of 1 to 100), (ii) hydrosilylation reaction And (iii) general formula: R32N-R4-NR32 (wherein R3 is the same or different, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R4 is an alkylene group having 2 to 4 carbon atoms) It is related with the one-pack type curable silicone composition which consists at least of the mixture formed by previously mixing the amine compound represented by this. This one-pack type curable silicone composition has storage stability.

Description

  The present invention relates to a one-part curable silicone composition that cures by a hydrosilylation reaction, and an optical semiconductor device manufactured using the composition.

  Priority is claimed on Japanese Patent Application No. 2013-179426 filed on August 30, 2013, the contents of which are incorporated herein by reference.

  A curable silicone composition having an aryl group and cured by a hydrosilylation reaction is quickly cured by heating to form a highly transparent cured product with a high refractive index, such as a light emitting diode (LED). It is used as a sealant and protective agent for semiconductor elements in optical semiconductor devices.

  Examples of such a curable silicone composition include a branched organopolysiloxane having a phenyl group and an alkenyl group, an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and a hydrosilylation reaction. Curable silicone composition comprising catalyst for use (see Patent Document 1), linear organopolysiloxane having at least two alkenyl groups and at least one aryl group in one molecule, at least one alkenyl in one molecule A curable silicone composition comprising a branched organopolysiloxane having a group and at least one aryl group, an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and a catalyst for hydrosilylation reaction ( Patent Document 2), at least one al in one molecule Linear organopolysiloxane having kenyl group and diphenylsiloxane unit, branched organopolysiloxane having vinyl group and phenyl group, organopolysiloxane having diorganohydrogensiloxy group, and catalyst for hydrosilylation reaction The curable silicone composition which consists of (refer patent document 3) is mentioned.

  Such a curable silicone composition is provided in a two-part type in which organopolysiloxane having a silicon atom-bonded hydrogen atom and a catalyst for hydrosilylation reaction are separately provided in order to ensure storage stability. Must be mixed uniformly. Therefore, if the mixing ratio of the two liquids fluctuates or is not mixed sufficiently, there is a problem that the original performance cannot be fully exhibited, so it has storage stability and does not require mixing during use. One-part curable silicone compositions are eagerly desired.

JP 11-001619 A JP 2004-143361 A Japanese Patent Laid-Open No. 2005-076003

  An object of the present invention is to provide a one-part curable silicone composition having storage stability and an optical semiconductor device having excellent reliability using the composition.

The one-component curable silicone composition of the present invention is
(A) Average unit formula:
(R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e
(Wherein, R ¹ is the same or different monovalent hydrocarbon groups, however, in one molecule at least 5 mole% of R ¹ is an alkenyl group, at least 30 mole percent of R ¹ is an aryl group, X Is a hydrogen atom or an alkyl group; a is a positive number; b is 0 or a positive number; c is 0 or a positive number; d is a number from 0 to 0.3; 0.4 and b / a is a number from 0 to 10, c / a is a number from 0 to 5, and a + b + c + d = 1.)
And (B) a mixture obtained by previously mixing the following (i) component to (iii) component (i) General formula:
HR ² ₂ SiO (R ² ₂ SiO) _m SiR ² ₂ H
(In the formula, R ² is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated bond, provided that at least 15 mol% of R ^{2 in} one molecule is an aryl group; It is an integer of 100.)
An organopolysiloxane represented by
(Ii) metal catalyst for hydrosilylation reaction (in the component (B), the amount in which the catalyst metal is 0.01 to 1,000 ppm by mass), and (iii) the general formula:
R ³ ₂ N—R ⁴ —NR ³ ₂
(In the formula, R ³ is the same or different and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ is an alkylene group having 2 to ⁴ carbon atoms.)
An amine compound represented by the formula {in the amount of 0.5 to 1,000 ppm in the mass unit in the component (B)}
It consists of at least.

  In the component (B), the component (ii) is preferably a platinum-alkenylsiloxane complex, and the component (iii) is preferably N, N, N ′, N′-tetramethylethylenediamine.

The composition further comprises (C) a general formula:
R ⁵ ₃ SiO (R ⁵ ₂ SiO) _n SiR ⁵ ₃
Wherein R ⁵ is the same or different monovalent hydrocarbon group, provided that at least two of R ⁵ are alkenyl groups in one molecule, at least 20 mol% of R ⁵ is an aryl group, and n is (It is an integer of 5 to 1,000.)
It is preferable to contain 100 parts by mass or less of the linear organopolysiloxane represented by the formula (A) with respect to 100 parts by mass of the component (A).

Further, the present composition further comprises (D) an average unit formula:
(HR ⁶ ₂ SiO _1/2 ) _f (R ⁶ SiO _3/2 ) _g (R ⁶ ₂ SiO _2/2 ) _h (R ⁶ ₃ SiO _1/2 ) _i (SiO _4/2 ) _j (YO _{1 / 2} ) _k
(In the formula, R ⁶ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated bond, provided that at least 10 mol% of R ^{6 in} one molecule is an aryl group, and Y is a hydrogen atom. Or an alkyl group, f is a positive number, g is a positive number, h is 0 or a positive number, i is 0 or a positive number, j is a number from 0 to 0.3, k is a number from 0 to 0.4, and f / g is a number from 0.1 to 4, h / g is a number from 0 to 10, and i / g is a number from 0 to 5. F + g + h + i + j = 1.)
1 to 20 mol of silicon atom-bonded hydrogen atoms in component (D) with respect to the total of silicon-bonded hydrogen atoms in components (B) and (D) It is preferable to contain the quantity used as%.

  The optical semiconductor device of the present invention is characterized in that an optical semiconductor element is sealed, protected, or covered with a cured product of the one-component curable silicone composition.

  The one-component curable silicone composition of the present invention has storage stability, and the optical semiconductor device of the present invention is characterized by reliability.

It is sectional drawing of LED which is an example of the optical semiconductor device of this invention.

  First, the one-component curable silicone composition of the present invention will be described in detail.

(A) component is the main ingredient of this composition, average unit formula:
(R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e
It is a branched organopolysiloxane represented by the formula:

In the formula, R ¹ is the same or different monovalent hydrocarbon group. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; phenyl Examples include aryl groups such as a group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; and halogenated alkyl groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group. However, in one molecule, at least 5 mol% of R ¹ is an alkenyl group, and preferably at least 10 mol% of R ¹ is an alkenyl group. Also, at least 30 mol% of R ¹ is an aryl group, and preferably at least 40 mol% of R ¹ is an aryl group. This is because the attenuation of the resulting cured product due to light refraction, reflection, scattering, etc. is reduced. In the formula, X is a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

  In the formula, a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is a number from 0 to 0.3, and e is a number from 0 to 0.4. And b / a is a number from 0 to 10, c / a is a number from 0 to 5, and a + b + c + d = 1.

Component (B) is a cross-linking agent and a catalyst for promoting cross-linking of the present composition. (I) General formula:
HR ² ₂ SiO (R ² ₂ SiO) _m SiR ² ₂ H
(Ii) a metal catalyst for hydrosilylation reaction, and (iii) a general formula:
R ⁴ ₂ N—R ⁵ —NR ⁴ ₂
Or a reaction mixture obtained by mixing an amine compound represented by the formula:

In the component (i), R ² is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group; aryl groups such as phenyl group, tolyl group, xylyl group; benzyl group, phenethyl group, etc. Aralkyl groups; halogenated alkyl groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group are exemplified. However, in one molecule, at least 15 mol% of ^{R 2} is an aryl group, preferably at least 20 mol% of ^{R 2,} or at least 30 mol% of ^{R 2} is an aryl group. This is because the attenuation of the resulting cured product due to light refraction, reflection, scattering, etc. is reduced. Moreover, in formula, m is an integer of 1-100, Preferably, it is an integer of 1-50, More preferably, it is an integer of 1-20. This is because the handling workability of the resulting composition is improved when m is not more than the upper limit of the above range.

  Examples of the component (ii) include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst, and preferably a platinum-based catalyst. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, chloroplatinic acid alcohol solution, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex, and platinum-alkenylsiloxane complex is particularly preferable. . As this alkenylsiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, and the like. From the viewpoint of good stability, 1,3-divinyl-1,1,3,3-toteramethyldisiloxane is preferred.

  Further, since the stability of the platinum-alkenylsiloxane complex can be further improved, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane and 1,3-divinyl-1,3-dimethyl are added to this complex. -1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclo It is preferable to add an alkenylsiloxane such as tetrasiloxane or an organosiloxane oligomer such as dimethylsiloxane oligomer.

  Component (ii) is added in such an amount that the catalyst metal contained in component (ii) in component (B) is 0.01 to 1,000 ppm by mass, preferably 0.1 to 1,000 ppm. The amount is 1,000 ppm, or the amount is 0.1 to 500 ppm.

In the component (iii), R ³ is the same or different and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. In the formula, R ⁴ is an alkylene group having 2 to ⁴ carbon atoms. Examples of the alkylene group include an ethylene group, a propylene group, a methylmethylene group, and a methylethylene group.

  (Iii) As the component, N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N, N ′, N '-Tetraethylethylenediamine is exemplified.

  The component (iii) is well known as a reaction inhibitor in the hydrosilylation reaction curable silicone composition, but the conventional composition simply contains this component, whereas in the present composition, the present component It was found that the storage stability of the resulting one-component curable silicone composition can be remarkably improved by previously mixing the components (i) and (ii).

  Component (iii) is added in an amount of 0.5 to 1,000 ppm, preferably 1 to 400 ppm in mass unit in component (B).

  The component (B) is prepared by mixing the above components (i) to (iii), but these components may be heated, and may be cured at room temperature after mixing.

  In the present composition, the content of the component (B) is such that the silicon-bonded hydrogen atom in the component (i) is 0.1 to 5 mol with respect to 1 mol of the alkenyl group in the component (A). Yes, and preferably in an amount of 0.5 to 2 moles. This is because the composition is sufficiently cured when the content of the component (B) is at least the lower limit of the above range, and on the other hand, the heat resistance of the resulting cured product is at most the upper limit of the above range. This is because it improves.

In order to adjust the hardness of the resulting cured product and impart flexibility to the composition, (C) general formula:
R ⁵ ₃ SiO (R ⁵ ₂ SiO) _n SiR ⁵ ₃
It may contain the linear organopolysiloxane represented by these.

In the formula, R ⁵ is the same or different monovalent hydrocarbon group, and the same group as R ¹ is exemplified. However, at least two of R ^{5 in} one molecule are alkenyl groups. Further, in one molecule, at least 20 mol% of R ⁵ is an aryl group, preferably, at least 30 mol% of R ⁵ is an aryl group, or at least 40 mol% of R ⁵ is an aryl group. This is because the attenuation of the resulting cured product due to light refraction, reflection, scattering, etc. is reduced. In the formula, n is an integer of 5 to 1,000, preferably an integer of 5 to 100, or an integer of 5 to 50.

  In the present composition, the content of the component (C) is not limited, but is preferably 100 parts by mass or less with respect to 100 parts by mass of the component (A) because the hardness of the resulting cured product is not significantly reduced. Or from 70 parts by mass or less, and since the hardness of the resulting cured product can be appropriately adjusted and flexibility can be imparted, preferably 1 part by mass or more with respect to 100 parts by mass of component (A) Or 5 parts by mass or more.

Moreover, in order to adjust the hardness of the hardened | cured material obtained and to give mechanical strength to this composition, (D) average unit formula:
(HR ⁶ ₂ SiO _1/2 ) _f (R ⁶ SiO _3/2 ) _g (R ⁶ ₂ SiO _2/2 ) _h (R ⁶ ₃ SiO _1/2 ) _i (SiO _4/2 ) _j (YO _{1 / 2} ) _k
It may contain the branched chain organopolysiloxane represented by these.

In the formula, R ⁶ is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond. Specifically, the same group as R ² is exemplified. However, in one molecule, at least 10 mol% of R ⁶ is an aryl group, preferably, at least 15 mol% of R ⁶ is an aryl group, or at least 20 mol% is an aryl group. This is because the attenuation of the resulting cured product due to light refraction, reflection, scattering, etc. is reduced. In the formula, Y is a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

  In the formula, f is a positive number, g is a positive number, h is 0 or a positive number, i is 0 or a positive number, j is a number from 0 to 0.3, k Is a number from 0 to 0.4, and f / g is a number from 0.1 to 4, h / g is a number from 0 to 10, i / g is a number from 0 to 5, f + g + h + i + j = 1.

  In the present composition, the content of the component (D) is not limited, but in order to impart an appropriate hardness and mechanical strength to the resulting cured product, preferably in the component (B) and the component (D) The amount of silicon atom-bonded hydrogen atoms in component (D) is 1 to 20 mol%, and the amount of 2 to 20 mol%, or 2 It is the quantity which becomes 10 mol%. This is because when the content of the component (D) is not less than the lower limit of the above range, mechanical strength can be imparted to the obtained cured product. This is because it is possible to impart a high hardness.

  In this composition, as other optional components, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, etc. Alkyne alcohols; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5 , 7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and a reaction inhibitor such as benzotriazole. Although content of this reaction inhibitor is not limited, Preferably, it is the range of 0.0001-5 mass parts with respect to 100 mass parts of this composition.

  Moreover, you may contain the adhesion imparting agent for improving the adhesiveness in this composition. As the adhesion-imparting agent, an organosilicon compound having at least one alkoxy group bonded to a silicon atom in one molecule is preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable. The group other than the alkoxy group bonded to the silicon atom of the organosilicon compound includes a substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a halogenated alkyl group; 3 -Glycidoxyalkyl groups such as glycidoxypropyl group and 4-glycidoxybutyl group; epoxies such as 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group Examples include cyclohexylalkyl group; oxiranylalkyl group such as 4-oxiranylbutyl group and 8-oxiranyloctyl group; acrylic group-containing monovalent organic group such as 3-methacryloxypropyl group; and hydrogen atom. This organosilicon compound preferably has an alkenyl group or a group capable of reacting with a silicon atom-bonded hydrogen atom in the composition, and specifically, preferably has a silicon atom-bonded alkenyl group or a silicon atom-bonded hydrogen atom. . Moreover, since it can provide favorable adhesiveness to various types of substrates, the organosilicon compound preferably has at least one epoxy group-containing monovalent organic group in one molecule. Examples of such organosilicon compounds include organosilane compounds, organosiloxane oligomers, and alkyl silicates. Examples of the molecular structure of the organosiloxane oligomer or alkyl silicate include linear, partially branched linear, branched, cyclic, and network, particularly linear, branched, and network. Preferably there is. Examples of such organosilicon compounds include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; A siloxane compound having at least one silicon atom-bonded alkenyl group or silicon atom-bonded hydrogen atom and silicon atom-bonded alkoxy group, and a silane compound or siloxane compound having at least one silicon atom-bonded alkoxy group and silicon in one molecule. Examples thereof include a mixture of a siloxane compound having at least one atom-bonded hydroxy group and at least one silicon atom-bonded alkenyl group, methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate. In the present composition, the content of the adhesion-imparting agent is not limited, but is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the present composition.

  Further, in the present composition, as long as the object of the present invention is not impaired, as other optional components, inorganic fillers such as silica, glass, alumina and zinc oxide; fine organic resin powders such as polymethacrylate resin; You may contain dye, a pigment, a flame-retarding agent, a solvent, etc.

  Although the present composition is cured by heating, it is preferably heated at 50 to 200 ° C. for rapid curing.

  Moreover, although this composition has sufficient storage stability also at 25 degreeC, it is preferable to refrigerate at 5 degrees C or less.

  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 an optical semiconductor element is sealed, protected or covered with a cured product of the one-component curable silicone composition. As this optical semiconductor element, a light emitting diode element is exemplified. An example of such an optical semiconductor device is a light emitting diode (LED).

  A cross-sectional view of a surface-mounted LED, which is an example of this apparatus, is shown in FIG. In the LED shown in FIG. 1, the optical semiconductor element 1 is die-bonded on a lead frame 2, and the optical semiconductor element 1 and the lead frame 3 are wire-bonded by bonding wires 4. Further, a frame material 5 is provided around the optical semiconductor element 1, and the optical semiconductor element 1 in the frame material 5 is sealed with a cured product 6 of the one-part curable silicone composition of the present invention. ing.

  As a method of manufacturing the surface-mounted LED shown in FIG. 1, the semiconductor element 1 is die-bonded to the lead frame 2, the optical semiconductor element 1 and the lead frame 3 are wire-bonded with a gold bonding wire 4, and then The method of sealing the optical semiconductor element 1 with the hardened | cured material 6 is illustrated by heating at 50-200 degreeC after filling the frame material 5 with the one-pack type curable silicone composition of this invention.

  The one-part curable silicone composition and the optical semiconductor device of the present invention will be described in detail with reference to examples. The viscosity is a value at 25 ° C. In the formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.

  The properties of the one-part curable silicone composition were evaluated as follows.

[Curing speed]
The torque change at 150 ° C. of the one-part curable silicone composition was measured using ALPHA TECHNOLOGIES RHEOMETER MDR2000P. In addition, the time from when the torque value reaches 1 dNm immediately after the measurement is indicated by TS-1 (seconds) and used as an index of the curing rate.

[Change in viscosity]
A change in viscosity of the one-pack curable silicone composition at 25 ° C. was measured using a TA Instruments AR550 under a condition of a share rate of 20 (1 / s).

[Example 1]
formula:
HMe ₂ SiO (Ph ₂ SiO) SiMe ₂ H
(Content of silicon atom-bonded hydrogen atom = 0.60 mass%, content of phenyl group in all silicon atom-bonded organic groups = 33 mol%) 100 mass parts, 1,3 of platinum -Divinyl-1,1,3,3-tetramethyldisiloxane complex (amount that platinum metal is 12 ppm by mass with respect to this mixture), and N, N, N ', N'-tetramethylethylenediamine ( An amount of 100 ppm in terms of mass unit) was uniformly mixed and cured at room temperature for one day.

Next, 20 parts by weight of this mixture is mixed with an average unit formula:
(PhSiO _3/2 ) _0.75 (ViMe ₂ SiO _1/2 ) _0.25
(Vinyl group content = 5.6 mass%, vinyl group content in silicon-bonded total organic groups = 17 mol%, phenyl group content in silicon-bonded total organic groups) (Rate = 50 mol%) 59 parts by mass, number average molecular weight is 2,260, average unit formula:
(PhSiO _3/2 ) _0.40 (HMe ₂ SiO _1/2 ) _0.60
Branched organopolysiloxane represented by (content of silicon atom-bonded hydrogen atoms = 0.65% by mass, content of phenyl groups in all silicon atom-bonded organic groups = 25 mol%) 3 parts by mass, formula:
ViMe ₂ SiO (PhMeSiO) ₂₆ SiViMe ₂
18 parts by mass of tetrapolytetravinylcyclotetrasiloxane (content of vinyl group = 1.4% by mass, content of phenyl group in all silicon-bonded organic groups = 45% by mol) A one-part curable silicone composition was prepared by uniformly mixing 0.2 parts by mass. The properties of this composition are shown in Table 1.

[Example 2]
formula:
HMe ₂ SiO (Ph ₂ SiO) SiMe ₂ H
(Content of silicon atom-bonded hydrogen atom = 0.60 mass%, content of phenyl group in all silicon atom-bonded organic groups = 33 mol%) 100 mass parts, 1,3 of platinum -Divinyl-1,1,3,3-tetramethyldisiloxane complex (in such an amount that platinum metal is 16 ppm by mass with respect to this mixture) and N, N, N ', N'-tetramethylethylenediamine ( An amount of 25 ppm in terms of mass unit) was uniformly mixed and cured at room temperature for one day.

Next, 20 parts by weight of this mixture is mixed with an average unit formula:
(PhSiO _3/2 ) _0.75 (ViMe ₂ SiO _1/2 ) _0.25
(Vinyl group content = 5.6 mass%, vinyl group content in silicon-bonded total organic groups = 17 mol%, phenyl group content in silicon-bonded total organic groups) (Rate = 50 mol%) 59 parts by mass, number average molecular weight is 2,260, average unit formula:
(PhSiO _3/2 ) _0.40 (HMe ₂ SiO _1/2 ) _0.60
(Content of silicon atom-bonded hydrogen atom = 0.65 mass%, content of phenyl group in all silicon-bonded organic groups = 25 mol%) 3 parts by mass, formula:
ViMe ₂ SiO (PhMeSiO) ₂₆ SiViMe ₂
18 parts by mass of tetrapolytetravinylcyclotetrasiloxane (content of vinyl group = 1.4% by mass, content of phenyl group in all silicon-bonded organic groups = 45% by mol) A one-part curable silicone composition was prepared by uniformly mixing 0.2 parts by mass. The properties of this composition are shown in Table 1.

[Comparative Example 1]
formula:
HMe ₂ SiO (Ph ₂ SiO) SiMe ₂ H
(Content of silicon atom-bonded hydrogen atoms = 0.60 mass%, content of phenyl groups in all silicon atom-bonded organic groups = 33 mol%) 20 mass parts, average unit formula:
(PhSiO _3/2 ) _0.75 (ViMe ₂ SiO _1/2 ) _0.25
(Vinyl group content = 5.6 mass%, vinyl group content in silicon-bonded total organic groups = 17 mol%, phenyl group content in silicon-bonded total organic groups) (Rate = 50 mol%) 59 parts by mass, number average molecular weight is 2,260, average unit formula:
(PhSiO _3/2 ) _0.40 (HMe ₂ SiO _1/2 ) _0.60
3 parts by mass of an organopolysiloxane represented by the formula (content of silicon-bonded hydrogen atoms = 0.65% by mass, content of phenyl groups in all silicon-bonded organic groups = 25 mol%), formula:
ViMe ₂ SiO (PhMeSiO) ₂₆ SiViMe ₂
(Vinyl group content = 1.4 mass%, phenyl group content in all silicon-bonded organic groups = 45 mol%) 18 parts by mass, platinum 1,3-divinyl- 1,1,3,3-tetramethyldisiloxane complex (in the present composition, the amount of platinum metal in the complex is 2.6 ppm by mass), 1-ethynyl-1-cyclohexanol 0.02 parts by mass And 0.2 part by mass of tetramethyltetravinylcyclotetrasiloxane were uniformly mixed to prepare a one-part curable silicone composition. The properties of this composition are shown in Table 1.

  The one-part curable silicone composition of the present invention has excellent storage stability, does not require mixing for use, and forms a cured product having a high refractive index and a high light transmittance. It is suitable as an adhesive, a coating agent, or a protective agent.

DESCRIPTION OF SYMBOLS 1 Optical semiconductor element 2 Lead frame 3 Lead frame 4 Bonding wire 5 Frame material 6 Hardened | cured material of one liquid type curable silicone composition

Claims (6)

(A) Average unit formula:
(R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e
(Wherein, R ¹ is the same or different monovalent hydrocarbon groups, however, in one molecule at least 5 mole% of R ¹ is an alkenyl group, at least 30 mole percent of R ¹ is an aryl group, X Is a hydrogen atom or an alkyl group; a is a positive number; b is 0 or a positive number; c is 0 or a positive number; d is a number from 0 to 0.3; 0.4 and b / a is a number from 0 to 10, c / a is a number from 0 to 5, and a + b + c + d = 1.)
And (B) a mixture obtained by previously mixing the following components (i) to (iii): (i) a general formula:
HR ² ₂ SiO (R ² ₂ SiO) _m SiR ² ₂ H
(In the formula, R ² is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated bond, provided that at least 15 mol% of R ^{2 in} one molecule is an aryl group; It is an integer of 100.)
An organopolysiloxane represented by
(Ii) metal catalyst for hydrosilylation reaction (in the component (B), the amount in which the catalyst metal is 0.01 to 1,000 ppm by mass), and (iii) the general formula:
R ³ ₂ N—R ⁴ —NR ³ ₂
(In the formula, R ³ is the same or different and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ is an alkylene group having 2 to ⁴ carbon atoms.)
An amine compound represented by the formula {in the amount of 0.5 to 1,000 ppm in the mass unit in the component (B)}
A one-component curable silicone composition comprising at least   The one-component curable silicone composition according to claim 1, wherein component (ii) in component (B) is a platinum-alkenylsiloxane complex.   The one-component curable silicone composition according to claim 1 or 2, wherein in component (B), component (iii) is N, N, N ', N'-tetramethylethylenediamine. Furthermore, (C) the general formula:
R ⁵ ₃ SiO (R ⁵ ₂ SiO) _n SiR ⁵ ₃
Wherein R ⁵ is the same or different monovalent hydrocarbon group, provided that at least two of R ⁵ are alkenyl groups in one molecule, at least 20 mol% of R ⁵ is an aryl group, and n is (It is an integer of 5 to 1,000.)
The one-component curable silicone composition according to any one of claims 1 to 3, which comprises 100 parts by mass or less of the linear organopolysiloxane represented by the formula (A) with respect to 100 parts by mass of the component (A). . Further, (D) average unit formula:
(HR ⁶ ₂ SiO _1/2 ) _f (R ⁶ SiO _3/2 ) _g (R ⁶ ₂ SiO _2/2 ) _h (R ⁶ ₃ SiO _1/2 ) _i (SiO _4/2 ) _j (YO _{1 / 2} ) _k
(In the formula, R ⁶ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated bond, provided that at least 10 mol% of R ^{6 in} one molecule is an aryl group, and Y is a hydrogen atom. Or an alkyl group, f is a positive number, g is a positive number, h is 0 or a positive number, i is 0 or a positive number, j is a number from 0 to 0.3, k is a number from 0 to 0.4, and f / g is a number from 0.1 to 4, h / g is a number from 0 to 10, and i / g is a number from 0 to 5. F + g + h + i + j = 1.)
1 to 20 mol of silicon atom-bonded hydrogen atoms in component (D) with respect to the total of silicon-bonded hydrogen atoms in components (B) and (D) The one-component curable silicone composition according to any one of claims 1 to 4, which is contained in an amount of%.   An optical semiconductor device in which an optical semiconductor element is sealed, protected, or covered with a cured product of the one-component curable silicone composition according to any one of claims 1 to 5.

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