JP2005042099A - Silicone rubber composition, light emitting semiconductor coating protective material, and light emitting semiconductor device - Google Patents

Abstract

(A) Organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule,
(B) Resin-structured organopolysiloxane composed of SiO ₂ units, R ³ _n R ⁴ _p SiO _0.5 units and R ³ _q R ⁴ _r SiO _0.5 units (R ³ is vinyl group or allyl group, R ⁴ is aliphatic group Monovalent hydrocarbon group not containing a saturated bond, n is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, q + r = 3)
(C) organohydrogenpolysiloxane,
(D) Silicone rubber comprising a platinum group metal catalyst, wherein the component (B) is blended in an amount of 20 to 70% by mass with respect to the total amount of the components (A) and (B). Composition.
[Effect] According to the present invention, it is possible to obtain a cured product which is excellent in impact resistance and free from adhesion of dust due to surface tack which is a drawback of silicone elastomer.
[Selection] Figure 1

Description

The present invention relates to an addition-curing type silicone rubber composition, and more particularly to a silicone rubber composition that provides a silicone rubber having good rubber properties and strength properties and almost no surface tackiness.
The present invention also relates to a light-emitting semiconductor coating protective material having no dust adhesion on the surface of a cured product, having low elasticity and excellent crack resistance, and a light-emitting semiconductor device formed by coating a light-emitting semiconductor element using the same. is there.

  Silicone rubber compositions are used in various applications because they form cured products with excellent properties such as weather resistance and heat resistance, and rubber properties such as hardness and elongation. In addition, the adhesion of dust has been a problem with coating agents for electric and electronic parts (Patent Document 1: Japanese Patent Application Laid-Open No. 2001-2922).

  Moreover, in the silicone varnish which solved this, generation | occurrence | production of a crack occurred and became a problem. For this reason, there is a demand for a silicone rubber composition that can form a cured product that is free from dust on the surface of the cured product and has excellent crack resistance in a package such as an electric / electronic component.

  In this case, it is conventionally known that, in addition-curable silicone rubber compositions, the strength of the cured product can be improved by adding a resinous organopolysiloxane. However, even when the strength of the cured product is increased by the resinous organopolysiloxane, tack remains on the surface and there is a problem of dust adhesion.

  On the other hand, a light emitting semiconductor device such as a light emitting diode (LED) or the like, which is called a shell type in which an element is disposed on a lead electrode and the periphery thereof is covered with a transparent resin, is used. However, in recent years, light-emitting semiconductor devices called “surface mount type” as shown in FIGS. 1 and 2 are becoming mainstream due to simplification of the mounting process.

  1-3, 1 is a glass fiber reinforced epoxy resin housing, 2 is a light emitting element, 3 and 4 are lead electrodes, 5 is a die bond material, 6 is a gold wire, and 7 is a covering protective material.

  As a resin composition for protecting a light-emitting semiconductor element such as a light-emitting diode (LED), the cured product is required to have transparency, and is generally an epoxy such as a bisphenol A type epoxy resin or an alicyclic epoxy resin. What is obtained using resin and an acid anhydride type hardening | curing agent is used (refer patent document 2: patent 3241338, patent document 3: Unexamined-Japanese-Patent No. 7-25987).

  However, even in such a transparent epoxy resin, the moisture absorption resistance of the resin is high, so the moisture resistance durability is low, particularly the light resistance to low-wavelength light is low, so the light resistance is low, or it is colored due to light deterioration. Had.

  Therefore, it consists of an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, a silicon compound containing at least two SiH groups in one molecule, and a hydrosilylation catalyst. A resin composition for protecting the coating of an optical semiconductor element has also been proposed (see Patent Document 4: JP 2002-327126 A, Patent Document 5: JP 2002-338833 A).

  However, in order to improve the crack resistance, such a silicone-based cured product generally has a drawback that the surface of the cured product is tacky and dust easily adheres and impairs light transmission. Therefore, what uses the high hardness silicone resin for protective coating is proposed (refer patent document 6: Unexamined-Japanese-Patent No. 2002-314139, patent document 7: Unexamined-Japanese-Patent No. 2002-314143).

  However, these high-hardness silicone resins still have poor adhesion, and in a case-type light-emitting semiconductor device in which a light-emitting element is arranged in a ceramic and / or plastic housing and the inside of the housing is filled with silicone resin, −40 ° C. In the thermal shock test at ˜120 ° C., there was a problem that the silicone resin was peeled off from the ceramic or plastic of the housing.

  Furthermore, since the refractive index of the optical crystal of various compound semiconductors such as SiC, GaAs, GaP, GaAsP, GaAlAs, InAlGaP, InGaN, and GaN used in the light emitting element is high, the refractive index of the coating protective resin is dimethyl silicone. When it is as low as a resin, there is a drawback in that the light emission efficiency decreases due to reflection at the interface between the coating resin and the optical crystal.

  For this reason, methods such as attaching an antireflection film have been proposed as means for increasing the light emission rate (see Patent Document 8: Japanese Patent Laid-Open No. 2001-246236, Patent Document 9: Japanese Patent Laid-Open No. 2001-217467). . However, the number of steps is increased to produce an antireflection film, resulting in an increase in cost.

JP 2001-2922 A Japanese Patent No. 3241338 JP 7-25987 A JP 2002-327126 A JP 2002-338833 A JP 2002-314139 A JP 2002-314143 A JP 2001-246236 A JP 2001-217467 A

Accordingly, an object of the present invention is to provide an addition-curing type silicone rubber composition capable of forming a cured product having improved hardness and surface tackiness without impairing rubber properties such as elongation.
Another object of the present invention is to provide a light emitting semiconductor coating protective material that has no surface tackiness, is excellent in adhesiveness, and is excellent in impact resistance and light transmittance, and a light emitting semiconductor that is coated using the same and has high luminous efficiency. To provide an apparatus.

As a result of intensive studies to solve the above problems, the present inventors have found that an addition-curable silicone rubber composition has SiO ₂ units, R ³ _n R ⁴ _p SiO _0.5 units, and R ³ _q R ⁴ _r SiO. Resin-structured organopolysiloxane composed of _0.5 units (wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group containing no aliphatic unsaturated bond, and n is 2 or 3) , P is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, and q + r = 3), by blending a specific amount without impairing rubber properties such as elongation. It has been found that hardness and surface tackiness can be improved and dust adhesion can be prevented.

  Further, it is obtained by using together an organopolysiloxane represented by the following general formula (1) and having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C. and a specific amount of the organopolysiloxane having the above resin structure. It was found that the cured product of the addition reaction curable silicone rubber composition has no surface tackiness, has low elasticity and transparency, has good adhesion, and can be effectively used as a light-emitting semiconductor coating protective material. The present invention has been made.

Therefore, the present invention
(A) an organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule and having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C.,
(B) Resin-structured organopolysiloxane composed of SiO ₂ units, R ³ _n R ⁴ _p SiO _0.5 units and R ³ _q R ⁴ _r SiO _0.5 units (wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, n is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, q + r = 3.)
(C) an organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule;
(D) A platinum group metal catalyst is contained, and the component (B) is blended in an amount of 20 to 70% by mass with respect to the total amount of the components (A) and (B). A silicone rubber composition is provided.

  The present invention also relates to the above-mentioned silicone rubber composition, particularly an organopolysiloxane in which the component (A) is represented by the following general formula (1) and has a viscosity of 10 to 1,000,000 mPa · s at 25 ° C. A transparent light-emitting semiconductor coating protective material comprising a silicone rubber composition is provided.

（式中、Ｒ¹は互いに同一又は異種の非置換又は置換一価炭化水素基、Ｒ²は互いに同一又は異種の脂肪族不飽和結合を有さない非置換又は置換一価炭化水素基であり、ｋ，ｍは０又は正の整数であり、ｋ＋ｍがこのオルガノポリシロキサンの２５℃の粘度を１０〜１，０００，０００ｍＰａ・ｓとする数である。）

(Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² is an unsubstituted or substituted monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond. , K, m is 0 or a positive integer, and k + m is a number that makes the viscosity of this organopolysiloxane at 25 ° C. 10 to 1,000,000 mPa · s.)

  Furthermore, the present invention is a light emitting semiconductor device in which a light emitting semiconductor element is disposed in a ceramic and / or plastic housing having an opening, and the inside of the housing is covered and protected with a cured product of the above covering protective material. , And a light emitting semiconductor device in which the light emitting semiconductor element is disposed on a lead electrode in a ceramic and / or plastic housing having an opening, and the inside of the housing is covered and protected with a cured product of the covering protective material. I will provide a.

  According to the present invention, a cured product having excellent impact resistance and free from dust adhesion due to surface tack, which is a drawback of silicone elastomers, can be obtained. In addition, the light-emitting semiconductor device coated and protected with the light-emitting semiconductor coating protective material of the present invention can provide a light-emitting semiconductor device that has long life and excellent energy saving because of less discoloration due to a heat resistance test and high light emission efficiency. The above benefits are enormous.

(A) Organopolysiloxane The organopolysiloxane of component (A) is a fat represented by an alkenyl group having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms such as two or more vinyl groups and allyl groups in one molecule. Any one can be used as long as it has a group unsaturated bond and has a viscosity of 10 to 1,000,000 mPa · s, particularly 100 to 100,000 mPa · s at 25 ° C. A linear organopolysiloxane having at least one alkenyl group on each of the silicon atoms at both ends of the molecular chain represented by the formula (1), having a viscosity at 25 ° C. of 10 to 1,000 as described above. 1,000 mPa · s is desirable from the viewpoint of workability and curability. The linear organopolysiloxane may contain a small amount of a branched structure (trifunctional siloxane unit) in the molecular chain.

（式中、Ｒ¹は互いに同一又は異種の非置換又は置換一価炭化水素基、Ｒ²は互いに同一又は異種の脂肪族不飽和結合を有さない非置換又は置換一価炭化水素基であり、ｋ，ｍは０又は正の整数であり、ｋ＋ｍがこのオルガノポリシロキサンの２５℃の粘度を１０〜１，０００，０００ｍＰａ・ｓとする数である。）

(Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² is an unsubstituted or substituted monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond. , K, m is 0 or a positive integer, and k + m is a number that makes the viscosity of this organopolysiloxane at 25 ° C. 10 to 1,000,000 mPa · s.)

Here, the monovalent hydrocarbon group for R ¹ is preferably a group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Group, alkyl group such as tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group , Aralkyl groups such as phenylethyl group and phenylpropyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and octenyl group, and hydrogen atoms of these groups Are substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group, etc., such as a chloromethyl group, Roropuropiru group, bromoethyl group, and a halogen-substituted alkyl group or cyanoethyl group such trifluoropropyl group.
Further, the monovalent hydrocarbon group for R ² is preferably one having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and the same examples as the specific examples for R ¹ described above can be exemplified, but an alkenyl group is not included.
k and m are generally 0 or a positive integer satisfying 5 ≦ k + m ≦ 10,000, preferably 10 ≦ k + m ≦ 2,000, and 0 <k / (k + m) ≦ 0.2. A satisfying integer.

（上記式において、ｔは８〜２，０００の整数である。） Specific examples of the component (A) include the following.

(In the above formula, t is an integer of 8 to 2,000.)

（上記式において、ｋ，ｍは上述した通りである。）

(In the above formula, k and m are as described above.)

(B) Resin-structured organopolysiloxane Resin-structured (ie, three-dimensional network) organopolysiloxane, which is an important component of the composition of the present invention, comprises SiO ₂ units, R ³ _n R ⁴ _p SiO _0.5 units and Resin-structured organopolysiloxane composed of R ³ _q R ⁴ _r SiO _0.5 unit (in the above formula, R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group containing no aliphatic unsaturated bond) And n is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, and q + r = 3.
Examples of the monovalent hydrocarbon group for R ⁴ include those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, similar to the above R ² .

Here, when the SiO ₂ unit is a unit, the R ³ _n R ⁴ _p SiO _0.5 unit is b unit, and the R ³ _q R ⁴ _r SiO _0.5 unit is c unit,
(B + c) /a=0.3-3, especially 0.7-1
c / a = 0.01 to 1, especially 0.07 to 0.15
It is preferable that the organopolysiloxane of component (B) has a polystyrene-equivalent weight average molecular weight in the range of 500 to 10,000 by GPC.

  In addition to the a unit, b unit, and c unit, the organopolysiloxane having a resin structure as the component (B) is further difunctional siloxane unit or trifunctional siloxane unit (that is, organosilsesquioxane). (Unit) may be contained in a small amount within a range not impairing the object of the present invention.

  Such an organopolysiloxane having a resin structure can be easily synthesized by combining the compounds serving as the unit sources so as to have the above molar ratio, and performing cohydrolysis in the presence of an acid, for example.

  Here, examples of the a unit source include sodium silicate, alkyl silicate, polyalkyl silicate, and silicon tetrachloride.

Moreover, as a b unit source, the following can be illustrated.

Further, examples of the c unit source include the following.

  The (B) component resin-structured organopolysiloxane is blended to improve the physical strength and surface tack of the cured product, and as described above, It is blended in an amount of 20 to 70 mass% per total amount. Preferably 30-60 mass% is mix | blended. If the blending amount of the component (B) is too small, the above effect cannot be achieved sufficiently, and if it is too large, there are disadvantages such as the viscosity of the composition being remarkably increased and cracks being easily generated in the cured product.

(C) Organohydrogenpolysiloxane The (C) component organohydrogenpolysiloxane acts as a crosslinking agent, and the SiH group in the component is added to the vinyl groups in the (A) and (B) components. A cured product is formed by reaction. The organohydrogenpolysiloxane may be any one as long as it has two or more hydrogen atoms (that is, SiH groups) bonded to a silicon atom in one molecule. In particular, the following average composition formula (2)
H _a (R ⁵ ) _b SiO _{(4-ab) / 2} (2)
Wherein R ⁵ is the same or different unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and a and b are 0.001 ≦ a <2, 0.7 ≦ b ≦ 2 and 0.8 ≦ a + b ≦ 3.)
And one having at least 2, preferably 3 or more hydrogen atoms (SiH groups) bonded to a silicon atom in one molecule.

Here, R ⁵ in the above formula (2) is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 7 carbon atoms, which does not contain an aliphatic unsaturated bond. It is preferable that there are, for example, lower alkyl groups such as a methyl group, aryl groups such as a phenyl group, and those exemplified for the substituent R ² in the above general formula (1). A and b are numbers satisfying 0.001 ≦ a <2, 0.7 ≦ b ≦ 2, and 0.8 ≦ a + b ≦ 3, preferably 0.05 ≦ a ≦ 1, 0.8 ≦ b ≦ 2 and 1 ≦ a + b ≦ 2.7. The position of the hydrogen atom bonded to the silicon atom is not particularly limited, and may be at the end of the molecule or in the middle.

Examples of the organohydrogenpolysiloxane include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends Trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy Blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer on both ends Body, (CH _{3) 2} HSiO copolymer comprising a _1/2 units and SiO _4/2 units, and, (CH _{3) 2} HSiO _1/2 units, and SiO _4/2 units (C ₆ H _{5) 3} SiO And a copolymer composed of _3/2 units.
Moreover, a compound as shown by the following structure can also be used.

  The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is 3 to 1. , Especially about 3 to 300 can be used.

Such organohydrogenpolysiloxanes are usually R ⁵ SiHCl ₂ , (R ⁵ ) ₃ SiCl, (R ⁵ ) ₂ SiCl ₂ , (R ⁵ ) ₂ SiHCl (R ⁵ is as described above). Such chlorosilanes can be hydrolyzed or siloxanes obtained by hydrolysis can be equilibrated.

  The amount of the organohydrogenpolysiloxane is the effective curing amount of the above components (A) and (B). In particular, the SiH group is an alkenyl group (for example, vinyl) in the components (A) and (B). It is preferable to use at a molar ratio of 0.1 to 4.0, particularly preferably 1.0 to 3.0, and more preferably 1.2 to 2.8 per total amount of (base). If it is less than 0.1, the curing reaction does not proceed and it is difficult to obtain a cured silicone rubber. If it exceeds 4.0, a large amount of unreacted SiH groups remain in the cured product, so that the rubber physical properties are deteriorated over time. May cause a change.

(D) Platinum group metal-based catalyst This catalyst component is blended in order to cause the addition curing reaction of the composition of the present invention, and there are platinum-based, palladium-based, and rhodium-based ones. From the viewpoint of platinum, platinum-based materials such as platinum, platinum black, chloroplatinic acid, for example, H ₂ PtCl ₆ · mH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ Examples include mH ₂ O, PtO ₂ .mH ₂ O (m is a positive integer), and complexes thereof with hydrocarbons such as olefins, alcohols or vinyl group-containing organopolysiloxanes. These can be used alone or in combination of two or more. The compounding amount of these catalyst components may be a so-called catalyst amount, and is usually 0.1 to 1,000 ppm in terms of platinum group metal (mass) with respect to the total amount of the components (A) to (C), preferably Used in the range of 0.5 to 200 ppm.

(E) Adhesion aid In the composition of the present invention, an organosilicon compound such as organosilane or organopolysiloxane having a silicon atom-bonded alkoxy group is used to improve the adhesion of a cured product obtained by curing the composition. These adhesion assistants may be added and blended as optional components as required. Examples of such organosilicon compounds include tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and vinyl. Alkoxysilane compounds such as trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and hydrogen atoms bonded to silicon atoms in one molecule ( SiH group), alkenyl groups bonded to silicon atom (e.g., Si-CH = CH ₂ groups), such as trialkoxysilyl groups alkoxysilyl group (e.g., such as trimethoxysilyl group), an epoxy group (eg Glycidoxypropyl group, 3,4-epoxycyclohexylethyl group) containing at least 2, preferably 2 or 3 functional groups, usually having 4 to 30 silicon atoms, particularly about 4 to 20 And a siloxane compound (organosiloxane oligomer) having a linear or cyclic structure.

（式中、Ｒ⁶は、下記式（４）

で表される有機基又は脂肪族不飽和結合を含有する一価炭化水素基であるが、少なくとも１個は式（４）の有機基であり、Ｒ⁷は水素原子又は炭素数１〜６の一価炭化水素基、ｓは１〜６、特に１〜４の整数である。） In this case, an organooxysilyl-modified isocyanurate compound represented by the following general formula (3) and / or a hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound) is preferably used as an adhesion assistant.

(Wherein R ⁶ represents the following formula (4)

Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of which is an organic group of the formula (4), and R ⁷ is a hydrogen atom or having 1 to 6 carbon atoms. A monovalent hydrocarbon group, s is an integer of 1-6, especially 1-4. )

In this case, the monovalent hydrocarbon group containing an aliphatic unsaturated bond of R ⁶ includes vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, cyclohexenyl group. And alkenyl groups having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms. Examples of the monovalent hydrocarbon group for R ⁷ include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, hexyl groups, cyclohexyl groups, and other alkyl groups, vinyl A monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms such as an alkenyl group and an aryl group such as a phenyl group, which are the same as those exemplified as R ⁶ such as a group, an allyl group, a propenyl group and an isopropenyl group. And preferably an alkyl group.

（式中、ｍ，ｎはそれぞれｍ＋ｎが２〜５０、好ましくは４〜２０を満足する正の整数である。） (E) As an adhesion assistant of a component, the compound shown by a following formula is illustrated.

(In the formula, m and n are each a positive integer satisfying m + n of 2 to 50, preferably 4 to 20.)

  Among such organosilicon compounds, compounds having particularly excellent adhesion of the resulting cured product include organic compounds having silicon-bonded alkoxy groups and alkenyl groups or silicon-bonded hydrogen atoms (SiH groups) in one molecule. A silicon compound is preferred.

  In the present invention, the blending amount of the above-mentioned (E) component (arbitrary component) adhesion assistant is usually 10 parts by mass or less (ie 0 10 parts by mass), preferably 0.01-5 parts by mass, more preferably about 0.1-1 part by mass. If the amount of component (E) is too small, the adhesion to the substrate may be inferior, and if too large, the hardness and surface tackiness of the cured product may be adversely affected.

  In addition, although the silicone rubber composition of the present invention can be used as a light emitting semiconductor coating protective material, the coating protective material obtained by blending an adhesion assistant as described above has a strong adhesive force. No peeling due to IR reflow during resin curing or mounting. Further, the cured product is durometer type A, has a hardness of 70 or more, has no adhesion of dust to the surface of the cured product, and has a low elastic property, so it depends on a difference in thermal expansion coefficient from a ceramic or plastic casing. Since stress can be absorbed, cracks do not occur even when 1,000 cycles of the thermal shock test at −40 ° C. on the low temperature side and 120 ° C. on the high temperature side are performed.

  In addition to the components (A) to (E) described above, various additives known per se can be blended with the composition of the present invention as necessary. For example, reinforcing inorganic fillers such as fumed silica and fumed titanium dioxide, non-reinforcing inorganic fillers such as calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, and zinc oxide, (A) It can mix | blend suitably in the range of 600 mass parts or less per 100 mass parts of total amounts of a component and (B) component.

The silicone rubber composition of the present invention is prepared by uniformly mixing the above-described components. Usually, the silicone rubber composition is stored in two liquids so that curing does not proceed. Curing is performed. Of course, in order to increase the workable time, a small amount of a reaction inhibitor such as an acetylene alcohol compound, a triazole, a nitrile compound, or a phosphorus compound can be added and used as one liquid. Further, a phosphor for changing the wavelength, a light scattering agent such as fine titanium oxide powder (TiO ₂ ), etc. can be added to the silicone rubber composition of the present invention. This composition is cured immediately by heating as necessary to form an elastic cured product having high hardness and no surface tack. Silicone, including protective coating agents for electrical and electronic parts, potting, casting, molding agents, etc. It can be widely used as a general purpose application in which the adhesiveness of silicone such as a surface coat of a rubber keyboard is a problem. The curing conditions are not particularly limited, but are usually 60 to 200 ° C., preferably 80 to 180 ° C. for 5 minutes to 8 hours, preferably about 10 minutes to 4 hours.

  In addition, the composition of the present invention can be prepared in a liquid state, and particularly when used as a light-emitting semiconductor coating protective material, it is preferably in a liquid state, and the viscosity at 25 ° C. is 10 to 1,000,000 mPa · s. About 100 to 1,000,000 mPa · s is preferable.

  The coating protective material of the present invention is used for coating protection of a light emitting semiconductor. In this case, examples of the light emitting semiconductor include a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array. The mode of covering and protecting the light emitting semiconductor is not particularly limited, but as shown in FIGS. 1 and 2, the casing is filled with a covering protective material covering the light emitting semiconductor disposed in the housing having the opening. Then, a method such as curing it can be adopted.

  In addition, the curing conditions of the coating protective material of the present invention are arbitrary depending on the working conditions from 72 hours to 200 ° C. for 3 minutes at room temperature (25 ° C.). It is possible to select appropriately from the balance.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, a part shows a mass part and the viscosity is a value of 25 degreeC in the following example. Further, Me represents a methyl group, and Vi represents a vinyl group.

で示されるポリシロキサン（ＶＦ）５０部に、ＳｉＯ₂単位５０モル％、（ＣＨ₃）₃ＳｉＯ_0.5単位４２．５モル％及びＶｉ₃ＳｉＯ_0.5単位７．５モル％からなるレジン構造のビニルメチルシロキサン（ＶＭＱ）５０部、ＳｉＨ基量が前記ＶＦ及びＶＭＱ成分中のビニル基の合計量当り１．５倍モルとなる量の下記式（ｉｉ）

で示されるオルガノハイドロジェンポリシロキサン及び塩化白金酸のオクチルアルコール変性溶液（Ｐｔ濃度２質量％、以下同様）０．０５部を加え、よく撹拌し、シリコーンゴム組成物を調製した。 [Example 1]
Formula (i) below

And 50 parts by weight of polysiloxane (VF) represented by the following formula: Resin-structure vinylmethyl consisting of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₃ SiO _0.5 units 50 parts by weight of siloxane (VMQ), and the amount of SiH group is 1.5 times mol per total amount of vinyl groups in the VF and VMQ components.

An organohydrogenpolysiloxane represented by the above formula and 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid (Pt concentration: 2% by mass, the same applies hereinafter) were added and stirred well to prepare a silicone rubber composition.

  This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the tensile strength, hardness (measured using an A-type spring tester) and elongation were measured according to JIS K 6301. In addition to confirming the tackiness of the surface with a finger, a cured product was placed in cotton dust, and after taking out, it was tested whether the surface dust could be removed with air. Further, the resin was sealed in an aluminum dish (diameter 6 cm, depth 0.6 mm), and the cured sample was put into a -50 ° C. to 150 ° C. cooling cycle to check for cracks. The measurement results are shown in Table 1.

を使用した以外は実施例１と同じ組成にてシリコーンゴム組成物を調製し、硬化物を形成し、実施例１と同様に測定した結果を表１に示した。 [Example 2]
As VF, the following formula (iii)

Table 1 shows the results of preparing a silicone rubber composition with the same composition as in Example 1 except that was used, forming a cured product, and measuring the same as in Example 1.

[Example 3]
70 parts of VF used in Example 1, 30 parts of VMQ used in Example 1 (containing 0.043 mol / 100 g of SiVi bond as the total amount of VF and VMQ), organohydrogenpolysiloxane used in Example 1 (SiH 4.3 parts of a bond (containing 0.74 mol / 100 g) and 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid were mixed to prepare a silicone rubber composition in the same manner as in Example 1 to form a cured product. The results measured in the same manner as in Example 1 are shown in Table 1.

[Example 4]
In Example 1, the VMQ resin used was a vinylmethylsiloxane having a resin structure consisting of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₂ MeSiO _0.5 units ( VMQ) Examples except that the organohydrogenpolysiloxane of the above formula (ii) was used in an amount of 50 parts, and the amount of SiH groups was 1.5 times mol per the total amount of vinyl groups in the VF and VMQ components. A silicone rubber composition was prepared in the same manner as in Example 1 to form a cured product, and the results of measurement in the same manner as in Example 1 are shown in Table 1.

[Example 5]
Resin-structured vinyl comprising 50 mol% of SiO ₂ units, 40 mol% of (CH ₃ ) ₃ SiO _0.5 units and 10 mol% of Vi ₃ SiO _0.5 units in 50 parts of polysiloxane (VF) represented by the above formula (i) 50 parts of methylsiloxane (VMQ), organohydrogenpolysiloxane represented by the above formula (ii) and platinum chloride in an amount such that the amount of SiH groups is 1.5 times mol per total amount of vinyl groups in the VF and VMQ components 0.05 parts of an acid octyl alcohol-modified solution was added and stirred well to prepare a silicone rubber composition. The composition was heat-molded at 150 ° C./4 hr to form a cured product, and the results measured in the same manner as in Example 1 are shown in Table 1.

[Comparative Example 1]
50 parts by weight of polysiloxane (VF) represented by the above formula (iii) is composed of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of ViMe ₂ SiO _0.5 units. 50 parts of vinyl methylsiloxane (VMQ) having a resin structure, and an organohydrogenpolypolyol represented by the above formula (ii) in an amount such that the amount of SiH groups is 1.5 times mol per total amount of vinyl groups in the VF and VMQ components 0.05 parts of octyl alcohol modified solution of siloxane and chloroplatinic acid was added and stirred well to prepare a silicone rubber composition. This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the results of measurement in the same manner as in Example 1 are shown in Table 2.

[Comparative Example 2]
50 parts by weight of polysiloxane (VF) represented by the above formula (i) is composed of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of ViMe ₂ SiO _0.5 units. 50 parts of vinyl methylsiloxane (VMQ) having a resin structure, and an organohydrogenpolypolyol represented by the above formula (ii) in an amount such that the amount of SiH groups is 1.5 times mol per total amount of vinyl groups in the VF and VMQ components 0.05 parts of octyl alcohol modified solution of siloxane and chloroplatinic acid was added and stirred well to prepare a silicone rubber composition. This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the results of measurement in the same manner as in Example 1 are shown in Table 2.

[Comparative Example 3]
Commercially available silicone varnish KJR-632 (manufactured by Shin-Etsu Chemical Co., Ltd.) was cured in the same manner to form a cured product, and the results measured in the same manner as in Example 1 are shown in Table 2.

で示されるオルガノハイドロジェンポリシロキサン８部、下記式（ｖ）

で示されるオルガノハイドロジェンポリシロキサン５部、下記式（ｖｉ）

で示される接着助剤０．３部及び塩化白金酸のオクチルアルコール変性溶液０．０５部を加え、よく撹拌し、シリコーンゴム組成物を調製した。 [Example 6]
50 parts by weight of polysiloxane (VF) represented by the above formula (i) is composed of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₃ SiO _0.5 units. Resin structure vinylmethylsiloxane (VMQ) 50 parts, the following formula (iv)

8 parts of an organohydrogenpolysiloxane represented by the following formula (v)

5 parts of an organohydrogenpolysiloxane represented by the following formula (vi)

A silicone rubber composition was prepared by adding 0.3 part of an adhesion aid represented by the above and 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid and stirring well.

  This composition is heat-molded at 150 ° C./4 hr to form a cured product, and in accordance with JIS K 6301, the shear bond strength, hardness (measured using an A-type spring tester) and elongation rate to aluminum are measured. It was measured. In addition to confirming the tackiness of the surface with a finger, a cured product was placed in cotton dust, and after taking out, it was tested whether the surface dust could be removed with air. Further, the resin was sealed in an aluminum dish (diameter 6 cm, depth 0.6 mm), and the cured sample was put into a -50 ° C. to 150 ° C. cooling cycle to check for cracks. Table 3 shows the measurement results.

[Example 7]
A silicone rubber composition was prepared with the same composition as in Example 6 except that the above formula (iii) was used as VF, a cured product was formed, and the results measured in the same manner as in Example 6 are shown in Table 3.

で示される接着助剤０．２部及び塩化白金酸のオクチルアルコール変性溶液０．０５部を加え、よく撹拌し、シリコーンゴム組成物を調製した。この組成物を１５０℃／４ｈｒにて硬化物を形成し、実施例６と同様に測定した結果を表３に示した。 [Example 8]
50 parts by weight of the polysiloxane represented by the above formula (i) is added to a vinylmethylsiloxane having a resin structure consisting of 50 mol% of SiO ₂ units, 40 mol% of (CH ₃ ) ₃ SiO _0.5 units and 10 mol% of Vi ₃ SiO _0.5 units ( VMQ) 50 parts, 3 parts of an organohydrogenpolysiloxane represented by the above formula (ii), 5 parts of an organohydrogenpolysiloxane represented by the above formula (iv), and the following formula (vii)

And 0.2 part of an adhesion assistant represented by the above and 0.05 part of chloroplatinic acid octyl alcohol-modified solution were added and stirred well to prepare a silicone rubber composition. Table 3 shows the results obtained by forming a cured product of this composition at 150 ° C./4 hr and measuring it in the same manner as in Example 6.

[Comparative Example 4]
50 parts by weight of the polysiloxane represented by the above formula (iii) has a resin structure composed of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of ViMe ₂ SiO _0.5 units. 50 parts of vinylmethylsiloxane (VMQ), 8 parts of organohydrogenpolysiloxane represented by the above formula (iv), 5 parts of organohydrogenpolysiloxane represented by the above formula (v), adhesion represented by the above formula (vi) 0.3 parts of auxiliary agent and 0.05 parts of chloroplatinic acid octyl alcohol-modified solution were added and stirred well to prepare a silicone rubber composition. This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the results of measurement in the same manner as in Example 6 are shown in Table 3.

[Comparative Example 5]
50 parts by weight of the polysiloxane represented by the above formula (i) has a resin structure composed of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of ViMe ₂ SiO _0.5 units. 50 parts of vinylmethylsiloxane (VMQ), 3 parts of organohydrogenpolysiloxane represented by the above formula (ii), 5 parts of organohydrogenpolysiloxane represented by the above formula (iv), adhesion represented by the above formula (vii) 0.2 part of auxiliary agent and 0.05 part of octyl alcohol modified solution of chloroplatinic acid were added and stirred well to prepare a silicone rubber composition. This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the results of measurement in the same manner as in Example 6 are shown in Table 3.

  As shown in the results of Tables 1 to 3, according to the present invention, a cured product having excellent impact resistance and free from dust adhesion due to surface tack, which is a defect of the silicone elastomer, can be obtained.

で表される末端ビニルジメチルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体（粘度３Ｐａ・ｓ）１００部、下記式（ＩＩ） Next, examples and comparative examples of the transparent semiconductor coating protective material are shown.
The evaluation methods of the coating protective materials of Examples 9 to 12 and Comparative Examples 6 to 8 are as follows.
[Evaluation methods]
Preparation of silicone die bond material

A terminal vinyldimethylsiloxy group-capped dimethylsiloxane / diphenylsiloxane copolymer (viscosity 3 Pa · s) represented by the following formula (II):

で表されるメチルハイドロジェンポリシロキサン（粘度１５ｍＰａ・ｓ）２．５部、塩化白金酸２−エチルヘキシルアルコール変性溶液（Ｐｔ濃度２質量％）０．０３部、エチニルシクロヘキシルアルコール０．０５部、３−グリシドキシプロピルトリメトキシシラン７部及び平均粒径９μｍの球状アルミナ微粉末４００部を均一混合してシリコーンダイボンド材を調製した。

Methyl hydrogen polysiloxane (viscosity 15 mPa · s) 2.5 parts, chloroplatinic acid 2-ethylhexyl alcohol modified solution (Pt concentration 2% by mass) 0.03 parts, ethynylcyclohexyl alcohol 0.05 parts, 3 A silicone die bond material was prepared by uniformly mixing 7 parts of glycidoxypropyltrimethoxysilane and 400 parts of spherical alumina fine powder having an average particle size of 9 μm.

Method for Manufacturing Light-Emitting Semiconductor Device A light-emitting semiconductor device as shown in FIG. 1 was manufactured using an LED chip having a light-emitting layer made of InGaN and having a main light emission peak of 470 nm as a light-emitting element. The light emitting element 2 was fixed by heating at 180 ° C. for 10 minutes using a silicone die bond material 5 as a lead electrode. After the light emitting element 2 and the lead electrodes 3 and 4 were connected by the gold wire 6, the covering protective material 7 was potted and cured at 180 ° C. for 1 hour to produce a light emitting semiconductor device.
Thermal Shock Resistance Test Method The manufactured light-emitting semiconductor device was subjected to 1,000 cycles of thermal shock tests at a low temperature side of −40 ° C. and a high temperature side of 120 ° C., and the number of appearance cracks was observed.
Surface dust adhesion The light-emitting semiconductor device produced was sprinkled with fine powder silica and adhered to the surface, and then air was blown to confirm whether the fine powder silica adhered to the surface of the semiconductor device could be removed.

で示されるポリシロキサン（ＶＦ）５０部に、ＳｉＯ₂単位５０モル％、（ＣＨ₃）₃ＳｉＯ_0.5単位４２．５モル％及びＶｉ₃ＳｉＯ_0.5単位７．５モル％からなるレジン構造のビニルメチルシロキサン（ＶＭＱ）５０部、

で示されるオルガノハイドロジェンポリシロキサン８部、

で示されるオルガノハイドロジェンポリシロキサン５部、

で示される接着助剤０．３部、及び、塩化白金酸のオクチルアルコール変性溶液０．０５部を加え、よく撹拌し、シリコーンゴム組成物を調製した。この組成物を１５０℃／４ｈｒにて加熱成型して硬化物を形成し、ＪＩＳ Ｋ ６３０１に準拠して、硬度（Ａ型スプリング試験機を用いて測定）を測定した。この組成物を硬化させたものは無色透明なものであった。このゴム組成物を用いて発光半導体装置を作製した。 [Example 9]
Following formula

And 50 parts by weight of polysiloxane (VF) represented by the following formula: Resin-structure vinylmethyl consisting of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₃ SiO _0.5 units 50 parts of siloxane (VMQ),

8 parts of an organohydrogenpolysiloxane represented by

5 parts of an organohydrogenpolysiloxane represented by

A silicone rubber composition was prepared by adding 0.3 part of an adhesion aid represented by the above and 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid and stirring well. This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the hardness (measured using an A-type spring tester) was measured in accordance with JIS K 6301. The cured product was colorless and transparent. A light-emitting semiconductor device was manufactured using this rubber composition.

を使用した以外は実施例９と同じ組成にてシリコーンゴム組成物を調製し、硬化物を形成し、実施例９と同様に測定した結果を表４に示した。硬化物は無色透明であった。このゴム組成物を用いて発光半導体装置を作製した。 [Example 10]
The following formula as VF

Table 4 shows the results of preparing a silicone rubber composition with the same composition as in Example 9 except that was used, forming a cured product, and measuring the same as in Example 9. The cured product was colorless and transparent. A light-emitting semiconductor device was manufactured using this rubber composition.

で示されるオルガノハイドロジェンポリシロキサン１０部を使用した以外は、実施例９と同様にしてシリコーンゴム組成物を調製し、硬化物を形成し、実施例９と同様に測定した結果を表４に示した。硬化物は無色透明であった。このゴム組成物を用いて発光半導体装置を作製した。 [Example 11]
70 parts of polysiloxane (VF) used in Example 9, 50 mol% of SiO ₂ units as VMQ resin, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₂ MeSiO _0.5 units Resin structure vinyl methylsiloxane (VMQ) 30 parts, following formula

A silicone rubber composition was prepared in the same manner as in Example 9 except that 10 parts of the organohydrogenpolysiloxane shown in FIG. Indicated. The cured product was colorless and transparent. A light-emitting semiconductor device was manufactured using this rubber composition.

で示されるポリシロキサン５０部に、ＳｉＯ₂単位５０モル％、（ＣＨ₃）₃ＳｉＯ_0.5単位４０モル％及びＶｉ₃ＳｉＯ_0.5単位１０モル％からなるレジン構造のビニルメチルシロキサン（ＶＭＱ）５０部、下記式

で示されるオルガノハイドロジェンポリシロキサン３部、

で示されるオルガノハイドロジェンポリシロキサン５部、

で示される接着助剤０．２部、及び、塩化白金酸のオクチルアルコール変性溶液０．０５部を加え、よく撹拌し、シリコーンゴム組成物を調製した。この組成物を１５０℃／４ｈｒにて加熱成型して硬化物を形成し、実施例９と同様に測定した結果を表４に示した。この硬化物は無色透明なものであった。このゴム組成物を用いて発光半導体装置を作製した。 [Example 12]
Following formula

50 parts by weight of polysiloxane represented by the following formula: 50 parts by weight of SiO ₂ units, 50 parts by weight of (CH ₃ ) ₃ SiO _0.5 units and 50 parts by weight of vinyl methylsiloxane (VMQ) having a resin structure consisting of 10 mol% of Vi ₃ SiO _0.5 units, Following formula

3 parts of an organohydrogenpolysiloxane represented by

5 parts of an organohydrogenpolysiloxane represented by

And 0.2 part of an adhesion assistant represented by the above and 0.05 part of a chloroplatinic acid octyl alcohol-modified solution were added and stirred well to prepare a silicone rubber composition. This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the results of measurement similar to Example 9 are shown in Table 4. This cured product was colorless and transparent. A light-emitting semiconductor device was manufactured using this rubber composition.

で示されるポリシロキサン５０部に、ＳｉＯ₂単位５０モル％、（ＣＨ₃）₃ＳｉＯ_0.5単位４２．５モル％及びＶｉＭｅ₂ＳｉＯ_0.5単位７．５モル％からなるレジン構造のビニルメチルシロキサン（ＶＭＱ）５０部、下記式

で示されるオルガノハイドロジェンポリシロキサン８部、

で示されるオルガノハイドロジェンポリシロキサン５部、

で示される接着助剤０．３部、及び、塩化白金酸のオクチルアルコール変性溶液０．０５部を加え、よく撹拌し、シリコーンゴム組成物を調製した。この組成物を１５０℃／４ｈｒにて加熱成型して硬化物を形成し、実施例９と同様に測定した結果を表４に示した。硬化物は無色透明であった。このゴム組成物を用いて発光半導体装置を作製した。 [Comparative Example 6]
Following formula

And 50 parts by weight of polysiloxane represented by the formula: Resin-structured vinylmethylsiloxane (VMQ) consisting of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of ViMe ₂ SiO _0.5 units. 50 parts, following formula

8 parts of an organohydrogenpolysiloxane represented by

5 parts of an organohydrogenpolysiloxane represented by

A silicone rubber composition was prepared by adding 0.3 part of an adhesion aid represented by the above and 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid and stirring well. This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the results of measurement similar to Example 9 are shown in Table 4. The cured product was colorless and transparent. A light-emitting semiconductor device was manufactured using this rubber composition.

で示されるポリシロキサン５０部に、ＳｉＯ₂単位５０モル％、（ＣＨ₃）₃ＳｉＯ_0.5単位４２．５モル％及びＶｉＭｅ₂ＳｉＯ_0.5単位７．５モル％からなるレジン構造のビニルメチルシロキサン（ＶＭＱ）５０部、下記式

で示されるオルガノハイドロジェンポリシロキサン３部、

で示されるオルガノハイドロジェンポリシロキサン５部、

で示される接着助剤０．２部、及び、塩化白金酸のオクチルアルコール変性溶液０．０５部を加え、よく撹拌し、シリコーンゴム組成物を調製した。この組成物を１５０℃／４ｈｒにて加熱成型して硬化物を形成し、実施例９と同様に測定した結果を表４に示した。硬化物は無色透明であった。このゴム組成物を用いて発光半導体装置を作製した。 [Comparative Example 7]
Following formula

And 50 parts by weight of polysiloxane represented by the formula: Resin-structured vinylmethylsiloxane (VMQ) consisting of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of ViMe ₂ SiO _0.5 units. 50 parts, following formula

3 parts of an organohydrogenpolysiloxane represented by

5 parts of an organohydrogenpolysiloxane represented by

And 0.2 part of an adhesion assistant represented by the above and 0.05 part of a chloroplatinic acid octyl alcohol-modified solution were added and stirred well to prepare a silicone rubber composition. This composition was heat-molded at 150 ° C./4 hr to form a cured product, and the results of measurement similar to Example 9 are shown in Table 4. The cured product was colorless and transparent. A light-emitting semiconductor device was manufactured using this rubber composition.

[Comparative Example 8]
Commercially available silicone varnish KJR-632 (manufactured by Shin-Etsu Chemical Co., Ltd.) was cured in the same manner to form a cured product, and the results measured in the same manner as in Example 9 are shown in Table 4. The cured product was colorless and transparent. A light emitting semiconductor device was manufactured using this varnish.

The light emitting element was sealed using the silicone rubber compositions and varnishes of Examples 9 to 12 and Comparative Examples 6 to 8, and the characteristics were evaluated.
Table 4 shows the evaluation results of the coating protective materials of Examples 9 to 12 and Comparative Examples 6 to 8.

  As shown in the results of Table 4, the light-emitting semiconductor device coated and protected with the light-emitting semiconductor coating protective material of the present invention has a long life and excellent energy saving because there is little discoloration due to the heat resistance test and high light emission efficiency. An apparatus can be provided, and the industrial merit is great.

It is sectional drawing of the light emitting diode which shows an example (thing by which the light emitting element was die-bonded on the insulating housing | casing) of a surface mount type semiconductor light-emitting device. It is sectional drawing of the light emitting diode which shows the other example (The thing by which the light emitting element was die-bonded on the lead electrode inserted in the housing | casing). It is sectional drawing of the light emitting diode which shows a shell-type semiconductor light-emitting device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Case 2 Light emitting element 3, 4 Lead electrode 5 Die-bonding material 6 Gold wire 7 Covering protective material

Claims (7)

(A) an organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule and having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C.,
(B) Resin-structured organopolysiloxane composed of SiO ₂ units, R ³ _n R ⁴ _p SiO _0.5 units and R ³ _q R ⁴ _r SiO _0.5 units (wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, n is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, q + r = 3.)
(C) an organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule;
(D) A platinum group metal catalyst is contained, and the component (B) is blended in an amount of 20 to 70% by mass with respect to the total amount of the components (A) and (B). A silicone rubber composition. (A) component is the following general formula (1)

(Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² is an unsubstituted or substituted monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond. , K, m is 0 or a positive integer, and k + m is a number that makes the viscosity of this organopolysiloxane at 25 ° C. 10 to 1,000,000 mPa · s.)
The silicone rubber composition according to claim 1, which is an organopolysiloxane represented by the formula:   The silicone rubber composition according to claim 1 or 2, further comprising (E) an adhesion assistant. (E) The adhesion assistant of the component is represented by the following general formula (3)

(Wherein R ⁶ represents the following formula (4)

Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of which is an organic group of the formula (4), and R ⁷ is a hydrogen atom or having 1 to 6 carbon atoms. A monovalent hydrocarbon group, s is an integer of 1-6. )
The silicone rubber composition according to claim 3, which is an isocyanurate compound represented by the formula:   A transparent light-emitting semiconductor coating protective material comprising the silicone rubber composition according to any one of claims 1 to 4.   6. A light emitting semiconductor device in which a light emitting semiconductor element is disposed in a ceramic and / or plastic casing having an opening, and the inside of the casing is covered and protected with a cured product of the covering protective material according to claim 5.   A light emitting semiconductor device in which a light emitting semiconductor element is disposed on a lead electrode in a ceramic and / or plastic casing having an opening, and the inside of the casing is covered and protected with a cured product of the covering protective material according to claim 5. Semiconductor device.

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