JP2012052035A - Addition-curable silicone composition, optical element encapsulating material comprising the composition, and semiconductor device in which optical element is encapsulated with cured product of the optical element encapsulating material - Google Patents

Abstract

（Ｂ）ケイ素に結合した水素原子を１分子あたり少なくとも２つ有し、かつ脂肪族不飽和基を有さない、下記ヒドロシリル化触媒の存在下本組成物を硬化させるのに十分な量の有機ケイ素化合物、
及び
（Ｃ）白金族金属を含むヒドロシリル化触媒
を含む付加硬化型シリコーン組成物。
【選択図】なしAn object of the present invention is to provide an addition-curable silicone resin composition having excellent antisulfurization properties and high light emission efficiency in optical applications.
At least, at least
(A) a compound represented by the following general formula (1),
[Chemical 1]

(B) an amount of organic sufficient to cure the composition in the presence of the following hydrosilylation catalyst having at least two hydrogen atoms bonded to silicon per molecule and having no aliphatic unsaturated group Silicon compounds,
And (C) an addition-curable silicone composition comprising a hydrosilylation catalyst comprising a platinum group metal.
[Selection figure] None

Description

  The present invention relates to an addition-curable type curable silicone composition, and in particular, an addition-curable type silicone composition that is excellent in antisulfurization property and gives a cured product having high luminous efficiency when used for optics, and the composition. The present invention also relates to an optical element sealing material and a semiconductor device using the optical element sealing material.

  The addition-curable silicone composition contains a polyorganosiloxane containing an aliphatic unsaturated group such as an alkenyl group, and is cured by a hydrosilylation reaction to give a cured product. The cured product thus obtained is excellent in heat resistance, cold resistance and electrical insulation, and is transparent, and thus is used for various optical applications.

Silicone resins used for optical applications are required to have high transparency, excellent antisulfurization properties, and high luminous efficiency. To achieve this, dimethylsiloxane-diphenylsiloxane copolymer or polymethylphenylsiloxane is used as the main skeleton. Compositions used for base polymers have been proposed (see, for example, Patent Documents 1 to 7). A composition using a base polymer consisting only of diphenylsiloxane units has also been proposed (see, for example, Patent Document 8).
However, they do not fully satisfy the antisulfurization property and the high luminous efficiency.

JP 2005-307015 A JP 2004-143361 A JP 2004-186168 A JP 2004-292807 A JP 2004-359756 A Japanese Patent Laid-Open No. 2005-076003 JP 2005-105217 A JP 2010-132895 A

  The present invention has been made in view of the above circumstances, and is an addition-curable silicone composition that is excellent in antisulfurization properties and provides high light emission efficiency in optical applications, an optical element sealing material comprising the composition, and the sealing material An object of the present invention is to provide a semiconductor device using this.

（式中、Ｒ^１は脂肪族不飽和基であり、Ｒ^２は互いに同一又は異種の、非置換又は置換可一価炭化水素基であり、Ａｒは同一又は異種の、ヘテロ原子を有してもよい芳香族基である。ｎは１〜５０の整数である。）
（Ｂ）ケイ素に結合した水素原子を１分子あたり少なくとも２つ有し、かつ脂肪族不飽和基を有さない、下記ヒドロシリル化触媒の存在下本組成物を硬化させるのに十分な量の有機ケイ素化合物、
及び
（Ｃ）白金族金属を含むヒドロシリル化触媒
を含む付加硬化型シリコーン組成物を提供する。 In order to solve the above problems, the present invention provides at least
(A) a compound represented by the following general formula (1),

Wherein R ¹ is an aliphatic unsaturated group, R ² is the same or different, unsubstituted or substituted monovalent hydrocarbon group, and Ar has the same or different hetero atom. (N is an integer of 1 to 50.)
(B) an amount of organic sufficient to cure the composition in the presence of the following hydrosilylation catalyst having at least two hydrogen atoms bonded to silicon per molecule and having no aliphatic unsaturated group Silicon compounds,
And (C) an addition-curable silicone composition comprising a hydrosilylation catalyst comprising a platinum group metal.

Thus, in the addition-curable silicone composition of the present invention containing the components (A) to (C), the component (A) has a short main skeleton, the Ar ₂ SiO units are not adjacent to each other, and Since it has a methyl group in the middle, it has excellent antisulfurization properties and can give high luminous efficiency in optical applications.

In this case, in the general formula (1), Ar is preferably a phenyl group.
Thus, if Ar is all phenyl groups, the composition of the present invention can be easily prepared at low cost.

Moreover, as said (B) component, the organohydrogenpolysiloxane represented, for example by the following average compositional formula (2) can be used.
R ³ _a H _b SiO _{(4-ab) / 2} (2)
Wherein R ³ is the same or different from each other, and is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group, and a and b are 0.7 ≦ a ≦ 2.1, 0. (It is a positive number satisfying 001 ≦ b ≦ 1.0 and 0.8 ≦ a + b ≦ 3.0.)

  Thus, for example, if it is organohydrogenpolysiloxane represented by the said average compositional formula (2), it can be used without a restriction | limiting in molecular structure.

  The present invention also provides an optical element sealing material comprising the addition-curable silicone composition, and a semiconductor device in which the optical element is sealed with a cured product of the optical element sealing material.

  The addition-curable silicone composition of the present invention is excellent in antisulfurization properties and provides high luminous efficiency when used for optics, and is therefore suitable for optical applications, particularly as an optical element sealing material. In addition, the semiconductor device in which the optical element is sealed with the cured product of the optical element sealing material of the present invention is excellent in reliability.

  As described above, the cured product obtained by curing the addition-curable silicone composition of the present invention has excellent antisulfurization properties and can provide high luminous efficiency in optical applications. In particular, a semiconductor device using such an optical element sealing material has excellent reliability.

It is sectional drawing which shows typically an example of the light emitting semiconductor device with which the addition-curable silicone composition of this invention is used suitably.

Hereinafter, the present invention will be described in more detail.
As mentioned above, silicone resins using dimethylsiloxane / diphenylsiloxane copolymer or polymethylphenylsiloxane in the main skeleton, which have been used in the past, are excellent in transparency, but are particularly important for optical use as an anti-sulfur property. And with respect to the luminous efficiency, a satisfactory effect has not been obtained.

  Therefore, as a result of intensive studies in view of the above problems, the present inventor has obtained an addition-curable silicone that is excellent in antisulfurization property and provides high luminous efficiency in optical applications by using a siloxane having a specific main skeleton. The inventors have found that a resin can be obtained and have reached the present invention.

（式中、Ｒ^１は脂肪族不飽和基であり、Ｒ^２は互いに同一又は異種の、非置換又は置換可一価炭化水素基であり、Ａｒは同一又は異種の、ヘテロ原子を有してもよい芳香族基である。ｎは１〜５０の整数である。）
（Ｂ）ケイ素に結合した水素原子を１分子あたり少なくとも２つ有し、かつ脂肪族不飽和基を有さない、下記ヒドロシリル化触媒の存在下本組成物を硬化させるのに十分な量の有機ケイ素化合物、
及び
（Ｃ）白金族金属を含むヒドロシリル化触媒
を含むことを特徴とする。 That is, the addition-curable silicone composition of the present invention has at least
(A) a compound represented by the following general formula (1),

Wherein R ¹ is an aliphatic unsaturated group, R ² is the same or different, unsubstituted or substituted monovalent hydrocarbon group, and Ar has the same or different hetero atom. (N is an integer of 1 to 50.)
(B) an amount of organic sufficient to cure the composition in the presence of the following hydrosilylation catalyst having at least two hydrogen atoms bonded to silicon per molecule and having no aliphatic unsaturated group Silicon compounds,
And (C) a hydrosilylation catalyst containing a platinum group metal.

Hereinafter, the present invention will be described in detail.
[(A) component]
The component (A) is a component that functions as a base resin in the present invention, and is a compound represented by the following general formula (1).

As shown in the general formula (1), the component (A) does not have adjacent Ar ₂ SiO units and has a methyl group in the middle of the main skeleton, so it has excellent antisulfurization properties and high light emission in optical applications. It is possible to give efficiency.

In the component (A), in the general formula (1), the aromatic group represented by Ar is an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a heteroatom such as a furanyl group (O, S, N and the like, and the aromatic group may have a substituent such as a halogen atom (for example, a chlorine atom, a bromine atom, or a fluorine atom).
Among them, Ar is preferably an unsubstituted aromatic hydrocarbon group, and particularly preferably a phenyl group.

The aliphatic unsaturated group as R ¹ in the general formula (1) can stably maintain the composition of the present invention in an uncured state before the start of the addition reaction, and after the start of the addition reaction, The composition is not particularly limited as long as the composition can be easily cured, and examples thereof include an ethylenically unsaturated group and an acetylenically unsaturated group.

Here, the “ethylenically unsaturated group” refers to an organic group containing a carbon-carbon double bond and further having a hetero atom such as an oxygen atom or a nitrogen atom. An alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as a group, allyl group, 5-hexenyl group, propenyl group and butenyl group; an alkadienyl group having 4 to 10 carbon atoms such as a 1,3-butadienyl group A combination of the alkenyl group and the carbonyloxy group, such as an acryloyloxy group (—O (O) CCH═CH ₂ ), a methacryloyloxy group (—O (O) CC (CH ₃ ) ═CH ₂ ); A combination of the alkenyl group and the carbonylamino group such as (—NH (O) CCH═CH ₂ ) and the like can be mentioned.

  The “acetylenically unsaturated group” means an organic group containing a carbon-carbon triple bond and further having a heteroatom such as oxygen or nitrogen. Specific examples thereof include an ethynyl group and a propargyl group. And a combination of the alkynyl group and the carbonyloxy group such as an ethynylcarbonyloxy group (—O (O) CC≡CH) and the like.

  Among these, from the viewpoints of productivity and cost when obtaining the raw material of the component (A) and reactivity of the component (A), the aliphatic unsaturated group is preferably the alkenyl group, vinyl group, allyl group. And a 5-hexenyl group are more preferable, and a vinyl group is particularly preferable.

As the unsubstituted or substituted monovalent hydrocarbon group as R ² in the formula (1) of the component (A), the aliphatic unsaturated group specifically exemplified as the aliphatic unsaturated group of R ¹ , and Monovalent hydrocarbon groups other than the aliphatic unsaturated groups, for example, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, etc. An alkyl group having 6 carbon atoms; a haloalkyl group having 1 to 4 carbon atoms such as a chloromethyl group and a 3,3,3-trifluoropropyl group; an aryl group having 6 to 10 carbon atoms such as a phenyl group and a tolyl group. .
Among these, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a vinyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

  n is an integer of 1-50, preferably 1-20, particularly preferably an integer of 1-10. When n exceeds 50, synthesis is difficult and workability of the composition is lowered.

The component (A) is an end-capping agent containing an aliphatic unsaturated group after bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane is hydrolyzed / condensed or simultaneously with hydrolysis / condensation. It can be obtained by sealing the end.
In addition, (A) component may be used individually by 1 type, or may be used in combination of 2 or more types from which a polymerization degree and a substituent differ.

[Component (B)]
Component (B) is an organosilicon compound having a hydrogen atom bonded to at least two silicon atoms per molecule (that is, a SiH group) and having no aliphatic unsaturated group (SiH group-containing organic compound). And hydrosilylation addition reaction with the component (A) to act as a crosslinking agent.
(B) A component may be used individually by 1 type, or may use 2 or more types together.

  The organic group bonded to silicon in the component (B) is an unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated group, or adversely affects the storage stability and curing of the composition of the present invention. None, halogen atom (for example, chlorine atom, bromine atom, fluorine atom), epoxy group-containing group (for example, epoxy group, glycidyl group, glycidoxy group), alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group) A monovalent hydrocarbon group substituted with) or the like is preferred.

Specific examples of such a monovalent hydrocarbon group include, for example, “unsubstituted or substituted monovalent hydrocarbon group other than aliphatic unsaturated group” as R ² in formula (1) of the component (A). And an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
Among them, the organic group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group or a phenyl group.
Moreover, when it has an epoxy group containing group and / or an alkoxy group as a substituent of the said monovalent hydrocarbon group, adhesiveness can be provided to the hardened | cured material of this invention composition.

  As the organosilicon compound of component (B) having such an organic group, any known compound can be used as long as it is an organosilicon compound having at least two SiH groups per molecule. Examples thereof include organohydrogenpolysiloxanes, organohydrogensilanes, organic oligomers or organic polymers having at least two SiH groups per molecule.

Among these, organohydrogenpolysiloxane having at least 2 SiH groups per molecule is preferable.
As long as the component (B) is an organohydrogenpolysiloxane having at least two SiH groups per molecule, the molecular structure of the organohydrogenpolysiloxane is not particularly limited. For example, linear, cyclic, branched chain Various organohydrogenpolysiloxanes produced in the past, such as a shape and a three-dimensional network structure (resinous) can be used.

  The organohydrogenpolysiloxane contains at least 2 (usually about 2 to 200), preferably 3 or more (usually 3 to 100, preferably about 4 to 50) SiH groups in one molecule. Have. When the organohydrogenpolysiloxane has a linear structure or a branched structure, these SiH groups may be located only in either one of the molecular chain terminal and the molecular chain non-terminal part, or both. May be located.

  The number (degree of polymerization) of silicon atoms in one molecule of the organohydrogenpolysiloxane is preferably 2 to 200, more preferably 3 to 100, and even more preferably about 4 to 50. Further, the organohydrogenpolysiloxane is preferably liquid at 25 ° C., and the viscosity at 25 ° C. measured by a rotational viscometer is preferably 1 to 1,000 mPa · s, more preferably 10 to 100 mPa · s. Degree.

As said organohydrogenpolysiloxane, what is represented by the following average compositional formula (2) can be used, for example.
R ³ _a H _b SiO _{(4-ab) / 2} (2)
Wherein R ³ is the same or different from each other, and is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group, and a and b are 0.7 ≦ a ≦ 2.1, 0. 001 ≦ b ≦ 1.0 and 0.8 ≦ a + b ≦ 3.0, preferably 1.0 ≦ a ≦ 2.0, 0.01 ≦ b ≦ 1.0, and 1.5 ≦ a + b ≦ 2. (It is a positive number satisfying 5.)

As R ³ , for example, a carbon atom specifically exemplified as “an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group” as R ² in formula (1) in the component (A) Examples thereof include an alkyl group or a haloalkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
Among them, R ³ is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group or a phenyl group.

Examples of the organohydrogensiloxane represented by the above average composition formula (2) include, for example, a cyclic compound including at least four organohydrogensiloxane units represented by the formula: R ³ HSiO, formula: R ³ ₃ SiO (HR ³ SiO) _c SiR ³ ₃ compound, formula: HR ³ ₂ SiO (HR ³ SiO) _c SiR ³ ₂ H compound, formula: HR ³ ₂ SiO (HR ³ SiO) _c (R ³ ₂ SiO) _d SiR ³ ₂ H and the like. In the above formula, R ³ is as described above, and c and d are at least 1.

Alternatively, the organohydrogensiloxane represented by the above average composition formula (2) is a siloxane unit represented by the formula: HSiO _1.5 , a siloxane unit represented by the formula: R ³ HSiO, and / or a formula: R ^3. _It may contain a siloxane unit represented by ₂ HSiO _0.5 . Further, it may further contain a _{monoorganosiloxane} unit not containing a SiH group, a diorganosiloxane unit, a triorganosiloxane unit and / or a SiO _4/2 unit (R ³ in the above formula is as described above). .

  Especially, it is preferable that 30-100 mol% is a methylhydrogensiloxane unit among all the organosiloxane units contained in the organohydrogensiloxane represented by the said average compositional formula (2).

  When the component (B) is an organohydrogenpolysiloxane having at least two SiH groups per molecule, specific examples thereof include 1,1,3,3-tetramethyldisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, both ends of molecular chain Trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked diphenylsiloxane / methyl Idrogen siloxane copolymer, molecular chain both ends trimethylsiloxy group-capped methylphenylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, Molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / diphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpoly Siloxane, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, dimethylhydride at both ends of molecular chain Gensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane, molecular chain Examples thereof include a dimethylhydrogensiloxy group-capped diphenylpolysiloxane having both ends and a dimethylhydrogensiloxy group-capped diphenylsiloxane / methylhydrogensiloxane copolymer having both molecular chains.

In each of the above exemplary compounds, an organohydrogenpolysiloxane in which part or all of the methyl group is substituted with another alkyl group such as an ethyl group or a propyl group, represented by the formula: R ³ ₃ SiO _0.5 An organosiloxane copolymer comprising a siloxane unit and a siloxane unit represented by the formula: R ³ ₂ HSiO _0.5 and a siloxane unit represented by the formula: SiO ₂ , represented by the formula: R ³ ₂ HSiO _0.5 An organosiloxane copolymer comprising a siloxane unit represented by formula: SiO ₂ , a siloxane unit represented by formula: R ³ HSiO, a siloxane unit represented by formula: R ³ SiO _1.5 , and formula: organosiloxane copolymers consisting of one or both of the siloxane units represented by HSiO _1.5, and these Olga Mixtures of two or more of the polysiloxanes.
In the above formula, R ³ has the same meaning as described above.

  The blending amount of the component (B) may be an amount sufficient to cure the present composition in the presence of the hydrosilylation catalyst of the component (C). Usually, the aliphatic unsaturated group in the component (A) The molar ratio of the SiH group in the component (B) to 0.2 to 5, preferably 0.5 to 2.

[Component (C)]
(C) The platinum group metal hydrosilylation catalyst of component (C) is one that promotes the hydrosilylation addition reaction between the silicon-bonded aliphatic unsaturated group in component (A) and the SiH group in component (B). Any catalyst may be used. (C) A component may be used individually by 1 type, or may use 2 or more types together.

  Examples of the component (C) include platinum group metals such as platinum, palladium and rhodium; chloroplatinic acid; alcohol-modified chloroplatinic acid; coordination compound of chloroplatinic acid and olefins, vinylsiloxane or acetylene compound; Examples include platinum group metal compounds such as triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, with platinum compounds being particularly preferred.

  The compounding amount of the component (C) may be an effective amount (catalytic amount) as a hydrosilylation catalyst, and is preferably 0.1 in terms of the mass of the platinum group metal element with respect to the total mass of the components (A) and (B). It is the range of -1000 ppm, More preferably, it is the range of 1-500 ppm.

[Other ingredients]
In addition to the components (A) to (C), the composition of the present invention can contain other optional components as long as the object of the present invention is not impaired. Specific examples thereof include the following. Each of these other components may be used alone or in combination of two or more.
<Aliphatic unsaturated group-containing compound other than component (A)>
In addition to the component (A), the composition of the present invention may contain an aliphatic unsaturated group-containing compound that undergoes an addition reaction with the component (B). As such an aliphatic unsaturated group-containing compound other than the component (A), a compound involved in the formation of a cured product is preferable. For example, other than the component (A) having at least two aliphatic unsaturated groups per molecule Of polyorganosiloxane. The molecular structure may be any of linear, cyclic, branched, three-dimensional network, etc.

For example, it is also possible to mix | blend an aliphatic unsaturated group containing organic compound other than the said polyorganosiloxane. Specific examples of the organic compound containing an aliphatic unsaturated group include monomers such as butadiene and diacrylates derived from polyfunctional alcohols; polyethylene, polypropylene or styrene and other ethylenically unsaturated compounds (for example, acrylonitrile or butadiene). And the like, and oligomers or polymers derived from functionally substituted organic compounds such as esters of acrylic acid, methacrylic acid, or maleic acid.
The aliphatic unsaturated group-containing compound other than the component (A) may be liquid or solid at room temperature.

<Addition reaction control agent>
In order to ensure the pot life, an addition reaction control agent may be added to the composition of the present invention. The addition reaction control agent is not particularly limited as long as it is a compound having a curing inhibitory effect on the hydrosilylation catalyst of the component (C), and conventionally known ones can also be used.
Specific examples thereof include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; sulfur-containing compounds; acetylene alcohols (for example, 1-ethynylcyclohexanol, 3,5- Acetylene compounds such as dimethyl-1-hexyn-3-ol); compounds containing two or more alkenyl groups; hydroperoxy compounds; and maleic acid derivatives.

  The degree of the curing inhibitory effect of the addition reaction control agent varies depending on the chemical structure of the addition reaction control agent. Therefore, it is preferable to adjust the addition amount to an optimum amount for each of the addition reaction control agents to be used. By adding an optimal amount of addition reaction control agent, the composition has excellent long-term storage stability at room temperature and heat curability.

<Other optional components>
In addition, a conventionally known antioxidant such as 2,6-di-t-butyl-4-methylphenol is added to the composition of the present invention in order to suppress the occurrence of coloring, white turbidity, oxidative degradation, etc. of the cured product. can do. In addition, a light stabilizer such as a hindered amine stabilizer can be added to the composition of the present invention in order to impart resistance to light deterioration. Furthermore, an inorganic filler such as fumed silica may be added to the composition of the present invention in order to improve the strength as long as the transparency of the cured product obtained from the composition of the present invention is not affected. Depending on the case, dyes, pigments, flame retardants and the like may be added to the composition of the present invention.

  The composition of the present invention containing such components can be cured by a known curing method under known curing conditions. Specifically, the composition can be cured usually by heating at 80 to 200 ° C, preferably 100 to 160 ° C. The heating time may be about 0.5 minutes to 5 hours, particularly about 1 minute to 3 hours, but when accuracy such as LED sealing is required, it is preferable to lengthen the curing time.

  The cured product of the composition of the present invention is excellent in antisulfurization properties and light emission efficiency in optical applications, and is excellent in heat resistance, cold resistance, and electrical insulation in the same manner as a cured product of a normal addition-curable silicone composition. Therefore, it is suitable for various optical applications, particularly as an optical element sealing material. As an optical element sealed with the sealing material (optical element sealing material of the present invention) comprising the composition of the present invention, for example, an LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, a CCD, and the like can be given. It is done.

  In the semiconductor device of the present invention, the sealing material comprising the composition of the present invention is applied to the optical element, and the applied sealing agent is specifically described above by a known curing method under known curing conditions. It can be obtained by curing and sealing as described above.

EXAMPLES Hereinafter, although a preparation example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following example etc.
In the following examples, the viscosity is a value measured at 25 ° C. using a rotational viscometer.
[Preparation Example 1]
Compound represented by the following formula (hereinafter referred to as “compound A”) (viscosity 2 Pa · s) 100 parts by mass; viscosity 0.02 Pa · s, average composition formula HMe ₂ SiO (MeHSiO) ₂ (Ph ₂ SiO) ₂ 41 parts by mass of organohydrogenpolysiloxane represented by SiMe ₂ H; 0.14 parts by mass of toluene solution containing 1% by mass of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as platinum atom content; control A silicone composition (I) was prepared by uniformly mixing 0.05 parts by mass of ethynylcyclohexanol as an agent; and 3 parts by mass of γ-glycidoxypropyltrimethoxysilane. When the silicone composition (I) was cured by heating at 150 ° C. for 4 hours, the hardness was 66 for Type A.

[Preparation Example 2]
Compound A26 parts by mass; average composition formula (PhSiO _3/2 ) _0.75 [(CH ₂ ═CH) Me ₂ SiO _0.5 ] _0.25 Solid branched organopolysiloxane represented by _0.25 [silicon atom Bonded vinyl group content = 17 mol%, silicon atom bonded phenyl group content in all silicon atom bonded organic groups = 50 mol%, standard styrene equivalent weight average molecular weight = 1600] 74 parts by mass; average composition formula HMe ₂ SiO (Ph ₂ SiO) ₁ SiMe ₂ H organohydrogenpolysiloxane 32 parts by mass; chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex containing 1% by mass as a platinum atom 0.13 parts by mass of solution; 0.05 parts by mass of ethynylcyclohexanol; and γ-glycidoxypropyltrimethoxysilane A silicone composition (II) was prepared by uniformly mixing an amount part. When this silicone composition (II) was cured by heating at 150 ° C. for 4 hours, the hardness was 43 in Shore D.

[Preparation Example 3]
Compound A 80 parts by mass; average composition formula (PhSiO _3/2 ) _0.75 [(CH ₂ ═CH) Me ₂ SiO _0.5 ] _0.25 Solid branched organopolysiloxane represented by _0.25 [silicon atom Bonded vinyl group content = 17 mol%, silicon atom bonded phenyl group content in all silicon atom bonded organic groups = 50 mol%, standard styrene equivalent weight average molecular weight = 1600] 20 parts by mass; average composition formula HMe 32 parts by mass of an organohydrogenpolysiloxane represented by ₂ SiO (MeHSiO) ₂ (Ph ₂ SiO) ₂ SiMe ₂ H; 1 mass in terms of platinum atom content of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex % Toluene solution containing 0.13 parts by mass; ethynylcyclohexanol 0.05 parts by mass; and γ-glycidoxypropyl They were uniformly mixed silane 3 parts by weight, the silicone composition (III) was prepared. When the silicone composition (III) was cured by heating at 150 ° C. for 4 hours, the hardness was 50 in Shore D.

[Preparation Example 4]
Compound represented by the following formula (hereinafter referred to as “compound B”) (viscosity 6 Pa · s) 100 parts by mass; viscosity 0.02 Pa · s, average composition formula HMe ₂ SiO (MeHSiO) ₂ (Ph ₂ SiO) ₂ 26 parts by mass of organohydrogenpolysiloxane represented by SiMe ₂ H; 0.14 parts by mass of toluene solution containing 1% by mass of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as platinum atom content; control A silicone composition (IV) was prepared by uniformly mixing 0.05 parts by mass of ethynylcyclohexanol as an agent; and 3 parts by mass of γ-glycidoxypropyltrimethoxysilane. When this silicone composition (IV) was cured by heating at 150 ° C. for 4 hours, the hardness was 50 in Type A.

[Comparative Preparation Example 1]
Instead of compound A, a compound represented by the following formula (hereinafter referred to as “compound C”) (viscosity 2 Pa · s) was used according to Example 1 except that 100 parts by mass was used, and composition (V) was prepared. Prepared. When the silicone composition (V) was cured by heating at 150 ° C. for 4 hours, the hardness was 66 for Type A.

[Comparative Preparation Example 2]
Instead of compound A, compound (VI) was prepared by blending according to Example 2 except that 26 parts by mass of compound C was used. When the silicone composition (VI) was cured by heating at 150 ° C. for 4 hours, the hardness was 43 in Shore D.

[Comparative Preparation Example 3]
A composition (VII) was prepared by blending according to Example 3 except that 80 parts by mass of Compound C was used instead of Compound A. When the silicone composition (VII) was cured by heating at 150 ° C. for 4 hours, the hardness was 50 in Shore D.

[Comparative Preparation Example 4]
Viscosity 4.0 Pa · s, average composition formula ViMe ₂ SiO (Me ₂ SiO) ₆₈ (Ph ₂ SiO) ₃₀ SiMe ₂ Vi 50 parts by mass of silicone oil; viscosity 2.0 Pa · s, average composition formula Me ₃ SiO (Me ₂ SiO) _3.4 (ViMeSiO) _6.5 (Ph ₂ SiO) _8.6 50 parts by mass of silicone oil represented by SiMe ₃ ; viscosity 0.02 Pa · s, average composition formula HMe ₂ SiO (MeHSiO) ) 19 (parts by mass) of organohydrogenpolysiloxane represented by ₂ (Ph ₂ SiO) ₂ SiMe ₂ H; toluene containing 1% by mass of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as platinum atom content 0.13 parts by weight of solution; 0.05 parts by weight of ethynylcyclohexanol; and γ-glycidoxypropyl Were uniformly mixed to trimethoxysilane 3 parts by weight, the silicone composition (VIII) was prepared. When this silicone composition (VIII) was cured by heating at 150 ° C. for 4 hours, the hardness was 38 in Type A.

[Examples 1-4, Comparative Examples 1-4]
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 to a glass fiber reinforced epoxy resin casing 1 having a pair of lead electrodes 3 and 4 by heating at 180 ° C. for 10 minutes using a silicone die bond material 5. After the light emitting element 2 and the lead electrodes 3 and 4 were connected by the gold wire 6, the covering protective material (sealing material) 7 was potted and cured at 180 ° C. for 1 hour to produce a light emitting semiconductor device.
In addition, as the coating protective material (sealing material) 7, the silicone compositions obtained in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 4 were used.

Method of Measuring Luminance of Light-Emitting Semiconductor Device A constant current was passed through the light-emitting semiconductor device manufactured by the above-described protection method, and the luminance was measured by obtaining the output current value of the light receiving element 5 seconds after the current application as the luminance (the light emission of Example 1). It was obtained by a comparative value where the luminance of the semiconductor device was 1.00). The results are shown in Table 1.

Sulfur exposure test This composition is press-molded on a silver-plated copper plate (film thickness: about 1.5 mm, 150 ° C. for 10 minutes), and then cured by post-curing (150 ° C. for 3 hours) for sulfur exposure. A test piece was prepared. The test piece was put in a 100 g glass bottle containing 0.2 g of sulfur powder, and after sealing, stored in an environment of 80 ° C. for 72 hours, and the appearance was observed. The results are shown in Table 1.
In Table 1, ○: no corrosion, x: corrosion (blackening).

As shown in Table 1, Examples 1 to 4 were excellent in antisulfurization properties and provided high luminous efficiency.
On the other hand, although Comparative Examples 1-3 were excellent in sulfidation prevention property, they were inferior in luminous efficiency. Moreover, although the comparative example 4 gave high luminous efficiency, it was inferior to sulfidation prevention property.

That is, if the main skeleton of the base resin component (component (A)) is short, the Ar ₂ SiO units are not adjacent to each other, and has a methyl group in the middle as in the present invention, the sulfuration prevention It has been found that it has excellent properties and can give high luminous efficiency in optical applications.

  From the above, the addition-curable silicone composition of the present invention is suitable for various optical applications because the cured product has excellent antisulfurization properties and provides high luminous efficiency when used for optics. It was proved that.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

DESCRIPTION OF SYMBOLS 1 ... Housing | casing 2 ... Light emitting element 3, 4 ... Lead electrode 5 ... Die-bonding material,
6 ... gold wire, 7 ... coating protective material (sealing material).

Silicone resins used for optical applications are required to have high transparency, excellent sulfidation resistance, and high luminous efficiency. To achieve this, dimethylsiloxane / diphenylsiloxane copolymer or polymethyl is used as the main skeleton of the base polymer. compositions had use of siloxanes has been proposed (e.g. see Patent Document 1-7). A composition using a base polymer consisting only of diphenylsiloxane units has also been proposed (see, for example, Patent Document 8).
However, they do not fully satisfy the antisulfurization property and the high luminous efficiency.

Claims (5)

at least,
(A) a compound represented by the following general formula (1),

Wherein R ¹ is an aliphatic unsaturated group, R ² is the same or different, unsubstituted or substituted monovalent hydrocarbon group, and Ar has the same or different hetero atom. (N is an integer of 1 to 50.)
(B) an amount of organic sufficient to cure the composition in the presence of the following hydrosilylation catalyst having at least two hydrogen atoms bonded to silicon per molecule and having no aliphatic unsaturated group Silicon compounds,
And (C) an addition-curable silicone composition comprising a hydrosilylation catalyst comprising a platinum group metal.   The addition-curable silicone composition according to claim 1, wherein Ar in the general formula (1) is a phenyl group. The addition-curable silicone composition according to claim 1 or 2, wherein the component (B) is an organohydrogenpolysiloxane represented by the following average composition formula (2).
R ³ _a H _b SiO _{(4-ab) / 2} (2)
Wherein R ³ is the same or different from each other, and is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group, and a and b are 0.7 ≦ a ≦ 2.1, 0. (It is a positive number satisfying 001 ≦ b ≦ 1.0 and 0.8 ≦ a + b ≦ 3.0.)   An optical element sealing material comprising the addition-curable silicone composition according to any one of claims 1 to 3.   A semiconductor device in which an optical element is sealed with a cured product of the optical element sealing material according to claim 4.

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