JP2012251166A - Highly transparent silicone composition and light-emitting semiconductor device sealed with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone composition that is made by compounding silica particles in the silicone composition and gives a cured substance having a small expansion coefficient and small gas permeability while maintaining transparency, and to provide an excellently reliable light-emitting semiconductor device such as LED or the like which shows excellence in impact resistance and temperature cycle resistance by being sealed with the cured substance, and whose sealed component such as an LED chip or the like seal-protected from corrosion due to permeation of corrosive gas is prevented from the corrosion.SOLUTION: The highly transparent silicone composition includes on the surface the silica particles which are grafted with 4% or more of organopolysiloxane represented by general formula (1) based on the mass of silica before treatment, wherein Ris a 1-10C non-substituted or substituted monovalent hydrocarbon group and may be identical or different from each other; Ris a methyl group or ethyl group; and a is an integer of 1 to 50, b is 0 or 1, d is 0 or 1, c and e are integers of 0 to 10, and a+b+d is an integer of 3 to 52. The silicone composition in which the silica particles are compounded gives the cured substance showing high transparency, little permeation of corrosive gas and an excellent coating protective property, and is suitable for sealing light-emitting semiconductor devices.

Description

  The present invention relates to a silicone composition that gives a cured product in which gas permeability such as oxygen is lowered while maintaining transparency by filling a large amount of silica particles grafted with a specific organopolysiloxane on the surface, particularly The present invention relates to a silicone composition optimal for sealing an optical semiconductor device typified by an LED or the like, and a light-emitting semiconductor device sealed with a cured product thereof.

  Silicone compositions are used for various applications because they form cured products having excellent properties such as weather resistance, heat resistance, transparency, and rubber properties such as hardness and elongation. In particular, silicone resin has recently been widely applied as a sealing material for light-emitting semiconductor devices such as blue and white high-brightness LEDs because of its excellent heat resistance and ultraviolet resistance. However, since conventional silicone resins have a large expansion coefficient and gas permeability, cracks are likely to occur in the resin due to temperature cycles, and problems such as disconnection occur. Moreover, the silicone resin sealed with corrosive gas is permeated to corrode the silver surface of a light reflecting plate such as an LED, thereby reducing the luminance.

  In addition, the following is mentioned as a prior art relevant to this invention.

JP 2005-524737 A JP 2004-179644 A Japanese Patent Laid-Open No. 10-284759

  The present invention has been made in view of the above circumstances, and a silicone composition containing silica particles blended with a silicone composition to give a cured product having a low expansion coefficient and gas permeability while maintaining transparency, and the cured product LED with excellent reliability, such as LED chip, which has excellent impact resistance and temperature cycle resistance by sealing with, and prevents corrosion of sealed components such as LED chips that are sealed and protected by permeation of corrosive gas An object of the present invention is to provide a light emitting semiconductor device.

  As a result of intensive studies to achieve the above object, the present inventors have found that the total of the silane and siloxane components in the addition-curable or condensation-curable silicone composition (that is, the alkenyl group-containing component (A) described later) Total of organopolysiloxane and (B) component organohydrogenpolysiloxane, or (D) component hydroxyl group or hydrolyzable group-capped organopolysiloxane and (E) component hydrolyzable group-containing silane and / or Or the total of the partially hydrolyzed condensate thereof) with respect to 100 parts by mass, 5 to 400 parts by mass, in particular 50 to 250 parts, of silica particles grafted with an organopolysiloxane represented by the following general formula (1) By adding 100 parts by mass, and further 100 to 200 parts by mass, a cured product having high transparency and low expansion coefficient and corrosive gas permeability. It can be formed and sealed with this cured product, which has excellent impact resistance and temperature cycle resistance. For example, light emission from highly reliable LEDs, etc. in which corrosion of the silver surface of the light reflector due to transmission of corrosive gas is prevented The inventors have found that a semiconductor device can be obtained, and have made the present invention.

（式中、Ｒ¹は互いに同一又は異種の炭素数１〜１０の非置換又は置換の一価炭化水素基、Ｒ²はメチル基又はエチル基、ａは１〜５０、ｂは０又は１、ｄは０又は１、ｃ及びｅは０〜１０の整数であり、ａ＋ｂ＋ｄは３〜５２の整数を示す。）
〔２〕 硬化物が４００〜８００ｎｍで８０％以上の光透過率を有する〔１〕記載のシリコーン組成物。
〔３〕 付加硬化型シリコーン組成物が、
（Ａ）アルケニル基含有オルガノポリシロキサン、
（Ｂ）オルガノハイドロジェンポリシロキサン、
（Ｃ）白金族金属系触媒
を含有することを特徴とする〔１〕又は〔２〕記載のシリコーン組成物。
〔４〕 縮合硬化型シリコーン組成物が、
（Ｄ）分子鎖末端が水酸基又は加水分解性基で封鎖されたオルガノポリシロキサン、
（Ｅ）珪素原子に結合した加水分解可能な基を１分子中に３個以上有するシランもしくはその部分加水分解縮合物、
（Ｆ）縮合触媒
を含有することを特徴とする〔１〕又は〔２〕記載のシリコーン組成物。
〔５〕 更に、蛍光体を含有する〔１〕〜〔４〕のいずれかに記載のシリコーン組成物。
〔６〕 シリカ粒子の平均粒径が１ｎｍ以上１，０００ｎｍ未満である〔１〕〜〔５〕のいずれかに記載のシリコーン組成物。
〔７〕 〔１〕〜〔６〕のいずれかに記載のシリコーン組成物の硬化物で封止した発光半導体装置。 Accordingly, the present invention provides a silicone composition and a light emitting semiconductor device containing the following silica particles.
[1] With respect to a total of 100 parts by mass of the silane and siloxane components in the addition-curable or condensation-curable silicone composition, the surface is treated with an organopolysiloxane represented by the following general formula (1) based on the silica mass before treatment. A highly transparent silicone composition comprising 5 to 400 parts by mass of silica particles grafted at least 4%.

(Wherein R ¹ is the same or different from each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is a methyl group or an ethyl group, a is 1 to 50, b is 0 or 1, d is 0 or 1, c and e are integers of 0 to 10, and a + b + d is an integer of 3 to 52.)
[2] The silicone composition according to [1], wherein the cured product has a light transmittance of 80% or more at 400 to 800 nm.
[3] An addition-curable silicone composition is
(A) an alkenyl group-containing organopolysiloxane,
(B) organohydrogenpolysiloxane,
(C) The silicone composition according to [1] or [2], which contains a platinum group metal catalyst.
[4] A condensation-curable silicone composition is
(D) an organopolysiloxane whose molecular chain end is blocked with a hydroxyl group or a hydrolyzable group,
(E) a silane having three or more hydrolyzable groups bonded to a silicon atom in one molecule or a partially hydrolyzed condensate thereof,
(F) The silicone composition according to [1] or [2], comprising a condensation catalyst.
[5] The silicone composition according to any one of [1] to [4], further containing a phosphor.
[6] The silicone composition according to any one of [1] to [5], wherein the silica particles have an average particle size of 1 nm or more and less than 1,000 nm.
[7] A light emitting semiconductor device sealed with a cured product of the silicone composition according to any one of [1] to [6].

  According to the present invention, it is suitable for sealing a light emitting semiconductor device that is blended with a silicone composition and blended with silica particles that are highly transparent, have a low corrosive gas permeability, and provide a cured product with excellent coating protection. A silicone composition can be provided.

  Silica grafted with siloxane according to the present invention is obtained by grafting an organopolysiloxane represented by the following general formula (1) to silica.

  Typical examples of the silica to be used include nano-sized (that is, an average particle diameter of 1 nm or more and less than 1,000 nm, preferably 5 to 500 nm, more preferably 10 to 200 nm), wet or dry fumed silica, fused silica, and the like. It is a thing. For example, Aerosil 200 (average particle size: 12 nm) of Nippon Aerosil Co., Ltd. Hydrosil surface-treated silica such as Aerosil 300, Aerosil RX300, Leorosil HM-30S manufactured by Tokuyama, and Admafine (Co., Ltd.) classified to 200 nm or less Admatechs) can be used.

  Conventionally, high-strength silicone resins using various coupling materials and silica surface-treated with organopolysiloxane are known (for example, Japanese Patent No. 3029680). All of these have obtained a high-strength silicone resin by kneading silica, a silicone compound having a specific structure, and a silicone resin with a kneader and heat-treating them. Specific silicone compounds used individually are compounds with a degree of polymerization of 4. Also, this type of silicone resin cannot be obtained with good transparency.

  In the present invention, silica particles obtained by reliably grafting the organopolysiloxane represented by the following general formula (1) onto the silica surface are used. When grafting is insufficient, transparency in a low wavelength region may not be ensured.

（式中、Ｒ¹は互いに同一又は異種の炭素数１〜１０の非置換又は置換の一価炭化水素基、Ｒ²はメチル基又はエチル基、ａは１〜５０、ｂは０又は１、ｄは０又は１、ｃ及びｅは０〜１０の整数であり、ａ＋ｂ＋ｄは３〜５２の整数を示す。）

(Wherein R ¹ is the same or different from each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is a methyl group or an ethyl group, a is 1 to 50, b is 0 or 1, d is 0 or 1, c and e are integers of 0 to 10, and a + b + d is an integer of 3 to 52.)

In this case, as R ¹ , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, Alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, vinyl group, allyl group, propenyl group, isopropenyl group Alkenyl groups such as butenyl group, hexenyl group, cyclohexenyl group, octenyl group, etc., and those in which part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, cyano groups, etc., for example Chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyano Chill group, and the like.

Specific examples of the organopolysiloxane used for the surface treatment include the following.

  The organopolysiloxane described above must have a degree of polymerization (or the number of silicon atoms present in the siloxane units constituting the main chain) of 5 or more and 54 or less. If it is less than 5, sufficient light transmittance cannot be obtained even if the grafted silica is mixed with the silicone composition. Moreover, since reaction with a silica surface will not advance easily when it exceeds 54, there exists a problem of having a long time. The degree of polymerization is preferably 6 to 44, more preferably 10 to 34.

  In addition, when the silicone composition used is a composition mainly composed of dimethylpolysiloxane as an organopolysiloxane, in order to obtain good light transmittance, the substituent in which the organopolysiloxane to be grafted is substituted with silicon is a methyl group or Those mainly composed of an ethyl group or the like are preferable. On the other hand, in a silicone composition using an organopolysiloxane whose main substituent is a phenyl group, it is preferable that the ratio of the phenyl group of the organopolysiloxane to be grafted is matched to the ratio of the composition.

  In a silicone composition that cures by an addition reaction, if the organopolysiloxane to be grafted contains a vinyl group, both light transmittance and strength can be achieved.

  The graft reaction of the organopolysiloxane onto the surface of the silica particles can be generally carried out by putting the surface treatment agent and silica in a solvent and refluxing at a temperature of 50 to 200 ° C. for 1 to 50 hours.

  As typical solvents, aromatic solvents such as toluene and xylene, alcohols such as methanol, ethanol and isopropyl alcohol, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used. You may mix this kind of solvent and adjust reflux temperature to 50-200 degreeC. Furthermore, other solvents can be used if there is no problem.

  In the grafting reaction, it is preferable to mix and react at a ratio of 10 to 50 parts by mass of the processing agent and 100 to 500 parts by mass of the solvent with respect to 100 parts by mass of silica. If the amount of the treatment material is less than 10 parts by mass, the target grafting rate may not be achieved. Moreover, when it exceeds 50 mass parts, it will cost too much for the grafting rate, and the case where it does not match economically arises.

  Silica particles grafted with organopolysiloxane on the surface can be easily obtained by separating the solvent and particles by centrifugation after the reaction is completed and drying.

  In order to obtain high transparency, the grafting rate of the treatment agent on the silica surface is preferably 4% or more with respect to the mass of the silica before the surface treatment. More preferably, it is 4-30%, More preferably, it is 5-15%. If this is insufficient, sufficient transparency cannot be obtained even if the surface-treated silica is filled in the silicone resin. This grafting rate can be achieved by selecting the type of silica, the type of organopolysiloxane of formula (1), the amount used, and the like.

The silicone composition of the present invention is a blend of silica grafted with the above organopolysiloxane. In this case, the silicone composition is preferably an addition curable type or a condensation curable type. As an addition-curable silicone composition,
(A) an alkenyl group-containing organopolysiloxane,
(B) organohydrogenpolysiloxane,
(C) A platinum group metal catalyst is contained as an essential component.

Here, as the alkenyl group-containing organopolysiloxane of component (A), an organopolysiloxane containing two or more alkenyl groups bonded to a silicon atom in one molecule is used. This is an addition-curable silicone composition. It is a well-known organopolysiloxane used as a base polymer, and its weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) is usually about 3,000 to 300,000, and 100 to 100 at room temperature (25 ° C.). Those having a viscosity of about 1,000,000 mPa · s, particularly about 200 to 100,000 mPa · s are preferred, and those represented by the following average composition formula (2) are used. This viscosity is a value measured by a rotational viscometer.
R ³ _a SiO _{(4-a) / 2} (2)
(In the formula, R ³ is an identical or different monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and a is 1.5 to 2.8, preferably 1 .8 to 2.5, more preferably a positive number in the range of 1.95 to 2.05.)

Examples of the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, and a pentyl group. , Neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl group, etc. Aralkyl groups such as aralkyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, octenyl groups, etc., and some or all of the hydrogen atoms of these groups are fluorine, bromine Substituted with a halogen atom such as chlorine, cyano group, etc., such as chloromethyl group, chloropropylene Group, bromoethyl group, trifluoropropyl group, cyanoethyl group and the like.

In this case, at least two of R ³ must be alkenyl groups (particularly those having 2 to 8 carbon atoms are preferred, more preferably 2 to 6). The content of the alkenyl group is 0.01 to 20 in the total organic group bonded to the silicon atom (that is, in the unsubstituted or substituted monovalent hydrocarbon group as R ³ in the average composition formula (2)). It is preferable to set it as mol%, especially 0.1-10 mol%. The alkenyl group may be bonded to the silicon atom at the end of the molecular chain, bonded to the silicon atom in the middle of the molecular chain, or bonded to both. From the viewpoint of physical properties and the like, the organopolysiloxane used in the present invention preferably contains at least an alkenyl group bonded to a silicon atom at the molecular chain terminal.

The structure of the above-mentioned organopolysiloxane usually has a main chain consisting of repeating diorganosiloxane units ((R ³ ) ₂ SiO _2/2 units), and both ends of the molecular chain are triorganosiloxy groups ((R ³ ) ₃ SiO basically blocked with _1/2 unit) is a diorganopolysiloxane having a linear structure, in part branched containing R ³ SiO _3/2 units and SiO _4/2 units It may be a structure, a ring structure, or the like.

  The substituent for the silicon atom may be basically any of the above, but the alkenyl group is preferably a vinyl group, and the other substituents are preferably a methyl group or a phenyl group.

  Examples of the component (A) include compounds represented by the following general formula.

R in the above general formula is the same as R ³ , but does not include an alkenyl group. m and n are integers of m ≧ 1 and n ≧ 0, and are numbers having the above-described values for the weight average molecular weight or viscosity of the organopolysiloxane.

In the present invention, an organopolysiloxane having a resin structure can be used in combination with the above organopolysiloxane. The organopolysiloxane having this resin structure (that is, a three-dimensional network structure) is an organopolysiloxane having a resin structure composed of SiO ₂ units, R ⁴ _k R ⁵ _p SiO _0.5 units and R ⁴ _q R ⁵ _r SiO _0.5 units (provided that In the above formula, R ⁴ is a vinyl group or an allyl group, R ⁵ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, k is 2 or 3, p is 0 or 1, and k + p = 3, q is preferably 0 or 1, r is 2 or 3, and q + r = 3). Examples of the monovalent hydrocarbon group for R ⁵ include those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, similar to the above R ³ .

Here, the resin-structured organopolysiloxane is composed of SiO ₂ units as a units, R ⁴ _k R ⁵ _p SiO _0.5 units as b units, and R ⁴ _q R ⁵ _r SiO _0.5 units as c units. Is the molar ratio
(B + c) /a=0.3-3, especially 0.7-1
c / a = 0.01 to 1, especially 0.07 to 0.15
The organopolysiloxane preferably has a polystyrene-reduced weight average molecular weight in the range of 500 to 10,000 by GPC.

  The above-mentioned organopolysiloxane having a resin structure is blended in order to improve the physical strength and surface tackiness of the cured product, and is blended in an amount of 20 to 70% by mass in the component (A). Is more preferable, and more preferably 30 to 60% by mass. If the amount of the resin-structured organopolysiloxane is too small, the above effect may not be achieved sufficiently. If the amount is too large, the viscosity of the composition may be remarkably increased or cracks may easily occur in the cured product. .

The organohydrogenpolysiloxane as component (B) is an organohydrogenpolysiloxane having 2 or more, particularly 3 or more, hydrogen atoms bonded to 3 or more silicon atoms in one molecule. Here, the component (B) reacts with the component (A) and acts as a cross-linking agent, and the molecular structure is not particularly limited. For example, linear, cyclic, branched, tertiary Various types such as an original network structure (resin-like) can be used, but it is necessary to have hydrogen atoms (SiH groups) bonded to two or more silicon atoms in one molecule, preferably 2 to 300, More preferably, it is desirable to have about 3 to 200, more preferably about 4 to 100. The organohydrogenpolysiloxane should have a silicon atom number (or degree of polymerization) in a molecule of usually 2 to 300, preferably 3 to 200, more preferably about 4 to 100. Can do. As the organohydrogenpolysiloxane, those represented by the following average composition formula (3) are used.
R ⁶ _b H _c SiO _{(4-bc) / 2} (3)

In said formula (3), R < ⁶ > is a C1-C10 unsubstituted or substituted monovalent hydrocarbon group, As this R < ⁶ >, the group similar to R < ³ > in said formula (1) is mentioned. Although it is possible, it is preferable not to have an aliphatic unsaturated bond. B is 0.7 to 2.1, c is 0.001 to 1.0, and b + c is a positive number satisfying 0.8 to 3.0, preferably b is 1.0 to 2 0.0 and c are 0.01 to 1.0, and b + c is 1.5 to 2.5.

  The SiH group contained in at least 2, preferably 3 or more in one molecule may be located at either the molecular chain end or in the middle of the molecular chain, or may be located at both of them. The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures.

Specific examples of the organohydrogenpolysiloxane of the formula (2) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy). ) Methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked Dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy-blocked dimethylsiloxane Polyhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-end trimethylsiloxy group Blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group blocked methylhydrogensiloxane・ Dimethylsiloxane ・ Methylphenylsiloxane copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _1/2 unit and S a copolymer comprising iO _4/2 units, a copolymer comprising (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units and SiO _{4/2 Examples} thereof include a copolymer comprising units and (C ₆ H ₅ ) SiO _2/3 units.

  The amount of component (B) added is such that the hydrogen atom bonded to the silicon atom is 0.1 to 5.0 equivalents in terms of molar ratio to one alkenyl group bonded to the silicon atom in component (A). Preferably 0.5 to 3.0 equivalents, more preferably 0.8 to 2.0 equivalents. When the amount is less than 0.1 equivalent, the crosslinking density becomes too low, which may adversely affect the heat resistance of the silicone cured product. When the amount is more than 5.0 equivalent, a problem of foaming due to a dehydrogenation reaction occurs. Furthermore, there is a risk of adversely affecting the heat resistance.

  The (C) component platinum group metal catalyst is used as a catalyst for promoting the curing addition reaction (hydrosilylation) between the (A) component and the (B) component. Although a well-known thing can be used for a platinum group metal catalyst, it is preferable to use platinum or a platinum compound. Examples of the platinum compound include platinum black, secondary platinum chloride, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, complexes of chloroplatinic acid and olefins, aldehydes, vinyl siloxanes, acetylene alcohols, and the like.

  The amount of the platinum group metal catalyst may be appropriately increased or decreased according to the desired curing rate, but is usually 0.1 to 1,000 ppm in terms of the mass of the platinum group metal relative to the component (A). Preferably, it may be in the range of 1 to 200 ppm.

On the other hand, the condensation curable silicone composition is
(D) an organopolysiloxane whose molecular chain end is blocked with a hydroxyl group or a hydrolyzable group,
(E) a silane having three or more hydrolyzable groups bonded to a silicon atom in one molecule or a partially hydrolyzed condensate thereof,
(F) Contains a condensation catalyst.

  In this case, the component (D) preferably has a viscosity at 25 ° C. of 100 to 500,000 mPa · s, particularly 500 to 100,000 mPa · s, and the molecular chain terminal is blocked with a hydroxyl group or a hydrolyzable group. Organopolysiloxane is the base polymer of the condensation curable silicone composition. The component (D) needs to have its molecular chain end blocked with a hydroxyl group or a hydrolyzable group. As such an organopolysiloxane, α, ω-dihydroxy (or diorganooxy) -diorganopolysiloxane represented by the following general formula (4), (5) or (6) is exemplified.

（式中、Ｒ⁷は同一又は異種の置換又は非置換の１価炭化水素基であり、ｄ及びｎは一般式（４），（５），（６）で表されるジオルガノポリシロキサンの２５℃における粘度を１００〜５００，０００ｍＰａ・ｓ、好ましくは５００〜１００，０００ｍＰａ・ｓの範囲にするような値である。ｅは２又は３である。）

Wherein R ⁷ is the same or different substituted or unsubstituted monovalent hydrocarbon group, and d and n are diorganopolysiloxanes represented by the general formulas (4), (5) and (6). (The value at 25 ° C. is such that the viscosity is in the range of 100 to 500,000 mPa · s, preferably 500 to 100,000 mPa · s. E is 2 or 3.)

In the above formula, X is an alkylene group having 2 to 6 carbon atoms, particularly 2 to 4 carbon atoms such as ethylene group, trimethylene group, tetramethylene group, methylethylene group, etc., and R ⁷ is 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hexyl group and an octadecyl group, an alkenyl group such as a vinyl group and a hexenyl group, a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, Aralkyl groups such as benzyl group and β-phenylethyl group, aryl groups such as phenyl group, xenyl group, naphthyl group, tolyl group and xylyl group, and part or all of hydrogen atoms of these groups are cyano group or halogen atom Substituted with an organic group such as β-cyanoethyl group, 3,3,3-trifluoropropyl group, perfluorobutyl group, etc. Groups and the like, preferably a methyl group.

Examples of the hydrolyzable group represented by OR ⁸ include acyloxy groups such as acetoxy group, octanoyloxy group and benzoyloxy group; ketoxime groups such as dimethyl ketoxime group, methylethyl ketoxime group and diethyl ketoxime group (that is, Iminoxy group); alkoxy group such as methoxy group, ethoxy group, propoxy group; alkoxy alkoxy group such as methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group; vinyloxy group, isopropenyloxy group, 1-ethyl-2-methylvinyl Alkenyloxy group such as oxy group; Amino group such as dimethylamino group, diethylamino group, butylamino group, cyclohexylamino group; Aminoxy group such as dimethylaminoxy group, diethylaminoxy group; N-methylacetamide group, N-ethylacetoa De group, and amide groups such as N- methylbenzamide group.

  These hydrolyzable groups include, for example, trialkoxysiloxy groups, dialkoxyorganosiloxy groups, triacyloxysiloxy groups, diacyloxyorganosiloxy groups, triiminoxysiloxy groups (ie, triketoxime siloxy groups), diiminoxy groups 2 or 3 hydrolyzable group-containing siloxy groups such as organosiloxy group, trialkenoxysiloxy group, dialkenoxyorganosiloxy group, trialkoxysiloxyethyl group, dialkoxyorganosiloxyethyl group, or 2 or 3 The hydrolyzable group-containing siloxyalkyl group is preferably located at both ends of the molecular chain of the linear diorganopolysiloxane.

OR ⁸ is preferably an alkoxy group. In this case, R ⁸ is a chain alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hexyl group, and an octadecyl group, and a methyl group and an ethyl group are preferable.

R ⁷ and OR ⁸ may be the same or different types. Among these, 90 mol% or more or all of R ⁷ is a methyl group in terms of ease of synthesis, balance of mechanical properties after curing, and viscosity of an uncured composition, etc., and groups other than methyl groups When there is, it is preferable that it is a vinyl group or a phenyl group.

  Specific examples of such organopolysiloxane include, for example, molecular chain both ends silanol-blocked dimethylpolysiloxane, molecular chain both ends silanol-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends silanol-blocked dimethyl Siloxane / diphenylsiloxane copolymer, trimethoxysiloxy group-capped dimethylpolysiloxane with molecular chain at both ends, trimethoxysiloxy group-capped dimethylsiloxane / methylphenylsiloxane copolymer with molecular chain at both ends, and trimethoxysiloxy group-capped dimethyl with molecular chain at both ends Siloxane / diphenylsiloxane copolymer, dimethylpolysiloxane blocked with methyldimethoxysiloxy group blocked at both ends of molecular chain, dimethylpolysiloxane blocked with triethoxysiloxy group blocked at both ends of molecular chain, 2-trimethoxy at both ends of molecular chain Shirokishiechiru group-blocked dimethylpolysiloxane. These can be used singly or in combination of two or more.

(E) Silane containing at least 3 silicon atom-bonded hydrolyzable groups in one molecule of the component or a partially hydrolyzed condensate thereof (that is, at least 1, preferably 2 or more hydrolyzable groups remain) Organopolysiloxane) is a component that acts as a curing agent, but the base polymer of component (E) contains at least two silicon atom-bonded hydrolyzable groups other than silanol groups in one molecule. Can be omitted from the composition. As the silane, the formula: R ⁹ _f SiY _4-f (wherein R ⁹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, Y is a hydrolyzable group, f is 0 or 1.) is preferable. R ⁹ is particularly preferably an alkyl group such as a methyl group or an ethyl group; an alkenyl group such as a vinyl group, an allyl group or a propenyl group; and an aryl group such as a phenyl group. Examples of X include the same groups as those exemplified as the silicon atom-bonded hydrolyzable group (OR ⁸ ) in the component (D). For example, an alkoxy group, an alkenoxy group, a ketoxime group, an acetoxy group, an amino group, An aminoxy group etc. are mentioned.

  Specific examples of such silanes or partial hydrolysis condensates thereof include, for example, methyltriethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, ethyl orthosilicate, and the like, and partial hydrolysis condensates thereof. . These can be used singly or in combination of two or more.

  In the present composition, the content of the silane or its partially hydrolyzed condensate is usually preferably 0.01 to 20 parts by mass, particularly 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (D). Part. If the content is less than the lower limit of the above range, the storage stability of the resulting composition may decrease or the adhesiveness tends to decrease, while the amount exceeds the upper limit of the above range. And there exists a tendency for hardening of the composition obtained to become remarkably slow.

  In addition, (E) component as this hardening | curing agent (crosslinking agent) is when the said (D) component is organopolysiloxane by which the molecular chain terminal was blocked by the hydroxyl group as shown by General formula (4). Although it is essential, when the component (D) is an organopolysiloxane whose molecular chain end is blocked with a hydrolyzable group as represented by the general formula (5) or (6), The component (E) is not particularly essential, and is an optional component that may be appropriately blended as necessary.

  Moreover, the condensation catalyst of (F) component is arbitrary components, and when the said silane or its partial hydrolysis-condensation product has an aminoxy group, an amino group, a ketoxime group etc., it is not necessary to use it. . Examples of such condensation catalysts include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; organic titanium chelates such as diisopropoxy bis (ethyl acetoacetate) titanium and diisopropoxy bis (ethyl acetoacetate) titanium. Compound: Organoaluminum compound such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate); Organotirium compound such as zirconium tetra (acetylacetonate), zirconium tetrabutyrate; Dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin Organotin compounds such as di (2-ethylhexanoate); tin naphthenate, tin oleate, tin butyrate, cobalt naphthenate, zinc stearate, etc. Metal salts of organic carboxylic acids; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate and lithium nitrate; dimethylhydroxylamine And dialkylhydroxylamines such as diethylhydroxylamine; guanidyl group-containing organosilicon compounds and the like. These can be used singly or in combination of two or more.

  In this composition, when using the condensation catalyst of the said (F) component, the compounding quantity in particular is not restrict | limited, Although the effective amount as a catalyst may be sufficient, Usually, it is 0.00 with respect to 100 mass parts of (E) component. It is preferable that it is 01-20 mass parts, and it is especially preferable that it is 0.1-10 mass parts. When this catalyst is used, if the content of the catalyst is less than the lower limit of the above range, the resulting composition may not be sufficiently cured depending on the type of the crosslinking agent, while the upper limit of the above range is exceeded. When it exceeds, the storage stability of the composition obtained may fall.

  In the present invention, silica particles having the surface grafted with the organopolysiloxane represented by the above formula (1) are blended into the above addition reaction curable type or condensation curable type silicone composition. In this case, the silica grafted with the organopolysiloxane is added to the total of the silane and siloxane components in the addition reaction curable type or condensation reaction curable type silicone composition (that is, the total of the above components (A) and (B) or the above). (D), (E) total component) 5 to 400 parts by weight per 100 parts by weight, especially 50 to 250 parts by weight, and further 100 to 200 parts by weight is excellent in transparency, low expansion and low gas. A silicone composition giving a permeable cured product is obtained.

  In addition, even if a phosphor such as YAG is mixed in a system in which silica having an organopolysiloxane grafted on a nano-sized silica surface is uniformly dispersed in the silicone composition, the phosphor is precipitated when the silicone composition is cured. It also has the feature that can be prevented. Usually, a method of adding nano-sized silica is known to prevent this kind of sedimentation, but this method increases thixotropy and reduces workability (Japanese Patent Publication No. 2005-524737). .

  In the present invention, even if a large amount of the grafted nano-sized silica is added and blended, no thixotropy is observed. The silicone composition of the present invention has excellent characteristics such as no thixotropy, good fluidity, and no phosphor sedimentation.

In order to impart adhesion to the composition of the present invention, a hydrogen atom bonded to a silicon atom (SiH group), an alkenyl group bonded to a silicon atom (for example, Si—CH═CH ₂ group), alkoxy, A straight chain containing at least two, preferably two or three functional groups selected from a silyl group (for example, trimethoxysilyl group) and an epoxy group (for example, glycidoxypropyl group, 3,4-epoxycyclohexylethyl group) Or cyclic organoorganosiloxane oligomers having 4 to 50, preferably about 4 to 20, organooxysilyl-modified isocyanurate compounds represented by the following general formula (7) and / or their hydrolysis condensates ( An adhesion assistant such as an organosiloxane-modified isocyanurate compound) is preferably blended as an optional component as required.

（式中、Ｒ¹⁰は、下記式（７）

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（８）の有機基であり、Ｒ¹¹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。）

(Wherein R ¹⁰ represents the following formula (7)

Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, but at least one is an organic group of the formula (8), and R ¹¹ is a hydrogen atom or a C 1-6 carbon atom. 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 represented by R ¹⁰ includes a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group. And alkenyl groups having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms. R ¹¹ monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl 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, an aryl group such as a phenyl group, and the like similar to those exemplified as R ¹⁰ 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。） The following can be illustrated as such an adhesion assistant.

(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 a silicon atom-bonded alkoxy group and an alkenyl group or silicon atom-bonded hydrogen atom (SiH group) in one molecule. A silicon compound is preferred.

  In this invention, the compounding quantity of the adhesion assistant which is an arbitrary component is normally 10 mass parts or less (namely, 0-10 mass parts) with respect to a total of 100 mass parts of a base polymer and a hardening | curing agent, Preferably it is 0.00. About 01-5 mass parts, More preferably, about 0.1-1 mass part can be mix | blended. If the blending amount of the adhesion assistant 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.

  The silicone composition of the present invention is prepared by uniformly mixing the above-mentioned silica grafted with the organopolysiloxane and the other components of the silicone composition with a planetary mixer, three rolls, etc. Of course, in the addition-curable silicone composition, a small amount of a curing inhibitor such as acetylene alcohol can be added and used as one liquid.

  The cured product obtained by curing the silicone composition of the present invention is excellent in light transmittance even when highly filled with silica particles, and is usually 80% or more (80 to 100%) at 400 to 800 nm, particularly 90%. % Or more (90 to 100%), particularly 95% or more (95 to 100%).

The composition of the present invention is useful for LED element sealing, particularly for blue, white LED and ultraviolet LED element sealing. Various known phosphor powders can be added for whitening using a blue LED. As a typical yellow phosphor, a general formula A ₃ B ₅₀ O ₁₂ : M (wherein component A has at least one element consisting of a group consisting of Y, Gd, Tb, La, Lu, Se and Sm) , Component B has at least one element consisting of a group consisting of Al, Ga and In, and component M has at least one element consisting of a group consisting of Ce, Pr, Eu, Cr, Nd and Er). It is particularly advantageous to contain phosphor particles of the garnet group. Y ₃ Al ₅ O ₁₂ : Ce phosphor and / or (Y, Gd, Tb) ₃ (Al, Ga) as a phosphor for a light emitting diode element that emits white light with a light emitting diode chip that emits blue light. ) ₅ O ₁₂ : Ce phosphor is suitable. Other phosphors include, for example, CaGa ₂ S ₄ : Ce ³⁺ and SrGa ₂ S ₄ : Ce ³⁺ , YAlO ₃ : Ce ³⁺ , YGaO ₃ : Ce ³⁺ , Y (Al, Ga) O ₃ : Ce ³⁺ , Y ₂ SiO ₅ : Ce ^{3+ and the} like. In addition to these phosphors, aluminate doped with rare earths or orthosilicates doped with rare earths are suitable for producing mixed color light. The phosphor of this type is added to the composition of the present invention depending on the thickness of the resin layer, the sum of the silane and siloxane components in the composition (that is, the sum of components (A) and (B) or Blue) can be converted into white by blending 0.5 to 200 parts by mass with respect to 100 parts by mass. Since phosphors generally have a high specific gravity, they settle during the course of curing of the silicone composition, making it very difficult to achieve the desired uniform dispersion. However, this type of problem can be eliminated by using the composition of the present invention.

  When sealing a light-emitting semiconductor device such as an LED with the composition of the present invention, the composition is applied to an LED element mounted on a pre-molded package made of a thermoplastic resin, and the composition is cured. By forming the cured product on the LED element, the LED element can be sealed with the cured product. Moreover, it can apply | coat to this LED element in the state of the varnish produced | generated by melt | dissolving this composition in organic solvents, such as toluene and xylene.

  In addition, the composition of the present invention has the following display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical fibers, and the like because of its excellent heat resistance, ultraviolet resistance, transparency, and the like. -It can also be used for applications such as electronic functional organic materials and semiconductor integrated circuit peripheral materials.

-1. Display materials
Display materials include, for example, liquid crystal display substrate materials, light guide plates, prism sheets, deflector plates, retardation plates, viewing angle correction films, adhesives, liquid crystal display peripheral materials such as polarizer protective films, etc. ; Color plasma display (PDP) sealing material, next generation flat panel display, antireflection film, optical correction film, housing material, front glass protective film, front glass substitute material, adhesive, etc .; Plasma addressed liquid crystal (PALC) ) Display substrate material, light guide plate, prism sheet, deflection plate, retardation plate, viewing angle correction film, adhesive, polarizer protective film, etc .; protective film for front glass of organic EL (electroluminescence) display, substitute for front glass Materials, adhesives, etc .; field emission diss Various film substrate Ray (FED), front glass protective films, front glass substitute material, adhesives and the like.

-2. Optical recording material
Examples of optical recording materials include VD (video disc), CD, CD-ROM, CD-R / CD-RW, DVD ± R / DVD ± RW / DVD-RAM, MO, MD, PD (phase change disc). And a disk substrate material for an optical card, a pickup lens, a protective film, a sealing material, and an adhesive.

-3. Optical equipment materials
Optical equipment materials include, for example, steel camera lens materials, viewfinder prisms, target prisms, viewfinder covers, light receiving sensor sections, etc .; video camera shooting lenses, viewfinders, etc .; projection television projection lenses, protective films, sealing materials Adhesives, etc .; Lens materials for optical sensing devices, sealing materials, adhesives, films and the like.

-4. Optical component materials
Examples of optical component materials include fiber materials, lenses, waveguides, element sealing materials, and adhesives around optical switches in optical communication systems; optical fiber materials, ferrules, sealing materials, and adhesives around optical connectors. Etc .; Optical passive components / optical circuit components such as lenses, waveguides, adhesives, etc .; substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC).

-5. Optical fiber materials
Examples of the optical fiber material include decoration display lighting / light guides, etc .; industrial sensors, displays / signs, etc .; optical fibers for communication infrastructure and home digital equipment connection.

-6. Peripheral materials for semiconductor integrated circuits
Examples of the semiconductor integrated circuit peripheral material include resist materials for microlithography for LSI and VLSI materials.

-7. Optical and electronic functional organic materials
Examples of optical / electronic functional organic materials include organic EL element peripheral materials; organic photorefractive elements; optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells; fiber materials; Examples thereof include an element sealing material and an adhesive.

  EXAMPLES Hereinafter, although a synthesis 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. In the following examples, parts are parts by mass, Me is a methyl group, and Et is an ethyl group.

[Synthesis Example 1]
Grafting of nano silica 50 parts of Aerosil 200 (average particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.) and 25 parts of polysiloxane (1) (Shin-Etsu Chemical Co., Ltd.) having the following structure in a flask equipped with a reflux condenser Then, 500 parts of xylene was added, and the graft reaction was performed by refluxing at 150 ° C. for 24 hours. After completion of the reaction, the grafted silica, xylene and unreacted polysiloxane are separated using a centrifugal separator, and further 500 parts of xylene are added and stirred twice. The polysiloxane was removed. Thereafter, the separated silica was dried at 120 ° C. for 4 hours to obtain grafted silica (1). As a result of measuring the grafting rate of the obtained silica (1) by TGA, it was 8.7%. Grafting was also confirmed by analysis by FT-IR.
Grafting was performed in the same manner at the mixing ratio shown in Table 1, and five types of grafted silica (2) to (6) were obtained.

（但し、Ｌ＝４５０）
で示される両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン７５部にＳｉＯ₂単位５０モル％、（ＣＨ₃）₃ＳｉＯ_0.5単位４２．５モル％及び（ＣＨ₂＝ＣＨ）（ＣＨ₃）₂ＳｉＯ_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）２５部、下記式（ｉｉ）

（但し、Ｌ＝１０、Ｍ＝８）
で示されるオルガノハイドロジェンポリシロキサンを５．３部（即ち、上記ビニル基含有ジメチルポリシロキサン（ｉ）及び（ｉｉ）中のビニル基に対するＳｉＨ基のモル比が１．５となる量に相当する）、及び、塩化白金酸のオクチルアルコール変性溶液（白金濃度１質量％）を０．０５部加え、よく撹拌して得たシリコーン組成物１００部に合成例１で製造したシリカ（１）〜（６）をそれぞれ１００部添加して、プラネタリーミキサーで混合することで、液状シリコーン組成物１〜６を調製した。シリコーン組成物５はミキサー混合で粉体状となり、以下の評価はできなかった。シリコーン組成物１〜４と６を１５０℃×４時間の条件で硬化させた。
得られた硬化物の物性をＪＩＳ Ｋ６３０１に従い、測定した。なお、硬さはスプリング式ＴｙｐｅＡ型試験機による。その結果を表１に示す。 [Examples 1 to 4, Comparative Examples 1 and 2]
Formula (i) below

(However, L = 450)
In addition, 75 parts by weight of vinyl dimethylsiloxy group-blocked dimethylpolysiloxane represented by the formula: 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and (CH ₂ ═CH) (CH ₃ ) ₂ SiO _0.5 25 parts of a resin structure vinylmethylsiloxane (VMQ) composed of 7.5 mol% unit, the following formula (ii)

(However, L = 10, M = 8)
Is equivalent to 5.3 parts by weight of the organohydrogenpolysiloxane represented by the formula (i.e., the molar ratio of SiH groups to vinyl groups in the vinyl group-containing dimethylpolysiloxanes (i) and (ii) is 1.5). ), And 0.05 parts of a chloroplatinic acid octyl alcohol-modified solution (platinum concentration 1% by mass), and silica (1) to (1) produced in Synthesis Example 1 to 100 parts of a silicone composition obtained by thoroughly stirring. Liquid silicone compositions 1 to 6 were prepared by adding 100 parts of 6) and mixing with a planetary mixer. Silicone composition 5 was powdered by mixing with a mixer and could not be evaluated as follows. Silicone compositions 1-4 and 6 were cured under conditions of 150 ° C. × 4 hours.
The physical properties of the obtained cured product were measured according to JIS K6301. The hardness is determined by a spring type A type testing machine. The results are shown in Table 1.

Moreover, the board | substrate which plated silver on copper was set | placed on the glass substrate, the said composition was apply | coated to thickness 0.3mm from it, and it hardened | cured at 70 degreeC for 1 hour, and produced the evaluation sample. The evaluation sample is placed in a sealed container having a volume of 2 liters, and (NH ₄ ) ₂ S ( ₂₀ g) and H ₂ O ( ₁₀ g) are placed in the sealed container, and the time shown in Table 2 at 23 ° C. in a sealed state where H ₂ S gas is generated. And the occurrence of corrosion was evaluated on the copper-plated substrate. The results are shown in Table 2.
Further, a cured film having a thickness of 1 mm was produced from this composition under conditions of 150 ° C. × 4 hours, and light transmittance at a wavelength of 400 to 800 nm was measured. Moreover, the moisture permeability was measured based on the method prescribed | regulated to JISZ0208. The results are shown in Table 2.

○：腐食無 △：一部変色 ×：黒色に変色（完全腐食）

○: No corrosion △: Partial discoloration ×: Discoloration to black (complete corrosion)

[Examples 5 and 6, Comparative Examples 3 to 5]
A liquid silicone composition was prepared in the same manner as in Example 1 except that 100 parts of the silica (1) produced in Synthesis Example 1 was changed to 25 parts, 150 parts, 500 parts, 0 parts, and 3 parts, respectively. 7-11 were prepared. The silicone composition 9 became a high-viscosity paste, the workability was poor, and a test piece for measuring good physical properties could not be produced. A composition other than the silicone composition 9 was used and cured at 80 ° C. for 4 hours.
The physical properties, corrosion test, and light transmittance of the obtained cured product were measured in the same manner as in Example 1. The results are shown in Table 3.

○：腐食無 △：一部変色 ×：黒色に変色（完全腐食）

○: No corrosion △: Partial discoloration ×: Discoloration to black (complete corrosion)

（但し、Ｌ＝４５０）
で示される両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン１００部にチタンキレート触媒（商品名ＴＣ−７５０：マツモトファインケミカル社製）０．１部を加え、よく撹拌して得たシリコーン組成物１００部にシリカ（１）を５０部添加して、液状シリコーン組成物１２を調製した。
２３℃／５０％ＲＨ，２４ｈｒで硬化した以外は実施例１と同様に硬化物の物性、腐食試験及び光透過率を測定した。
硬化物の硬さは６８（Ｔｙｐｅ Ａ）、伸び９５％、引っ張り強さは５（ＭＰａ）であった。
また、腐食試験では８時間経過してもほとんど腐食は起こっていなかった。
更に、可視光範囲での光透過率は９６％と良好であった。 [Example 7]
The following formula (iii)

(However, L = 450)
To 100 parts of a silicone composition obtained by adding 0.1 part of a titanium chelate catalyst (trade name TC-750: manufactured by Matsumoto Fine Chemical Co., Ltd.) to 100 parts of dimethylpolysiloxane having both ends trimethoxysiloxy groups blocked by 50 parts of silica (1) was added to prepare a liquid silicone composition 12.
The physical properties, corrosion test and light transmittance of the cured product were measured in the same manner as in Example 1 except that it was cured at 23 ° C./50% RH for 24 hours.
The hardness of the cured product was 68 (Type A), the elongation was 95%, and the tensile strength was 5 (MPa).
In the corrosion test, corrosion hardly occurred even after 8 hours.
Furthermore, the light transmittance in the visible light range was as good as 96%.

[Example 8, Comparative Example 6]
10 parts of YAG yellow phosphor powder were mixed with 100 parts of silicone composition 1 and silicone composition 10 to obtain respective compositions.
This composition was put into a container formed of a thermoplastic resin having a thickness of 2 mm and a side of 3 mm square, and step cure was performed at 60 ° C. for 1 hour and 150 ° C. for 2 hours to cure the silicone composition.
After curing, the package was cut and the degree of sedimentation of the phosphor was examined. As a result, when the silicone composition 1 was filled with a phosphor, no precipitation of the phosphor was observed (Example 8). However, in the system filled with the silicone composition 10, sedimentation of the phosphor was observed (Comparative Example 6).

[Examples 9 to 14, Comparative Examples 7 to 9]
An InGaN-based blue light emitting element was fixed to a pre-mold package for LED having a recessed opening (thickness 1 mm, one side 3 mm, opening, diameter 2.6 mm, bottom side silver plated) using silver paste. Next, the external electrode and the light emitting element were connected to the external electrode with a gold wire. Thereafter, the silicone compositions of Examples and Comparative Examples shown in the following table were injected into the package opening and cured at 60 ° C. for 1 hour and further at 150 ° C. for 2 hours to form a light emitting semiconductor element.
Using the manufactured light emitting semiconductor device, the temperature cycle test and the initial luminance were measured by the following method.
“Temperature cycle test”: In a cooling / heating cycle test of −40 ° C./30 minutes to 125 ° C./30 minutes, a package that did not peel off after 1000 cycles was defined as “no defect”.
“Initial luminance”: Applying a current of 10 mA to the LED, causing the LED to emit light, and measuring the luminance with Otsuka Electronics (LP-3400). If the luminance is 15 mlm (milli-lumen) or more (good), the luminance A value of less than 15 mlm (milli-lumen) was regarded as “decrease”.

不可^*：シリコーン組成物が粉体状となり、パッケージに注型できなかった。

Impossible ^* : The silicone composition became powdery and could not be cast into a package.

Claims (7)

4% of the total mass of the silane and siloxane components in the addition-curable or condensation-curable silicone composition by 100% by mass with respect to the mass of silica before treatment with the organopolysiloxane represented by the following general formula (1) A highly transparent silicone composition comprising 5 to 400 parts by mass of the above-grafted silica particles.

(Wherein R ¹ is the same or different from each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is a methyl group or an ethyl group, a is 1 to 50, b is 0 or 1, d is 0 or 1, c and e are integers of 0 to 10, and a + b + d is an integer of 3 to 52.)   The silicone composition according to claim 1, wherein the cured product has a light transmittance of 80% or more at 400 to 800 nm. Addition-curable silicone composition is
(A) an alkenyl group-containing organopolysiloxane,
(B) organohydrogenpolysiloxane,
(C) The silicone composition according to claim 1 or 2, comprising a platinum group metal catalyst. The condensation curable silicone composition is
(D) an organopolysiloxane whose molecular chain end is blocked with a hydroxyl group or a hydrolyzable group,
(E) a silane having three or more hydrolyzable groups bonded to a silicon atom in one molecule or a partially hydrolyzed condensate thereof,
(F) Containing a condensation catalyst, The silicone composition according to claim 1 or 2 characterized by things.   Furthermore, the silicone composition of any one of Claims 1 thru | or 4 containing fluorescent substance.   The silicone composition according to any one of claims 1 to 5, wherein the silica particles have an average particle size of 1 nm or more and less than 1,000 nm.   The light emitting semiconductor device sealed with the hardened | cured material of the silicone composition of any one of Claims 1 thru | or 6.