JP6393659B2 - Addition-curing silicone composition and semiconductor device - Google Patents

Description

  The present invention relates to an addition-curable silicone composition, a cured product thereof, and a semiconductor device including the cured product. In particular, the present invention relates to an addition-curable silicone composition containing a branched organopolysiloxane having a siloxane branched chain having a short chain length.

  Addition-curable silicone resins have been used as a sealing material for sealing semiconductor elements such as LEDs since they are excellent in heat resistance, light resistance, fast curing properties and the like. For example, Patent Document 1 describes an addition-curable silicone resin that exhibits high adhesion to an LED package made of a thermoplastic resin such as PPA. Patent Document 2 describes a method for sealing an optical semiconductor element by compression molding of an addition-curable silicone resin composition.

  As described above, the addition-curable silicone resin is widely used as a semiconductor sealing material, but its characteristics are not yet satisfactory. In particular, LED encapsulants are exposed to external stresses such as changes in temperature and humidity in addition to internal stresses due to temperature changes caused by ON / OFF of the optical semiconductor device. Is also important. However, conventional addition-curable silicone resins are not sufficient for low-temperature properties and have a problem that they cannot withstand the stress of temperature change and cause cracks.

Patent Document 3 describes that a linear silicone chain has a branched structure in order to improve the low temperature characteristics of the cured product. In Patent Document 3, a branched organopolysiloxane is prepared by subjecting a mixture containing an organohydrogenpolysiloxane containing CH ₃ (H) SiO _1/2 units to an equilibration reaction using an alkali catalyst in the presence of water. A method of manufacturing is described. Patent Document 4 describes a branched organopolysiloxane obtained by polymerizing an alkoxy group-containing organopolysiloxane and a low molecular weight organopolysiloxane in the presence of an acidic or basic catalyst. However, in these production methods, the chain lengths of the main chain and the side chain cannot be controlled independently. The resulting organopolysiloxane has a long branched chain length or a network structure. For this reason, even if an attempt is made to form a desired TM branch structure, the chain lengths of the main chain and the side chain cannot be controlled independently, as in T-D _n -M (n is 5 or more) It becomes a branch with a long chain length. Although Patent Document 5 also describes branched organopolysiloxanes, the branched chain length is long, and such organopolysiloxanes cannot sufficiently satisfy temperature change resistance.

JP 2006-256603 A JP 2006-93354 A JP 2002-348377 A JP 2001-163981 A JP 2000-351949 A

  The present invention has been made in view of the above problems, and an addition-curable silicone composition that gives a cured product having good low-temperature characteristics and excellent temperature change resistance, and a semiconductor element sealed with the cured product of the composition. Another object of the present invention is to provide a highly reliable semiconductor device.

  As a result of intensive studies, the present inventors have a short branched chain length (that is, composed of 1 to 4 siloxane units) represented by the following formula (1), and have an alkenyl group and a hydrosilyl group in one molecule. A cured product of an addition-curable silicone composition containing a branched organopolysiloxane has been found to provide a semiconductor device having excellent low temperature and high temperature characteristics, excellent temperature change resistance, and high reliability. It came to be accomplished.

（式中、Ｒ^１は、互いに独立に、置換または非置換の、炭素数１〜８の飽和炭化水素基又は炭素数６〜１０の芳香族炭化水素基であり、Ｒ^３は、互いに独立に、水素原子、置換または非置換の、炭素数１〜８の飽和炭化水素基又は炭素数６〜１０の芳香族炭化水素基、及び炭素数２〜８のアルケニル基から選ばれる基であり、Ｒ^４は、互いに独立に、置換または非置換の、炭素数１〜１２の飽和炭化水素基又は炭素数６〜１２の芳香族炭化水素基であり、ｋは互いに独立に０〜３の整数であり、該化合物はＲ^３で示される基を１分子中に少なくとも２つ有し、Ｒ^３の少なくとも１は水素原子であり、且つＲ^３の少なくとも１はアルケニル基であり、ｘは０〜３の整数であり、ａは１〜７５の整数であり、ｂは０〜２３０の整数であり、１≦ａ＋ｂ≦３００であり、ａ又はｂで括られる括弧内にあるシロキサン単位はランダム構造を形成していてもブロック単位を形成していても良い）
及び
（Ｂ）ヒドロシリル化触媒 触媒量。 That is, the present invention provides an addition-curable silicone composition containing the following components (A) and (B).
(A) Branched organopolysiloxane represented by the following formula (1)

(In the formula, R ¹ is, independently of each other, a substituted or unsubstituted saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ³ is independently of each other. , A hydrogen atom, a substituted or unsubstituted saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms, R ⁴ is independently of each other a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and k is an integer of 0 to 3 independently of each other. , the compound has at least two groups represented by R ³ in the molecule, at least one of R ³ is a hydrogen atom, and at least one of R ³ is an alkenyl group, x is from 0 to 3 An integer, a is an integer from 1 to 75 , and b is an integer from 0 to 230 . 1 ≦ a + b ≦ 300 , and the siloxane unit in parentheses enclosed by a or b may form a random structure or a block unit)
And (B) hydrosilylation catalyst, catalytic amount.

  The addition-curable silicone composition of the present invention includes a composition containing a linear organopolysiloxane having the same chain length, and a branched organopolysiloxane having a long branched chain (particularly, having 5 or more siloxane units). A cured product having a glass transition temperature lower than that of a composition containing siloxane is obtained. In addition, the obtained cured product has good low temperature characteristics, excellent temperature change resistance, and improved crack resistance and the like. Therefore, a semiconductor device excellent in reliability can be provided by sealing the semiconductor element with the cured product of the addition-curable silicone composition of the present invention. Moreover, since the organopolysiloxane in this invention has a hydrosilyl group and an alkenyl group in a molecule | numerator simultaneously, a hardened | cured material can be obtained only with two components with a curing catalyst, and manufacturing cost can be made cheap.

上記式中、Ｒ^１は、互いに独立に、置換または非置換の炭素数１〜１２の飽和炭化水素基、又は置換または非置換の炭素数６〜１２の芳香族炭化水素基であり、Ｒ^３は、互いに独立に、水素原子、置換または非置換の炭素数１〜１２の飽和炭化水素基、置換または非置換の炭素数６〜１２の芳香族炭化水素基、及び炭素数２〜１０のアルケニル基から選ばれる基であり、Ｒ^４は、互いに独立に、置換または非置換の炭素数１〜１２の飽和炭化水素基、又は置換または非置換の炭素数６〜１２の芳香族炭化水素基であり、ｋは互いに独立に０〜３の整数であり、該化合物はＲ^３で示される基を１分子中に少なくとも２つ有し、Ｒ^３の少なくとも１は水素原子であり、且つＲ^３の少なくとも１はアルケニル基であり、ｘは０〜３の整数であり、ａは１〜１００の整数であり、ｂは０〜３００の整数であり、１≦ａ＋ｂ≦４００であり、ａ又はｂで括られる括弧内にあるシロキサン単位はランダム構造を形成していてもブロック単位を形成していても良い。 Hereinafter, the present invention will be described in detail.
(A) Branched polyorganosiloxane The composition of the present invention has at least one branched chain composed of 1 to 4 siloxane units represented by the following formula (1), and has at least one in one molecule. It contains a branched organopolysiloxane having an alkenyl group and at least one hydrosilyl group.

In the above formulas, R ^{1 s} are each independently a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ³ Are each independently a hydrogen atom, a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. R ⁴ is a group selected from the group, and independently of each other, R ⁴ is a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms. There, k are independently integers of 0 to 3 to each other, said compound having at least two groups represented by R ³ in the molecule, at least one of R ³ is a hydrogen atom, and the R ³ At least 1 is an alkenyl group, x is an integer from 0 to 3 a is an integer of 1 to 100, b is an integer of 0 to 300, 1 ≦ a + b ≦ 400, and a siloxane unit in parentheses enclosed by a or b is a block even if it forms a random structure Units may be formed.

R ¹ is independently of each other a substituted or unsubstituted, saturated hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. It is. Examples of the substituted or unsubstituted saturated hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; and a carbon atom of these groups A part or all of the hydrogen atoms bonded to is substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group, a glycidyloxy group, a methacryloxy group, a mercapto group, or an amino group, for example, a trifluoropropyl group, Halogenated monovalent hydrocarbon groups such as chloropropyl group; cyanoalkyl groups such as β-cyanoethyl group and γ-cyanopropyl group, 3-methacryloxypropyl group, 3-glycidyloxypropyl group, 3-mercaptopropyl group, 3 -Aminopropyl group is exemplified. Among these, a methyl group, a cyclohexyl group and the like are preferable, and a methyl group is particularly preferable. Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group and naphthyl group, and aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group. One or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom such as fluorine, bromine or chlorine or a cyano group. Of these, a phenyl group and a tolyl group are preferable, and a phenyl group is particularly preferable.

R ³ , independently of each other, is a hydrogen atom, a substituted or unsubstituted C 1-12, preferably 1-8 saturated hydrocarbon group, and a substituted or unsubstituted C 6-12, preferably 6 Is a group selected from 10 to 10 aromatic hydrocarbon groups and 2 to 10 carbon atoms, preferably 2 to 8 alkenyl groups. Examples of the saturated hydrocarbon group and the aromatic hydrocarbon group are the same as those exemplified for R ¹ above. Of these, a methyl group and a phenyl group are preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a hexenyl group, and a styryl group. A vinyl group and an allyl group are preferable, and a vinyl group is particularly preferable. However, at least one of the groups represented by R ³ is a hydrogen atom, and at least one is an alkenyl group. Preferably, the compound represented by the formula (1) has at least two hydrosilyl groups in one molecule and at least two alkenyl groups. The hydrosilyl group and the alkenyl group may be present at the terminal or in the molecular chain, respectively. In particular, a structure having hydrosilyl groups at both ends and an alkenyl group in the molecular chain, or a structure having alkenyl groups at both ends and a hydrosilyl group in the molecular chain is preferable.

R ⁴ is a group selected from a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, independently of each other. The substituted or unsubstituted saturated hydrocarbon group includes an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a hydrogen bonded to a carbon atom of these groups Some or all of the atoms substituted with halogen atoms such as fluorine, bromine, chlorine, cyano group, glycidyloxy group, methacryloxy group, mercapto group, or amino group, such as trifluoropropyl group, chloropropyl group, etc. A halogenated monovalent hydrocarbon group; a cyanoalkyl group such as β-cyanoethyl group, γ-cyanopropyl group, 3-methacryloxypropyl group, 3-glycidyloxypropyl group, 3-mercaptopropyl group, 3-aminopropyl group Is exemplified. Of the saturated hydrocarbon groups, a methyl group and a cyclohexyl group are preferable. Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, and naphthyl group, and aralkyl groups such as benzyl group, phenylethyl group, and phenylpropyl group, and those exemplified for R ¹ above. The same thing is mentioned. Of these, a phenyl group is preferred. In particular, R ⁴ is preferably a methyl group or a phenyl group.

k is an integer of 0 to 3, independently of each other, preferably 0 or 1, and more preferably 1. In particular, it is preferable that k at both ends have the same value. Both k at both ends may be 0. In this case, it is sufficient that each molecular chain has one or more alkenyl groups and hydrosilyl groups. R ³ which is an alkenyl group may be present in the molecular chain or may be present at 1 to 3 at the terminal. Accordingly, when R ³ present at the terminal is an alkenyl group, k is independently an integer of 1 to 3, preferably 1, and in particular, both k at both terminals are preferably 1. R ³ which is a hydrogen atom is preferably present only at the terminal or in the molecular chain from the viewpoint of availability of raw materials. Therefore, when R ³ present at the terminal is a hydrogen atom, both k at both terminals are preferably 1. x is an integer of 0 to 3, preferably 0 or 1, and particularly preferably 0. a is an integer of 1 to 100, preferably an integer of 1 to 75, and more preferably an integer of 1 to 50. b is an integer of 0-300, preferably an integer of 1-230, more preferably an integer of 1-110. However, 1 ≦ a + b ≦ 300 is preferable, 1 ≦ a + b ≦ 250 is more preferable, and 1 ≦ a + b ≦ 200 is more preferable. Further, 0.01 ≦ a / (a + b) ≦ 1.0, particularly 0.03 ≦ a / (a + b) ≦ 1.0 is preferable.

The branched organopolysiloxane and it is preferably at least one of the groups represented by R ¹ is an aromatic hydrocarbon group. In particular, the branched organopolysiloxane has a monovalent aromatic hydrocarbon group bonded to a silicon atom in a number of 3% to 90% of the total number of all substituents bonded to the silicon atom. It is preferable to have 5% or more. The upper limit is preferably 80% or less. By having an aromatic hydrocarbon group in an amount preferably in the above range, the resulting cured product has a high refractive index and low gas permeability, and thus can be suitably used for sealing a semiconductor element. .

  Moreover, the quantity from which the number of hydrosilyl groups with respect to the total number of the alkenyl groups in (A) component is 0.4-4 is preferable, More preferably, it is the quantity used as 0.6-2, More preferably, it is 0.8. It is the quantity which becomes -1.6. If it is less than the above lower limit, SiH groups are insufficient, resulting in poor curing, and if it exceeds the above upper limit, side reactions such as dehydrogenation due to residual SiH groups are likely to occur. In addition, what is necessary is just to adjust so that the total number of the alkenyl group in (A) and (C) component may become said range, when (C) component mentioned later is included. Moreover, what is necessary is just to adjust so that the total number of the hydrosilyl group in (A) and (D) component may satisfy | fill the said range, when (D) component mentioned later is included.

（式中、Ｒ^１、Ｒ^３、及びｘは上述の通りであり、Ｒ^２は水素原子または炭素数１〜６の飽和炭化水素基である） Hereinafter, the manufacturing method of the said branched organopolysiloxane is demonstrated.
The branched organopolysiloxane is obtained by subjecting an organosiloxane in which two hydrolyzable groups are bonded to one terminal silicon atom represented by the following formula (3) as a raw material for introducing a branched chain, and subjecting the organosiloxane to a condensation reaction. It is obtained by the manufacturing method characterized by these. The condensation reaction is preferably performed in the presence of a catalyst.

(Wherein R ¹ , R ³ , and x are as described above, and R ² is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms)

In the above formula (3), examples of R ² include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a hexyl group, and a cyclohexyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

  Examples of the organopolysiloxane represented by the above formula (3) include 1,1,1,3-tetramethyl-3,3-dimethoxydisiloxane, 1-phenyl-1,1,3-trimethyl-3,3. -Dimethoxydisiloxane, 1,1-diphenyl-1,3-dimethyl-3,3-dimethoxydisiloxane, 1,1-diphenyl-1,3-dimethyl-3,3-diethoxydisiloxane, 1,1, 1-triphenyl-3-methyl-3,3-dimethoxydisiloxane, 1,1,1-trimethyl-3-phenyl-3,3-dimethoxydisiloxane, 1,3-diphenyl-1,1-dimethyl-3 , 3-dimethoxydisiloxane, 1,1-diphenyl-1-methyl-3-phenyl-3,3-dimethoxydisiloxane, 1,1,1-triphenyl-3-phenyl-3, -Dimethoxydisiloxane, 1,1-diphenyl-1-methyl-3-cyclohexyl-3,3-dimethoxydisiloxane, 1,1-diphenyl-1-methyl-3-glycidyloxypropyl-3,3-dimethoxydisiloxane 1,1-diphenyl-1-methyl-3-trifluoropropyl-3,3-dimethoxydisiloxane, 1,1,1,3,3,5-hexamethyl-5,5-dimethoxytrisiloxane, 1,1 -Diphenyl-1,3,3,5-tetramethyl-5,5-dimethoxytrisiloxane, 1,1,1-triphenyl-3,3,5-trimethyl-5,5-dimethoxytrisiloxane, 1,1 , 1,3,3-pentamethyl-5-phenyl-5,5-dimethoxytrisiloxane, 1,1,5-triphenyl-1,3,3-trimethyl 5,5-dimethoxytrisiloxane, 1,1,1,5-tetraphenyl-3,3-trimethyl-5,5-dimethoxytrisiloxane, 1,1,1,5-tetramethyl-3,3-diphenyl- 5,5-dimethoxytrisiloxane, 1,1,1-trimethyl-3,3,5-triphenyl-5,5-dimethoxytrisiloxane, 1,1,1,3,3,5-hexaphenyl-5, 5-dimethoxytrisiloxane, 1,1-diphenyl-1-methyl-3-vinyl-3,3-dimethoxydisiloxane, 1,1-diphenyl-1-methyl-3,3-dimethoxydisiloxane, 1,1- Diphenyl-1-methyl-3,3-diphenyl-5-methyl-5,5-dimethoxytrisiloxane, 1,1-diphenyl-1-methyl-3,5,7-triphenyl-3,5 7-trimethyl-9-methyl-9,9-dimethoxypentasiloxane, 1,1-diphenyl-1-methyl-3,5,7-tri (3,3,3-trifluoropropyl) -3,5,7 -Trimethyl-9-methyl-9,9-dimethoxypentasiloxane and 1,1-diphenyl-1-methyl-3- (3,3,3-trifluoropropyl) -3,3-dimethoxydisiloxane .

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びｘは上記の通りであり、ａは１〜１００の整数であり、ｂ’は０〜３００の整数であり、１≦ａ＋ｂ’≦４００である） The compound represented by the above formula (3) is subjected to a condensation reaction alone or with another organosilicon compound, preferably in the presence of a catalyst, to produce an organopolysiloxane represented by the following formula (4) (hereinafter, (Referred to as a condensation reaction step), the end of the organopolysiloxane is reacted with another organosilicon compound and blocked to produce a branched organopolysiloxane represented by the above formula (1) (hereinafter referred to as end blocking reaction). Called stage). The end-capping reaction may optionally be performed in the presence of a catalyst.

Wherein R ¹ , R ² , R ³ and x are as described above, a is an integer of 1 to 100, b ′ is an integer of 0 to 300, and 1 ≦ a + b ′ ≦ 400. )

（式中、Ｒ^１、Ｒ^２、及びＲ^３は上記の通りであり、ｐは２〜３００の整数であり、好ましくは５〜２００の整数であり、さらに好ましくは１０〜１００の整数である。括弧内にある各シロキサン単位はブロック単位を形成していてもランダム構造を形成していてもよい） Examples of the organosilicon compound to be reacted with the compound represented by the above formula (3) include R ¹ R ³ SiX ₂ (wherein R ¹ and R ³ are as described above, and X is a hydrolyzable group or a halogen atom). 1) or two or more selected from organic silicon compounds represented by the following formula (5).

(In the formula, R ¹ , R ² and R ³ are as described above, and p is an integer of 2 to 300, preferably an integer of 5 to 200, more preferably an integer of 10 to 100. (Each siloxane unit in parentheses may form a block unit or a random structure)

Examples of the organosilicon compound represented by R ¹ R ³ SiX ₂ include chlorosilanes such as dimethyldichlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane, and benzylmethyldichlorosilane; dimethyldimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxy. Alkoxysilanes such as silane, benzylmethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, diphenyldiethoxysilane, and benzylmethyldiethoxysilane; disilanols such as diphenylsilanediol, benzylmethylsilanediol, and dibenzylsilanediol Etc. Of these, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, diphenylsilanediol and the like are preferable.

  Examples of the organosilicon compound represented by the above formula (5) include 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethyldisiloxane-1, 3-diol, 1,1,3,3,5,5-hexamethyl-1,5-dimethoxytrisiloxane, 1,3,5-triphenyl-1,3,5-trimethyl-1,5-dimethoxytrisiloxane 1,3,5-triphenyl-1,3,5-trimethyltrisiloxane-1,5-diol, 1,1,3,3,5,5-hexaphenyl-1,5-dimethoxytrisiloxane, , 1,3,3,5,5-hexaphenyltrisiloxane-1,5-diol and 1,3,5-tri (trifluoropropyl) -1,3,5-trimethyltrisiloxane-1,5- Diol, and Oligomers or polymers of these compounds.

  Alternatively, silanes having a hydrocarbon group containing halogen, oxygen, nitrogen, sulfur atoms such as 3-glycidyloxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-aminopropylmethyldimethoxysilane may be condensed. Good.

（式中、Ｒ^３、Ｒ^４、及びｋは上記の通りであり、Ｘは加水分解性基またはハロゲン原子である）

（式中、Ｒ^３、Ｒ^４、及びｋは上記の通りであり、Ｑは酸素原子または＝Ｎ−Ｈである）

（式中、Ｒ^１、Ｒ^３、Ｒ^４、及びｋは上記の通りであり、ｐ’は１から１００の整数である） The compound represented by the above formula (4) is further blocked with, for example, an organosilicon compound represented by the following formula (6), (7), or (8), thereby blocking the end. ) Can be obtained.

(Wherein R ³ , R ⁴ , and k are as described above, and X is a hydrolyzable group or a halogen atom)

(Wherein R ³ , R ⁴ , and k are as described above, and Q is an oxygen atom or ═N—H).

(Wherein R ¹ , R ³ , R ⁴ , and k are as described above, and p ′ is an integer of 1 to 100)

  In the above, X is a hydrolyzable group or a halogen atom. Examples of the halogen atom include a chlorine atom and a bromine atom. The hydrolyzable group is a group represented by -OR, and R is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the hydrolyzable group include a hydroxy group, a methoxy group, an ethoxy group, and an isopropoxy group. Of these, a chlorine atom, a hydroxy group, and a methoxy group are preferable, and a hydroxy group and a methoxy group are particularly preferable.

  Examples of the organosilicon compound represented by the above formula (6), (7), or (8) include 1,1,3,3-tetramethyldisiloxane and 1,3-diphenyl-1,3-dimethyldisiloxane. 1,1,3,3-tetraphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetravinyl-1,3-dimethyldi Disiloxanes such as siloxane, hexavinyldisiloxane, and 1,3-dimethyl-1,3-diphenyl-1,3-divinyldisiloxane; 1,1,3,3-tetramethyldisilazane, 1,3- Diphenyl-1,3-dimethyldisilazane, 1,1,3,3-tetraphenyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,1,3,3- Tetravinyl Silazanes such as 1,3-dimethyldisilazane, hexavinyldisilazane, and 1,3-dimethyl-1,3-diphenyl-1,3-divinyldisilazane; and 1,1,3,3,5,5 Hexamethyltrisiloxane, 1,5-divinyl-1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7,9,9-deca Methylpentasiloxane, 1,9-divinyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,1,3,5,5-pentamethyl-3-phenyl Trisiloxane, 1,5-divinyl-1,1,3,5,5-pentamethyl-3-phenyltrisiloxane, 1,1,3,5,7,9,9-heptamethyl-3,5,7-tri Phenylpentasiloxane, 1,9-divinyl-1 1,3,5,7,9,9-heptamethyl-3,5,7-triphenylpentasiloxane, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1,5-divinyl- 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1,5-dimethyl-1,3,3,5-tetraphenyltrisiloxane, 1,5-divinyl-1,5-dimethyl- 1,3,3,5-tetraphenyltrisiloxane, 1,1,9,9-tetramethyl-3,3,5,5,7,7-hexaphenylpentasiloxane, and 1,9-divinyl-1, Examples include siloxane oligomers or polymers such as 1,9,9-tetramethyl-3,3,5,5,7,7-hexaphenylpentasiloxane.

  The catalyst used in the above reaction may be at least one selected from an acid catalyst, a basic catalyst, and a metal element compound catalyst. Examples of the metal element compound catalyst include hydroxides of Group 2 elements of the periodic table, hydroxides of Group 2 elements of the periodic table, oxides of Group 2 elements of the periodic table, and periodic tables 3 to 3. A hydroxide or oxide of a metal element belonging to Group 15 is preferred. As the acid catalyst, dilute hydrochloric acid and acetic acid are preferable, and dilute hydrochloric acid is particularly preferable. As the basic catalyst, triethylamine and tetramethylammonium hydride are preferable, and triethylamine is particularly preferable.

  Metal element compound catalysts include radium hydroxide, barium hydroxide, strontium hydroxide, calcium hydroxide, magnesium hydroxide, beryllium hydroxide, barium hydroxide, barium hydroxide, strontium hydroxide, barium oxide, strontium oxide, oxidation Calcium, magnesium oxide, beryllium oxide, lanthanum hydroxide (III), cerium hydroxide (IV), zirconium hydroxide (IV), iron hydroxide (II), iron hydroxide (III), cobalt hydroxide (II), Nickel (II) hydroxide, copper (II) hydroxide, gold (III) hydroxide, zinc (II) hydroxide, cadmium hydroxide (II), aluminum (III) hydroxide, indium (III) hydroxide, water Thallium oxide (I), lead hydroxide (II), bismuth hydroxide (III), manganese oxide (IV , And iron oxide (II), include copper (II) oxide. Among these, from the viewpoint of availability and the like, hydroxides of Group 2 elements of the periodic table and hydroxides of metal elements belonging to Groups 3 to 15 of the periodic table are preferable. In particular, barium hydroxide, calcium hydroxide, magnesium hydroxide, strontium hydroxide, lanthanum hydroxide (III), aluminum hydroxide (III), iron hydroxide (II), iron hydroxide (III), and hydroxide Copper (II) is preferred. Further, it may be a hydroxide hydrate of the Group 2 element of the periodic table. In particular, barium hydroxide octahydrate, barium hydroxide monohydrate, and strontium hydroxide octahydrate are preferable.

  The metal element compound catalyst is preferably surface-treated with a silane coupling agent in advance. A conventionally well-known thing can be used for this silane coupling agent. In particular, from the viewpoint of the dispersibility of the catalyst, those having a structure similar to an organosilicon compound subjected to a condensation reaction, particularly an organosilicon compound containing an alkoxy group, are desirable. Examples of the silane coupling agent include trimethoxysilane, triethoxysilane, methyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, styryltrimethoxysilane, 3,3,3-tri Fluoro-propyltrimethoxysilane, 3-glycidyloxypropyldimethoxymethylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 1,1,3,3,5,5-hexamethoxy-1,3,5-trimethyltrisiloxane, 1,1,5,5-tetramethoxy-1,3,5- Trimethyl Polysiloxane-3-ol, dimethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyl dimethoxysilane, diphenyl dimethoxysilane, distyryl dimethoxysilane, di pentafluorophenyl dimethoxysilane, such as hexamethyldisilazane. Of these, trimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane are preferable.

  The surface treatment of the metal element compound catalyst with the silane coupling agent may be performed by a conventionally known method. For example, a wet method or a dry method can be used. The mixing ratio of the metal element compound catalyst and the silane coupling agent is not particularly limited, but in order not to impair the catalytic activity, the silane coupling agent 0.001 to 100 parts by mass of the metal element compound catalyst. It is preferable that it is 10 mass parts, Preferably it is 0.01-5 mass parts.

  The amount of the catalyst is not particularly limited as long as the condensation reaction proceeds sufficiently. For example, in the case of an acid-base catalyst, the amount is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight based on the total weight of the organosilicon compound and the catalyst. When an elemental compound is used as the catalyst, the amount is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 10% by weight based on the total weight of the organosilicon compound and the catalyst. The amount is 2 to 9% by weight, more preferably 0.5 to 5% by weight. If the amount of the catalyst is within the above range, it is preferable because a sufficient catalytic effect can be obtained in the condensation reaction.

  When a chlorosilane compound is used as the organosilane compound represented by the above formula (6) and the reaction is performed in the presence of water, the generated hydrochloric acid functions as a catalyst, so that it is not necessary to add a catalyst.

  The condensation reaction and end-capping reaction may be performed in the presence of at least one solvent. The solvent is used to adjust the reaction rate and reaction rate, or as a product diluent. The solvent may be one or more selected from nonpolar solvents and polar solvents. Examples of the nonpolar solvent include hydrocarbons such as n-hexane, n-heptane, and isooctane, and aromatic hydrocarbons such as toluene and xylene. Examples of the polar solvent include water; alcohols such as methanol, ethanol and isopropanol; alcohol esters; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as diethyl ether and dibutyl ether; ethyl acetate, isopropyl acetate and acetic acid. Esters such as butyl; Cyanide hydrocarbons such as acetonitrile; Amines; Amides such as acetamide; Halogenated hydrocarbons such as methylene chloride, chloroform and hexafluorometaxylene; Sulfur-containing compounds such as dimethyl sulfoxide Can be mentioned. The usage-amount of a solvent is not specifically limited, What is necessary is just to adjust suitably. Usually, the concentration of the organosilicon compound subjected to the reaction is 5 to 95% by mass, preferably 20 to 80% by mass. The above reaction can also be carried out in a solventless system.

  When a chlorosilane compound is used as the organosilane compound represented by the above formula (6), it is desirable to add an acid acceptor for neutralizing and removing hydrogen chloride generated by the reaction. Examples of the acid-accepting agent include alkylamines such as trimethylamine and triethylamine; nitrogen-containing heterocyclic compounds such as pyridine and piperazine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabiccyclo. Cyclic diamines such as [5.4.0] -7-undecene (DBU); 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetravinyl- Silazanes such as 1,3-dimethyldisilazane, hexavinyldisilazane, 1,3-dimethyl-1,3-diphenyl-1,3-divinyldisilazane; inorganic substances such as magnesium hydroxide, magnesium oxide, sodium bicarbonate And a system acid acceptor. Of these, triethylamine, pyridine, and magnesium oxide are preferable.

  The condensation reaction and the end-capping reaction may be performed as separate steps, and the end-capping reaction may be performed after the condensation reaction step, or the condensation reaction and the end-capping reaction may be performed in one step. According to the above production method, the catalyst can be easily removed from the reaction product. The catalyst filtration is preferably performed after completion of the condensation reaction, but may be performed after completion of the end-capping reaction. In the filtration, the above-mentioned solvent may be used for the purpose of adjusting the viscosity of the obtained reaction product. The production method of the present invention may further include a step of performing purification by a known method such as washing with water, reduced pressure strip, activated carbon treatment for the purpose of removing unreacted monomers from the reaction product.

  The condensation reaction may be performed under heating conditions. A preferable range of the reaction temperature is 0 to 160 ° C, more preferably 60 to 100 ° C. The end-capping reaction may also be performed under heating conditions. The preferable range of reaction temperature is 0-100 degreeC, More preferably, it is 20-80 degreeC. When the condensation reaction and the end-capping reaction are performed in one step, the reaction temperature is 0 to 160 ° C, preferably 20 to 80 ° C. The reaction time may be appropriately selected.

  The above production method may further include a step of performing purification by a known method such as washing with water, reduced-pressure strip, activated carbon treatment for the purpose of removing unreacted monomers from the reaction product. In particular, when the above-described acid acceptor is used, a hydrochloride derived from the acid acceptor is generated, and it is desirable to remove this by a known method such as filtration, washing with water, or activated carbon treatment. In particular, amine hydrochloride promotes the cleavage of siloxane bonds and may act as a catalyst poison for the hydrosilylation reaction. Therefore, when used as a raw material for addition-curable organopolysiloxane compositions, it should be removed from the product as much as possible. It is particularly preferred.

(B) Hydrosilylation catalyst (B) A component is a hydrosilylation catalyst. The catalyst may be any conventionally known catalyst and is not particularly limited. Among these, a catalyst selected from a platinum group metal simple substance and a platinum group metal compound is preferable. For example, platinum (including platinum black), platinum chloride, chloroplatinic acid, platinum-olefin complexes such as platinum-divinylsiloxane complex, platinum catalysts such as platinum-carbonyl complex, palladium catalysts, rhodium catalysts, and the like can be given. These catalysts may be used alone or in combination of two or more. Of these, platinum-olefin complexes such as chloroplatinic acid and platinum-divinylsiloxane complexes are particularly preferable.

(B) The compounding quantity of a component is not restrict | limited in particular, What is necessary is just a catalyst amount. The catalyst amount is an amount that allows the addition reaction to proceed, and may be adjusted as appropriate according to the desired curing rate. For example, when using a platinum group metal catalyst, from the viewpoint of reaction rate, 1.0 × 10 ^{−4 to} 1.0 with respect to 100 parts by mass of the component (A) on a mass basis converted to a platinum group metal atom. The amount of mass parts is preferable, and the amount of 1.0 × 10 ^{−3 to} 1.0 × 10 ⁻¹ mass parts is more preferable. In addition, when (C) component and (D) component which are mentioned later are included, it is good that it is the quantity used as the said mass part with respect to a total of 100 mass parts of (A), (C) and (D) component.

(C) Alkenyl group-containing organo (poly) siloxane The composition of the present invention may further comprise (C) an organo (poly) siloxane having at least two alkenyl groups in one molecule and having no hydrogen atom. it can. Examples of the organo (poly) siloxane include organo (poly) siloxanes represented by the following formula (2).
(R ⁸ ₃ SiO _1/2 ) _r (R ⁸ ₂ SiO _2/2 ) _s (R ⁸ SiO _3/2 ) _t (SiO _4/2 ) _u
(2)
In the above formulae, R ⁸ is independently of each other a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, and 2 carbon atoms. -10 alkenyl groups, provided that the compound has at least two alkenyl groups, r is an integer from 0 to 100, s is an integer from 0 to 300, t is an integer from 0 to 200, u Is an integer from 0 to 200, and 2 ≦ r + s + t + u ≦ 800, where r, s, t, and u are values in which the organo (poly) siloxane has at least two alkenyl groups in one molecule.

  The organo (poly) siloxane may be produced by a known method, or a commercially available product may be used.

Examples of the saturated hydrocarbon group and the aromatic hydrocarbon group include the same groups as those exemplified for R ¹ above. Examples of the alkenyl group include the same groups as those exemplified for R ³ above. At least two of the groups represented by R ⁸ are alkenyl groups, and the other R ⁸ is preferably a methyl group or a phenyl group.

  r is an integer of 0 to 100, preferably an integer of 1 to 75, and more preferably an integer of 2 to 50. s is an integer of 0 to 300, preferably an integer of 0 to 200, and more preferably an integer of 0 to 100. t is an integer of 0 to 200, preferably an integer of 1 to 100, and more preferably an integer of 1 to 50. u is an integer of 0-200, preferably an integer of 1-100, more preferably an integer of 1-50. The range is preferably 2 ≦ r + s + t + u ≦ 800, more preferably 2 ≦ r + s + t + u ≦ 400, and still more preferably 2 ≦ r + s + t + u ≦ 200.

  The organo (poly) siloxane may have any of linear, branched, network, and cyclic structures. Among these, a linear organopolysiloxane in which both t and u are 0 and r is 2 is preferable. In this case, s is an integer of 1 to 300, preferably an integer of 1 to 200, and more preferably. Is an integer from 1 to 100. A polysiloxane resin having a network shape is also preferable. In this case, 1 ≦ t + u ≦ 400, preferably 1 ≦ t + u ≦ 200, and more preferably 1 ≦ t + u ≦ 100.

  Such an organo (poly) siloxane can be obtained by co-condensing an organosilicon compound having an alkenyl group such as a vinyl group or an allyl group (for example, silane, siloxane, silazane) with another silane or siloxane. Preferred examples of the alkenyl group-containing silane include dimethylvinylchlorosilane, methylvinyldichlorosilane, vinyltrichlorosilane, trivinylchlorosilane, vinylmethylphenylchlorosilane, and alkoxy and silanol forms thereof. The siloxane is preferably a dimer, oligomer or polymer containing the alkenyl group-containing silane unit.

  Although the silane and siloxane to be co-condensed with the alkenyl group-containing organosilicon compound are not particularly limited, a silane having a hydrocarbon group containing a halogen, oxygen, nitrogen, or sulfur atom can be preferably used. For example, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, triphenylchlorosilane, diphenylmethylchlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, diphenyldichlorosilane, phenyltrichlorosilane, tetrachlorosilane, triethylchlorosilane, diethyldichlorosilane, ethyltri Chlorosilane, cyclohexylmethyldichlorosilane, cyclohexyltrichlorosilane and their alkoxy and silanol bodies, trifluoropropyltrimethoxysilane, β-cyanoethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3- Such as amino propyl trimethoxy silane can be used. Moreover, these oligomers and polymers can also be used suitably as siloxane. Cocondensation may be performed according to a conventionally known method.

In the component (C), at least one of the groups represented by R ⁸ is preferably an aromatic hydrocarbon group. In particular, it is preferable to have a monovalent aromatic hydrocarbon group bonded to a silicon atom in a number of 3% to 90% of the total number of all substituents bonded to the silicon atom, more preferably 5%. It is good to have above. The upper limit is preferably 80% or less. By having an aromatic hydrocarbon group in an amount preferably in the above range, the resulting cured product has a high refractive index and low gas permeability, and can be obtained because it is well compatible with other components. The composition gives a cured product having excellent transparency. Therefore, the composition can be suitably used for sealing a semiconductor device.

  (C) The compounding quantity of a component is 5-900 mass parts with respect to 100 mass parts of (A) component, Preferably it is 10-600 mass parts. When the component (C) is included in an amount within the above range, a rubber-like cured product is obtained, which is preferable. The ratio of the total number of hydrosilyl groups in component (A) or the total number of hydrosilyl groups in component (A) and component (D) to the total number of alkenyl groups in components (A) and (C) is 0. The amount of 4 to 4 is preferable, the amount of 0.6 to 2 is more preferable, and the amount of 0.8 to 1.6 is more preferable. If it is less than the above lower limit, SiH groups are insufficient, resulting in poor curing, and if it exceeds the above upper limit, side reactions such as dehydrogenation due to residual SiH groups are likely to occur.

(D) Organohydrogen (poly) siloxane The composition of the present invention may further contain an organohydrogen (poly) siloxane having at least two hydrosilyl groups and no alkenyl groups in one molecule. . Examples of the organohydrogen (poly) siloxane include siloxane represented by the following formula (4).
(R ⁶ ₃ SiO _1/2 ) _{r ′} (R ⁶ ₂ SiO _2/2 ) _{s ′} (R ⁶ SiO _3/2 ) _{t ′} (SiO _4/2 ) _{u ′}
(4)
In the above formula, R ⁶ is independently selected from a hydrogen atom, a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms. Provided that the compound has at least two hydrosilyl groups, r ′ is an integer from 0 to 100, s ′ is an integer from 0 to 300, t ′ is an integer from 0 to 200, and u ′ is from 0 to 200, 2 ≦ r ′ + s ′ + t ′ + u ′ ≦ 800, provided that r ′, s ′, t ′ and u ′ are at least two organo (poly) siloxanes in one molecule. It is a value having a hydrosilyl group.

  The organohydrogen (poly) siloxane may have any of linear, branched, network, and cyclic structures. Of these, linear and branched are preferable, and linear is particularly preferable. When it is linear, both t ′ and u ′ are 0, r ′ is 2, s ′ is an integer of 1 to 300, preferably an integer of 1 to 200, more preferably 1 It should be an integer of ~ 100. Further, it may be a polysiloxane resin having a network shape. In this case, 1 ≦ t ′ + u ′ ≦ 400, preferably 1 ≦ t ′ + u ′ ≦ 200, more preferably 1 ≦ t ′ + u ′ ≦ 100.

In the above formula (4), R ⁶ is a hydrogen atom or a group selected from the options of R ¹ described above. However, at least two of R ⁶ are hydrogen atoms. A substituent other than a hydrogen atom is preferably a methyl group or a phenyl group. r ′ is an integer of 0 to 100, preferably an integer of 0 to 75, more preferably an integer of 0 to 50, and s ′ is an integer of 0 to 300, preferably an integer of 0 to 200. More preferably, it is an integer of 0 to 100, t ′ is an integer of 0 to 200, preferably an integer of 0 to 100, more preferably an integer of 0 to 50, and u ′ is 0. It is an integer of ˜200, preferably an integer of 0 to 100, more preferably an integer of 0 to 50, and preferably 2 ≦ r ′ + s ′ + t ′ + u ′ ≦ 800. The range of r ′ + s ′ + t ′ + u ′ ≦ 400 is more preferable, and the range of 2 ≦ r ′ + s ′ + t ′ + u ′ ≦ 200 is even more preferable.

  Such an organohydrogen (poly) siloxane can be obtained by cocondensation of a silane or siloxane or silazane having a hydrosilyl group with another silane or siloxane. Examples of suitable hydrosilyl group-containing silanes are dimethylchlorosilane, methyldichlorosilane, trichlorosilane, monochlorosilane, methylphenylchlorosilane, and alkoxy and silanol forms thereof. Examples of suitable siloxanes include the above hydrosilyl group-containing silanes. Dimers, oligomers and polymers containing silane units.

  There are no particular limitations on the silane or siloxane that is co-condensed with the hydrosilyl group-containing silane, but trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, triphenylchlorosilane, diphenylmethylchlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, diphenyl. Dichlorosilane, phenyltrichlorosilane, tetrachlorosilane, triethylchlorosilane, diethyldichlorosilane, ethyltrichlorosilane, cyclohexylmethyldichlorosilane, cyclohexyltrichlorosilane and their alkoxy and silanol forms, trifluoropropyltrimethoxysilane, β-cyanoethyltrimethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxy B pills trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-aminopropyl halide and oxygen, such as trimethoxysilane, nitrogen, can be suitably used silanes having a hydrocarbon group containing a sulfur atom. Moreover, as siloxanes, these oligomers and polymers can also be suitably used.

In the component (D), at least one of the groups represented by R ⁶ is preferably an aromatic hydrocarbon group. In particular, it is preferable to have a monovalent aromatic hydrocarbon group bonded to a silicon atom in a number of 3% to 90% of the total number of all substituents bonded to the silicon atom, more preferably 5%. It is good to have above. The upper limit is preferably 80% or less. By having an aromatic hydrocarbon group in an amount preferably in the above range, the resulting cured product has a high refractive index and low gas permeability, and can be obtained because it is well compatible with other components. The composition gives a cured product having excellent transparency. Therefore, the composition can be suitably used for sealing a semiconductor device.

  The amount of component (D) is relative to the total number of alkenyl groups in (A), or to the total number of alkenyl groups in component (A) and component (C) if the component (C) is included. The amount in which the total number of hydrosilyl groups in component (A) and component (D) is 0.4 to 4 is preferable, more preferably 0.6 to 2, and still more preferably 0.8 to 1. The amount is .6. If it is less than the above lower limit, SiH groups are insufficient, resulting in poor curing, and if it exceeds the above upper limit, side reactions such as dehydrogenation due to residual SiH groups are likely to occur. Further, the amount of the component (A) relative to the total weight of the component (A) and the component (D) is preferably 5 to 95%, preferably 10 to 90%, more preferably 20 to 80%. The amount should be%.

  The silicone composition of the present invention contains, in addition to the components (A) to (D) described above, other additives such as phosphors, inorganic fillers, adhesion assistants, and curing inhibitors as necessary. May be. Hereinafter, each component will be described.

[Phosphor]
The phosphor is not particularly limited, and a conventionally known phosphor may be used. For example, it is preferable to absorb light from a semiconductor element, particularly a semiconductor light emitting diode having a nitride-based semiconductor as a light emitting layer, and convert the light to light having a different wavelength. Examples of such phosphors include nitride-based phosphors / oxynitride-based phosphors mainly activated by lanthanoid elements such as Eu and Ce, lanthanoid-based substances such as Eu, and transition metal-based substances such as Mn. Alkaline earth metal halogen apatite phosphor, alkaline earth metal borate phosphor, alkaline earth metal aluminate phosphor, alkaline earth metal silicate phosphor, alkaline earth metal activated mainly by elements Sulfide phosphor, alkaline earth metal thiogallate phosphor, alkaline earth metal silicon nitride phosphor, germanate phosphor, rare earth aluminate phosphor mainly activated by lanthanoid elements such as Ce, rare earth Organic and organic complex phosphors mainly activated by lanthanoid elements such as silicate phosphors or Eu, Ca—Al—Si—O—N oxynitride glass phosphors It is preferably at least one member selected from.

As a nitride phosphor mainly activated by a lanthanoid element such as Eu or Ce, M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn) There is). _{Further, MSi 7 N 10: Eu,} M 1.8 Si 5 O 0.2 N 8: Eu, and _{M 0.9 Si 7 O 0.1 N 10} : Eu (M is, Sr, Ca, Ba, Mg And at least one selected from Zn).

As an oxynitride phosphor mainly activated by a lanthanoid element such as Eu or Ce, MSi ₂ O ₂ N ₂ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn) Is).

Examples of alkaline earth metal halogen apatite phosphors mainly activated by lanthanoid-based elements such as Eu and transition metal-based elements such as Mn include M ₅ (PO ₄ ) ₃ X: R (M is Sr, Ca, Ba). X is at least one selected from F, Cl, Br and I. R is any one or more of Eu, Mn, Eu and Mn) Is mentioned.

As the alkaline earth metal borate phosphor, M ₂ B ₅ O ₉ X: R (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F, Cl, And at least one selected from Br and I. R is any one or more of Eu, Mn, Eu and Mn).

The alkaline earth metal aluminate _{phosphor, SrAl 2 O 4: R,} Sr 4 Al 14 O 25: R, CaAl 2 O 4: R, BaMg 2 Al 16 O 27: R, BaMg 2 Al 16 O 12 : R and BaMgAl ₁₀ O ₁₇ : R (R is any one or more of Eu, Mn, Eu and Mn).

Examples of the alkaline earth metal sulfide phosphor include La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu.

As rare earth aluminate phosphors mainly activated by a lanthanoid element such as Ce, Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ Examples thereof include YAG-based phosphors represented by the composition formula of (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce and (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ . Further, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is substituted with Tb, Lu or the like.

Other phosphors include ZnS: Eu, Zn ₂ GeO ₄ : Mn, MGa ₂ S ₄ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F) , Cl, Br, or I).

  The phosphor contains at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, Ti instead of Eu or in addition to Eu as desired. Can do.

The Ca—Al—Si—O—N-based oxynitride glass phosphor is in mol%, CaCO ₃ is converted to CaO, 20 to 50 mol%, Al ₂ O ₃ is 0 to 30 mol%, and SiO is doped. An oxynitride glass having 25 to 60 mol%, 5 to 50 mol% AlN, 0.1 to 20 mol% rare earth oxide or transition metal oxide, and a total of five components of 100 mol% is used as a base material. Phosphor. In addition, in the phosphor using oxynitride glass as a base material, the nitrogen content is preferably 15 wt% or less, and other rare earth element ions serving as a sensitizer in addition to rare earth oxide ions are used as rare earth oxides. It is preferable to contain as a co-activator in content in the range of 0.1-10 mol% in fluorescent glass.

  Moreover, it is also possible to use a phosphor other than the above phosphors and having the same performance and effect.

  As for the compounding quantity of fluorescent substance, 0.1-2,000 mass parts is preferable with respect to 100 mass parts of components other than fluorescent substance, for example (A) and (B) component, More preferably, it is 0.1-100 mass. Part. When making the hardened | cured material of this invention into a fluorescent substance containing wavelength conversion film, it is preferable that content of fluorescent substance shall be 10-2,000 mass parts. The phosphor preferably has an average particle diameter of 10 nm or more, more preferably 10 nm to 10 μm, and still more preferably 10 nm to 1 μm. The average particle diameter is measured by particle size distribution measurement by a laser light diffraction method such as a cirrus laser measuring apparatus.

[Inorganic filler]
Examples of the inorganic filler include silica, fumed silica, fumed titanium dioxide, alumina, calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, and zinc oxide. These can be used individually by 1 type or in combination of 2 or more types. Although the compounding quantity of an inorganic filler is not restrict | limited in particular, What is necessary is just to mix | blend suitably in the range of 20 mass parts or less, preferably 0.1-10 mass parts per 100 mass parts in total of (A) and (B) component.

[Adhesion aid]
The silicone composition of the present invention may contain an adhesion aid as necessary in order to impart adhesiveness. Examples of the adhesion assistant include organosiloxane oligomers having at least two, preferably three, functional groups selected from a hydrogen atom bonded to a silicon atom, an alkenyl group, an alkoxy group, and an epoxy group in one molecule. . The organosiloxane oligomer preferably has 4 to 50 silicon atoms, more preferably 4 to 20 silicon atoms. Moreover, as an adhesion assistant, an organooxysilyl-modified isocyanurate compound represented by the following general formula (9) and a hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound) can be used.

上記式（９）中、Ｒは互いに独立に、下記（１０）で示される有機基、又は酸素原子を有してよい脂肪族不飽和炭化水素基である。但し、Ｒの少なくとも１個は下記（１０）で示される基である。

In the above formula (9), R is independently an organic group represented by the following (10) or an aliphatic unsaturated hydrocarbon group which may have an oxygen atom. However, at least one R is a group represented by the following (10).

Ｒ^’は水素原子又は炭素数１〜６の一価炭化水素基であり、ｎは１〜６の整数、好ましくは１〜４の整数である。脂肪族不飽和炭化水素基としては、好ましくは炭素数２〜８、更に好ましくは炭素数２〜６の、直鎖状又は分岐を有するアルケニル基、例えば、ビニル基、アリル基、１−ブテニル基、１−ヘキセニル基、及び２−メチルプロペニル基、又は（メタ）アクリル基等が挙げられる。

R ^′ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6, preferably an integer of 1 to 4. The aliphatic unsaturated hydrocarbon group is preferably a linear or branched alkenyl group having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, such as a vinyl group, an allyl group, or a 1-butenyl group. , 1-hexenyl group, 2-methylpropenyl group, or (meth) acryl group.

  The compounding amount of the adhesion assistant is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, particularly preferably 0.2 to 100 parts by mass with respect to the total of 100 parts by mass of the components (A) and (B). 5 parts by mass. If the blending amount is less than or equal to the above upper limit value, the cured product hardness is high, and surface tackiness is also suppressed.

[Curing inhibitor]
The silicone composition of the present invention may contain a curing inhibitor in order to control the reactivity and increase the storage stability. The curing inhibitor is selected from the group consisting of triallyl isocyanurate, alkyl maleate, acetylene alcohols, silane-modified products and siloxane-modified products thereof, hydroperoxide, tetramethylethylenediamine, benzotriazole, and mixtures thereof. Compounds. As for the compounding quantity of a hardening inhibitor, 0.001-1 mass part is preferable per 100 mass parts of total of (A) and (B) component, More preferably, it is 0.005-0.5 mass part.

[Other additives]
In addition to the above components, other additives can be added to the silicone composition of the present invention. Examples of other additives include anti-aging agents, radical inhibitors, flame retardants, surfactants, ozone degradation inhibitors, light stabilizers, thickeners, plasticizers, antioxidants, thermal stabilizers, and conductivity. Examples include an imparting agent, an antistatic agent, a radiation blocking agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a physical property modifier, and an organic solvent. These optional components may be used alone or in combination of two or more.

  The simplest embodiment of the silicone composition of the present invention is a composition comprising a component (A) and a component (B). Furthermore, it is a composition comprising the component (A), the component (B), and the component (C), and a composition comprising the component (A), the component (B), the component (C), and the component (D). Good. A composition further containing a phosphor is also preferred. In particular, in order to obtain a cured product having high transparency, it is preferable not to contain an inorganic filler such as a silica filler. Examples of the inorganic filler are as described above.

  The method for preparing the silicone composition of the present invention is not particularly limited, and may be a conventionally known method. The component (A), the component (B), and optionally the component (C) and the component (D). And other optional components may be prepared by mixing by any method. For example, it can be prepared by putting in a commercially available stirrer (THINKY CONDITIONING MIXER (manufactured by Shinky Co., Ltd.)) and mixing uniformly for about 1 to 5 minutes.

  The method for curing the silicone composition of the present invention is not particularly limited, and may be a conventionally known method. For example, it can be cured at 60 to 180 ° C. for about 1 to 12 hours. In particular, it is preferable to cure by step cure at 60 to 150 ° C. In step cure, it is more preferable to go through the following two stages. First, the silicone composition is heated at a temperature of 60 to 100 ° C. for 0.5 to 2 hours to sufficiently degas. Next, the silicone composition is heat-cured at a temperature of 120 to 180 ° C. for 1 to 10 hours. By passing through these steps, even if the cured product is thick, it can be sufficiently cured, no bubbles are generated, and it can be colorless and transparent. In the present invention, the colorless and transparent cured product means that the light transmittance at 450 nm with respect to 1 mm thickness is 80% or more, preferably 85% or more, particularly preferably 90% or more.

  The silicone composition of the present invention provides a cured product having high light transmittance. Therefore, the silicone composition of the present invention is useful for LED element sealing, particularly for blue LED or ultraviolet LED element sealing. The method of sealing LED elements etc. with the silicone composition of this invention should just follow a conventionally well-known method. For example, a dispensing method and a compression molding method can be used.

  Furthermore, since the silicone composition of the present invention gives a cured product having excellent crack resistance, heat resistance, light resistance, transparency, etc., display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fibers It is also useful for applications such as materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.
The weight average molecular weight (Mw) shown in the following examples is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are shown below.
[GPC measurement conditions]
Developing solvent: Tetrahydrofuran Flow rate: 0.6 mL / min
Column: TSK Guardcolumn SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H3000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH2000 (6.0 mm ID × 15 cm × 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection amount: 20 μL (sample concentration: 0.5 wt% -tetrahydrofuran solution)
Detector: Differential refractometer (RI)

The Vi value (mol / 100 g) and SiH value (mol / 100 g) shown in the following Examples are obtained by measuring a 400 MHz ¹ H-NMR spectrum of a compound, and an integrated value of hydrogen atoms obtained using dimethyl sulfoxide as an internal standard. It is calculated from
Further, ¹ H-NMR measurement was performed using ULTRASHIELD ^™ 400PLUS (manufactured by BRUKER), and ²⁹ Si-NMR measurement was performed using RESONANCE 500 (manufactured by JEOL).

[Synthesis Example 1] Synthesis of branched organopolysiloxane (A-1) 60.9 g (0.2 mol) of 1,1-diphenyl-1-methyl-3,3-dimethoxydisiloxane, polymethylphenylsiloxane-α, 274.1 g (0.51 mol) of ω-diol (Mw = 537.43) and 27.9 g (0.24 mol) of dimethylvinylmethoxysilane were stirred and adjusted to 50 ° C. Thereafter, 3.6 g of Ca (OH) ₂ .8H ₂ O was added, and the reaction was performed at 50 ° C. for 12 hours. From the obtained product, the catalyst was removed by filtration, and methanol and water were distilled off under reduced pressure to obtain a branched organopolysiloxane which was oily and represented by the following formula. Mw = 3,606, Vi value = 0.059 mol / 100 g, SiH value = 0.056 mol / 100 g. ^{From the 29} Si-NMR spectrum, it was found that n = average 20 and m = average 1.9 in the following formula.

[Synthesis Example 2] Synthesis of branched organopolysiloxane (A-2) 1,1,3,3-tetraphenyl-1-methyl-5,5-dimethoxytrisiloxane 100.6 g (0.2 mol), polymethyl 687.9 g (1.28 mol) of phenylsiloxane-α, ω-diol (Mw = 537.43) and 27.9 g (0.24 mol) of dimethylvinylmethoxysilane were mixed and adjusted to 80 ° C. with stirring. Thereafter, 7.7 g of Sr (OH) ₂ .8H ₂ O was added, and the reaction was performed at 80 ° C. for 12 hours while distilling off the generated methanol. From the obtained product, the catalyst was removed by filtration, and methanol and water were distilled off under reduced pressure to obtain a branched organopolysiloxane which was oily and represented by the following formula. Mw = 7,928, Vi value = 0.026 mol / 100 g, SiH value = 0.024 mol / 100 g. ^{From 29} Si-NMR spectrum, it was found that n = average 49 and m = average 1.8 in the following formula.

[Synthesis Example 3] Synthesis of branched organopolysiloxane (A-3) 121.8 g (0.4 mol) of 1,1-diphenyl-1-methyl-3,3-dimethoxydisiloxane, 17.4 g of dimethylvinylmethoxysilane (0.15 mol) and 34.2 g of water were mixed, and 1.4 g of Sr (OH) ₂ .8H ₂ O was added with stirring. Then, it reacted at 80 degreeC for 12 hours, distilling off generated methanol. Water and methanol were distilled off from the obtained product, and the catalyst was removed by filtration to obtain a branched organopolysiloxane which was oily and represented by the following formula. The molecular weight was Mw = 2,128, Vi value = 0.10 mol / 100 g, SiH value = 0.36 mol / 100 g. ^{From 29} Si-NMR, it was found that n = average 7 in the following formula.

Synthesis Example 4 Synthesis of Branched Organopolysiloxane (A-4) 1,1-Diphenyl-1,3-dimethyl-3,3-dimethoxydisiloxane 127.4 g (0.4 mol), polymethylsiloxane-α , Ω-diol (Mw = 640) 640.0 g (1.0 mol) and dimethylvinylmethoxysilane 27.90 g (0.24 mol) were mixed and adjusted to 80 ° C. with stirring. Thereafter, 15.9 g of Ca (OH) ₂ .8H ₂ O was added, and the reaction was carried out at 80 ° C. for 12 hours while distilling off the generated methanol. From the obtained product, the catalyst was removed by filtration, and methanol and water were distilled off under reduced pressure to obtain a branched organopolysiloxane which was oily and represented by the following formula. Mw = 7,429, Vi value = 0.028 mol / 100 g, SiH value = 1.38 mol / 100 g. ^{From 29} Si-NMR, n = average 99 and m = average 3.9 in the following formula.

[Synthesis Example 5] Synthesis of branched organopolysiloxane (A-5) 1,1,1-trimethyl-3-vinyl-3,3-dimethoxydisiloxane 206.4 g (1 mol) and polydimethylsiloxane-α, ω -Diol (Mw = 1498) 749.0g (0.5mol) was mixed, and it adjusted to 80 degreeC, stirring. Thereafter, 23.1 g of Sr (OH) ₂ .8H ₂ O was added, and the reaction was carried out at 80 ° C. for 12 hours while distilling off the generated methanol. Next, after cooling to 10 ° C., 11.4 g (0.12 mol) of dimethylchlorosilane was added dropwise, the reaction was performed at 10 ° C. for 1 hour, and the reaction was further performed at 40 ° C. for 8 hours. The obtained product was washed with water, and water and unreacted substances were distilled off under reduced pressure to obtain an oily branched organopolysiloxane represented by the following formula. Mw = 18,358, Vi value = 0.12 mol / 100 g, SiH value = 0.111 mol / 100 g. ^{From 29} Si-NMR, it was found that n = average 198 and m = average 21 in the following formula.

上記式において、ＲはＣＨ_３またはＨであり、平均して少なくとも２つのＲは水素原子である。 [Comparative Synthesis Example 6] Synthesis of comparative branched organohydrogenpolysiloxane (A'-1) Octamethylcyclotetrasiloxane 1483 g (5 mol), 1,1,3,3-tetramethyldisiloxane 13.4 g (0 0.1 mol), 296.5 g (2 mol) of vinyltrimethoxysilane, 8.1 g (0.05 mol) of hexamethyldisiloxane, 8.9 g of potassium hydroxide, and 120 g of water, and methanol generated at 80 ° C. for 8 hours. The reaction was carried out while distilling off. Subsequently, after performing reaction for 12 hours, distilling off water at 140 degreeC, it cooled to 80 degreeC and neutralized with 10.1 g of acetic acid. Then, the branched organopolysiloxane which is oily and represented by the following formula was obtained by washing with water and distilling off under reduced pressure. Mw = 16,895, Vi value = 0.12 mol / 100 g, SiH value = 0.012 mol / 100 g. ^{From 29} Si-NMR, it was found that n and n ′ were each an average of 100 and m was an average of 20 in the following formula.

In the above formula, R is CH ₃ or H, and on average at least two R are hydrogen atoms.

ｎ単位数とｍ単位数の比率：ｎ＝０．２２、ｍ＝０．７８

（Ｃ−２）下記式で表されるシリコーンレジン（信越化学工業株式会社製、Ｖｉ価＝０．０９１ｍｏｌ／１００ｇ、重量平均分子量はＭｗ＝５２１１）

ｎ単位数、ｍ単位数、及びｊ単位数の比率：ｎ＝０．０６、ｍ＝０．３６、ｊ＝０．５８

（Ｃ−３）下記式で表されるシリコーンオイル（信越化学工業株式会社製、Ｖｉ価＝０．０３８ｍｏｌ／１００ｇ）

（Ｃ−４）下記式で表されるシリコーンオイル（信越化学工業株式会社製、Ｖｉ価＝０．０１３ｍｏｌ／１００ｇ）

（Ｄ−１）下記式で表される直鎖状オルガノハイドロジェンシロキサン（信越化学工業株式会社製、ＳｉＨ価＝０．６０ｍｏｌ／１００ｇ）

（Ｄ−２）下記式で表される分岐状オルガノハイドロジェンシロキサン（信越化学工業株式会社製、ＳｉＨ価＝０．９０ｍｏｌ／１００ｇ）

（Ｄ−３）下記式で表される直鎖状オルガノハイドロジェンポリシロキサン（信越化学工業株式会社製、ＳｉＨ価＝１．６３ｍｏｌ／１００ｇ）

The components (B), (C), and (D) used in the examples and comparative examples are as follows.
(B) Divinylsiloxane complex of chloroplatinic acid (C-1) Silicone resin represented by the following formula (Shin-Etsu Chemical Co., Ltd., Vi value = 0.147 mol / 100 g, weight average molecular weight is Mw = 1563)

Ratio of n unit number to m unit number: n = 0.22, m = 0.78

(C-2) Silicone resin represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 0.091 mol / 100 g, weight average molecular weight is Mw = 5211)

Ratio of n unit number, m unit number, and j unit number: n = 0.06, m = 0.36, j = 0.58

(C-3) Silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 0.038 mol / 100 g)

(C-4) Silicone oil represented by the following formula (Shin-Etsu Chemical Co., Ltd., Vi value = 0.013 mol / 100 g)

(D-1) Linear organohydrogensiloxane represented by the following formula (Shin-Etsu Chemical Co., Ltd., SiH value = 0.60 mol / 100 g)

(D-2) Branched organohydrogensiloxane represented by the following formula (Shin-Etsu Chemical Co., Ltd., SiH value = 0.90 mol / 100 g)

(D-3) Linear organohydrogenpolysiloxane represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 1.63 mol / 100 g)

[Examples 1 to 5 and Comparative Examples 1 to 3]
The above components other than the catalyst were mixed in the blending amounts shown in Table 1, and (B) the catalyst was added in an amount of 5 ppm as a platinum amount with respect to the total mass of the entire composition, and further mixed, and the silicone composition was mixed. It was adjusted. The following tests were conducted on the silicone compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3. In addition, the value of H / Vi described in Table 1 is a ratio of the total number of hydrosilyl groups to the total number of vinyl groups in the entire composition.

[(1) Viscosity of silicone composition]
According to JIS Z 8803: 2011, the viscosity of the silicone composition at 23 ° C. was measured using a B-type viscometer. The results are listed in Table 2.

[(2) Hardness of cured product]
The prepared silicone composition was poured into an aluminum petri dish with a diameter of 50 mm and a thickness of 10 mm, and cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, 150 ° C. × 4 hours to obtain a cured product. The hardness (durometer Type A or Type D) of the obtained cured product was measured according to JIS K 6253-3: 2012. The results are listed in Table 2.

[(3) Light transmittance of cured product]
A concave 1 mm thick Teflon (registered trademark) spacer is sandwiched between two 50 mm × 20 mm × 1 mm thick glass slides, and after fixing them, the silicone composition is poured, 60 ° C. × 1 hour, 100 ° C. × 1 hour Then, a sample was prepared by step curing in the order of 150 ° C. × 4 hours. The light transmittance at 450 nm of the obtained sample was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The results are listed in Table 2.

[(4) Tensile strength of cured product and elongation at break]
The prepared silicone composition was poured into a 150 mm × 200 mm × 2 mm thick concave Teflon (registered trademark) mold, and the sample was step-cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, and then 150 ° C. × 4 hours. Was made. In accordance with JIS K 6251: 2010, using EZ TEST (EZ-L, manufactured by Shimadzu Corporation), the sample was pulled under the conditions of a test speed of 500 mm / min, a distance between grippers of 80 mm, and a distance between gauge points of 40 mm. Strength and elongation at break were measured. The results are listed in Table 2.

[(5) Glass transition temperature of cured product]
The storage elastic modulus (MPa) of the cured product sample prepared in (4) above was measured in the range of −140 ° C. to 150 ° C. using DMA Q800 (manufactured by TA Instruments Co., Ltd.), and the storage elastic modulus obtained. The temperature at the peak top obtained from the graph plotting the value of Tan δ derived from the value of γ was the glass transition temperature: Tg. Measurement conditions were 20 mm long × 5 mm width × 1 mm thick sample, temperature rising rate 5 ° C./min, multi-frequency mode, tensile mode, and amplitude 15 μm. The results are listed in Table 2.

[(6) Temperature cycle test]
The silicone composition was dispensed into a Tigger 3528 package (manufactured by Shin-Etsu Chemical Co., Ltd.), step cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, then 150 ° C. × 4 hours, and the package was sealed with a cured product. Test specimens were manufactured. About 20 of the test specimens, a thermal cycle test (TCT) of -50 ° C. to 140 ° C. and 1,000 times was performed, and the number of the test specimens in which cracks occurred in the encapsulated material was measured. The results are listed in Table 2.

  As shown in Comparative Examples 1 to 3 in Table 2, obtained from a silicone composition containing a branched organopolysiloxane having a long siloxane chain in the branched chain and a silicone composition containing an organopolysiloxane having no branched chain The cured product is cracked in the TCT test and is inferior in low temperature and high temperature resistance. On the other hand, as shown in Examples 1 to 5 of Table 2, the silicone composition containing the branched organopolysiloxane of the present invention is a cured product excellent in low temperature and high temperature resistance without causing cracks in the TCT test. give. Further, as can be seen from the comparison between Example 1 and Comparative Example 1 and the comparison between Example 5 and Comparative Example 3, organopolysiloxane of the present invention having a short branched chain is used for the organopolysiloxane having the same chain length. The composition containing the glass transition temperature is lower than that of the composition containing an organopolysiloxane having a straight chain or a long branched chain. In addition, Examples 4-5 and Comparative Examples 2-3 have remarkably low glass transition temperatures compared with Examples 1-3 and Comparative Example 1. This is because one or more or all of the components (A), (C), and (D) do not have an aromatic group.

[Water vapor transmission rate]
The silicone compositions of Example 1, Example 5, and Comparative Example 1 were respectively poured into a concave Teflon (registered trademark) mold having a thickness of 150 mm × 200 mm × 2 mm, and 60 ° C. × 1 hour, 100 ° C. × 1 hour, 150 ° C. × Step cure in order of 4 hours to prepare each test sample. The water vapor transmission rate of the obtained sample was measured by the Lyssy method (device name L80-5000, manufactured by Lyssy) based on JIS K7129. The water vapor permeability of each cured product was as follows.
Example 1: 28 g · m ² / day
Example 5: 50 g · m ² / day
Comparative Example 1: 26 g · m ² / day
The component (A) and the component (D) contained in the compositions of Example 1 and Comparative Example 1 have an aromatic group. On the other hand, the component (A), the component (C) and the component (D) contained in the composition of Example 5 do not have an aromatic group. As shown in the above results, in order to obtain a cured product having lower gas permeability, the component (A), the component (C) and the component (D) preferably have an aromatic group.

  The cured product obtained from the addition-curable silicone composition of the present invention has good low temperature characteristics, excellent temperature change resistance, and good crack resistance. Therefore, by sealing the semiconductor element with the cured product of the addition-curable silicone composition of the present invention, a semiconductor device having excellent reliability can be provided. Moreover, in order to give the hardened | cured material which has high light transmittance, it is useful for LED element sealing, especially for blue LED and ultraviolet LED element sealing.

Claims (9)

Addition-curable silicone composition containing the following components (A) and (B) (A) Branched organopolysiloxane represented by the following formula (1)

(In the formula, R ¹ is, independently of each other, a substituted or unsubstituted saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ³ is independently of each other. , A hydrogen atom, a substituted or unsubstituted saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms, R ⁴ is independently of each other a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and k is an integer of 0 to 3 independently of each other. , the compound has at least two groups represented by R ³ in the molecule, at least one of R ³ is a hydrogen atom, and at least one of R ³ is an alkenyl group, x is from 0 to 3 An integer, a is an integer from 1 to 75 , and b is an integer from 0 to 230 . 1 ≦ a + b ≦ 300 , and the siloxane unit in parentheses enclosed by a or b may form a random structure or a block unit)
And (B) hydrosilylation catalyst, catalytic amount. Further, (C) an organo (poly) siloxane represented by the following formula (2) is converted into (R ⁸ ₃ SiO _1/2 ) _r (R ⁸ ₂ SiO _2/2 ) _s (R ⁸ SiO _3/2 ) _t (SiO _{4 / 2} ) _u (2)
(In the formula, R ⁸ is independently of each other a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. A group selected, provided that the compound has at least two alkenyl groups, r is an integer of 0 to 100, s is an integer of 0 to 300, t is an integer of 0 to 200, and u is an integer of 0 to 200. 2 ≦ r + s + t + u ≦ 800, where r, s, t and u are values in which the organopolysiloxane has at least two alkenyl groups in one molecule)
The amount of the component (A) is 5 to 900 parts by mass with respect to 100 parts by mass of the component, and the hydrosilyl group in the component (A) with respect to the total number of alkenyl groups in the component (A) and the component (C) The addition-curable silicone composition according to claim 1, wherein the addition-curable silicone composition is contained in an amount of 0.4 to 4. Further, (D) an organohydrogen (poly) siloxane represented by the following formula (4) is converted into (R ⁶ ₃ SiO _1/2 ) _{r ′} (R ⁶ ₂ SiO _2/2 ) _{s ′} (R ⁶ SiO _3/2 ) _{t ′} (SiO _4/2 ) _{u ′} (4)
(In the formula, R ⁶ is a group independently selected from a hydrogen atom and a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Wherein the compound has at least two hydrosilyl groups, r ′ is an integer from 0 to 100, s ′ is an integer from 0 to 300, t ′ is an integer from 0 to 200, u ′ is an integer from 0 to 200 Yes, 2 ≦ r ′ + s ′ + t ′ + u ′ ≦ 800, provided that r ′, s ′, t ′ and u ′ are at least two hydrosilyl groups in one molecule of the organohydrogen (poly) siloxane. Is a value with
The component (A) with respect to the total number of alkenyl groups in the component (A) or the total number of alkenyl groups in the component (A) and the component (C) when the component (C) is included. The ratio of the total number of hydrosilyl groups in component (D) is 0.4 to 4, and the mass of component (D) relative to the total mass of components (A) and (D) is 5 to 5. The addition-curable silicone composition according to claim 1 or 2, which is contained in an amount of 95%.   The addition-curable silicone composition according to any one of claims 1 to 3, wherein x = 0 in formula (1). The addition-curable silicone composition according to any one of claims 1 to 4, wherein in formula (1), at least one of R ¹ is an aromatic hydrocarbon group having 6 to 12 carbon atoms.   The component (A) has a monovalent aromatic hydrocarbon group bonded to a silicon atom in an amount of 3% to 90% of the total number of all substituents bonded to the silicon atom. The addition-curable silicone composition according to any one of the above.   A semiconductor device provided with the hardened | cured material obtained by hardening | curing the addition-curable silicone composition of any one of Claims 1-6.   The semiconductor device according to claim 7, wherein the semiconductor device includes a semiconductor element, and the semiconductor element is covered with the cured product.   The semiconductor device according to claim 8, wherein the semiconductor element is a light emitting element.