JP2019151767A - Thermosetting silicone composition, silicone resin cured product, and semiconductor device - Google Patents

Abstract

To provide a transparent thermosetting silicone composition which has high fluidity at room temperature and gives a cured product excellent in transparency and heat resistance (thermal stability), especially thermal discoloration resistance, and having high gas barrier properties.SOLUTION: The thermosetting silicone composition contains: (A-1) 30-70 pts.mass of an addition reaction product of (a) a compound having two hydrogen atoms bonded to silicon atoms in one molecule and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, the addition reaction product having at least two addition-reactive carbon-carbon double bonds in one molecule; (A-2) 30-70 pts.mass of a compound represented by general formula (3); (B) an organosilicon compound having three or more hydrogen atoms bonded to silicon atoms in one molecule; and (C) a hydrosilylation reaction catalyst.SELECTED DRAWING: None

Description

  The present invention provides a transparent thermosetting silicone composition that gives a cured silicone resin useful as an optical element sealing material, particularly a white LED (light emitting diode) sealing material, a cured product of the composition, and the cured product. The present invention relates to a semiconductor device in which an optical element is sealed.

  The thermosetting silicone composition contains an organopolysiloxane containing an addition-reactive carbon-carbon double bond and an organosilicon compound having a hydrogen atom bonded to silicon, and is cured by a hydrosilylation reaction to give a cured product. The cured product thus obtained is excellent in heat resistance, cold resistance, and electrical insulation, and is transparent, so it is used in various optical applications such as LED sealing materials (Patent Documents 1 and 2). ).

  However, since the optical element sealing material made of such a composition generally has a low gas barrier property, there is a drawback that the silver electrode is discolored by the invasion of corrosive gas from the outside. As a result, the brightness of the LED may decrease.

  Therefore, an optical element sealing material using a thermosetting silicone composition containing a polycyclic hydrocarbon skeleton-containing component has been proposed. Since the sealing material obtained from such a composition has a high gas barrier property, it is possible to prevent the entry of corrosive gas from the outside and suppress discoloration of the silver electrode. However, there is a problem that it cannot be used particularly for high-power LEDs due to the drawback of being easily discolored by heat (Patent Documents 3 and 4).

  An optical element sealing material using a thermosetting silicone composition having a phenyl group introduced into the main skeleton has been proposed. The sealing material obtained from such a composition is excellent in heat discoloration compared with the polycyclic hydrocarbon skeleton-containing sealing material described in Patent Documents 3 and 4 above, but silver due to corrosive gas from the outside. The point of suppressing the corrosion of the electrode is not fully satisfied (Patent Document 5).

JP 2004-186168 A JP 2004-143361 A JP 2008-069210 A JP 2012-0466604 A JP 2010-132895 A

  The present invention has been made in view of the above circumstances, and is a cured product having high fluidity at room temperature, excellent transparency, heat resistance (thermal stability), particularly heat discoloration, and further high gas barrier properties. A thermosetting silicone composition is provided. That is, the present invention provides a transparent thermosetting silicone composition that provides a cured silicone resin useful as an optical element sealing material, and a semiconductor device that is sealed with a cured product of the composition. Objective.

（式中Ａは下記一般式（２）で表される基から成る群から選ばれる２価の基であり、Ｒ^１は、独立に非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は炭素原子数１〜６のアルコキシ基である。）

（式中Ｐｈはフェニル基であり、Ｒ^２は独立に非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基であり、Ｒ^３は付加反応性炭素−炭素二重結合含有基であり、ｎは１〜２０の整数である。） In order to achieve the above object, in the present invention,
(A-1) (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule; and (b) 1 addition-reactive carbon-carbon double bond. 30 to 70 parts by mass of an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, which is an addition reaction product with two polycyclic hydrocarbons in the molecule
(A-2) 30 to 70 parts by mass of a compound represented by the following general formula (3) (however, the sum of the component (A-1) and the component (A-2) is 100 parts by mass),
(B) an organosilicon compound having 3 or more hydrogen atoms bonded to silicon atoms in one molecule (the total amount of hydrogen atoms bonded to silicon atoms in the composition is the addition-reactive carbon-carbon 2 in the composition) And (C) a thermosetting silicone composition containing a hydrosilylation reaction catalyst.

(In the formula, A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R ¹ is independently an unsubstituted or substituted monovalent carbon atom having 1 to 12 carbon atoms. It is a hydrogen group or an alkoxy group having 1 to 6 carbon atoms.)

(In the formula, Ph is a phenyl group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is an addition-reactive carbon-carbon double bond-containing group. And n is an integer from 1 to 20.)

  With such a thermosetting silicone composition, a cured product having high fluidity at room temperature, excellent transparency, heat resistance (thermal stability), particularly heat discoloration, and high gas barrier properties. A transparent thermosetting silicone composition is provided.

（式中、Ｒ^４は非置換又は置換の炭素原子数２〜１２のアルケニル基である。） Moreover, it is preferable that said (b) is what is represented by following General formula (4).

(Wherein R ⁴ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)

  In addition, (b) is any one of 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene, and combinations thereof. It is preferable that

  With such a raw material (b), higher gas barrier properties can be imparted.

（式中、Ｒ^５は独立に水素原子又はアルケニル基以外の非置換若しくは置換の炭素原子数
１〜１２の一価炭化水素基であり、Ｒ^６はメチル基あるいは水素原子であり、ｐは１〜１０の整数、ｑは０〜７の整数である。ｐが付されたシロキサン単位とｑが付されたシロキサン単位とは互いにランダムに配列している。） Moreover, it is preferable that the said (B) component is a siloxane compound represented by following General formula (5).

(In the formula, R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, R ⁶ is a methyl group or a hydrogen atom, and p is 1 And an integer of 0 to 10 and q is an integer of 0 to 7. The siloxane units marked with p and the siloxane units marked with q are randomly arranged.

  If it is such (B) component, when it is set as hardened | cured material, sufficient mechanical characteristics as an optical element sealing material can be provided.

  Moreover, in this invention, the silicone resin hardened | cured material which is obtained by hardening said thermosetting silicone composition is provided.

  Such a cured silicone resin can be suitably used as an optical element sealing material.

  At this time, the transmittance of light at a wavelength of 400 nm immediately after curing is 80% or more, and the transmittance of light at a wavelength of 400 nm after exposure for 500 hours in an environment of 150 ° C. is maintained at 70% or more. It is preferable.

  With such a cured silicone resin, when it is used as an optical element sealing material for a light-emitting device such as a lighting fixture, the light extraction efficiency becomes higher and sufficient brightness can be easily secured.

At this time, the cured product having a gas barrier property and having a thickness of 1 mm preferably has a water vapor permeability of 7 g / m ² · day or less at 40 ° C.

  With such a cured silicone resin, there is no possibility of discoloration of the silver electrode due to the invasion of corrosive gas from the outside, and the cured product was used as an optical element sealing material for light emitting devices such as lighting equipment. In this case, the light extraction efficiency is reduced, and there is no possibility that sufficient brightness cannot be secured.

  Moreover, in this invention, the semiconductor device which sealed the optical element with said silicone resin hardened | cured material is provided.

  In this case, the optical element is preferably an LED (light emitting diode).

  Such a semiconductor device is more reliable.

  Since the thermosetting silicone composition of the present invention has high fluidity at room temperature, it is excellent in workability and handleability. Moreover, the cured silicone resin obtained by thermosetting the above composition is excellent in transparency and heat resistance (thermal stability), particularly heat discoloration, and has a higher gas barrier property. Therefore, since the cured product is useful as an optical element sealing material, for example, a sealing material for a light emitting device, particularly a white LED, a highly reliable semiconductor device can be provided.

  As described above, a thermosetting silicone composition having high fluidity at room temperature, excellent transparency, heat resistance (thermal stability), particularly heat discoloration, and a cured product having further high gas barrier properties. Development was required.

  As a result of intensive studies on the above problems, the present inventors have found that a thermosetting silicone composition containing a reaction addition product by a hydrosilylation reaction having a specific structure and an organopolysiloxane having a specific structure. For example, it has high fluidity at room temperature, has transparency, heat resistance (thermal stability), particularly excellent heat discoloration, and gives a cured product having higher gas barrier properties. The present invention was completed by finding it useful as a sealing material.

That is, the present invention
(A-1) (a) a compound having two hydrogen atoms bonded to the silicon atom represented by the general formula (1) in one molecule, and (b) 1 addition-reactive carbon-carbon double bond. 30 to 70 parts by mass of an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, which is an addition reaction product with two polycyclic hydrocarbons in the molecule
(A-2) 30 to 70 parts by mass of the compound represented by the general formula (3) (however, the total of the component (A-1) and the component (A-2) is 100 parts by mass),
(B) an organosilicon compound having 3 or more hydrogen atoms bonded to silicon atoms in one molecule (the total amount of hydrogen atoms bonded to silicon atoms in the composition is the addition-reactive carbon-carbon 2 in the composition) (C) a hydrosilylation reaction catalyst, and a thermosetting silicone composition characterized by containing a hydrosilylation reaction catalyst.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. In this specification, Me and Ph represent a methyl group and a phenyl group, respectively, and the viscosity is a value measured by a rotational viscometer.

[(A-1) component]
The component (A-1) of the thermosetting silicone composition of the present invention is a component that imparts gas barrier properties in addition to imparting strength and high hardness to the cured product after curing.

（式中、Ａは、下記一般式（２）で表される基から成る群から選ばれる２価の基であり、Ｒ^１は、独立に非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は炭素原子数１〜６のアルコキシ基である。）

The component (A-1) includes (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule, and (b) an addition-reactive carbon-carbon double. An addition reaction product with a polycyclic hydrocarbon having two bonds in one molecule, and an addition reaction product having at least two addition-reactive carbon-carbon double bonds in one molecule. Hereinafter, the raw material (a) and the raw material (b) used as the raw material of the component (A-1) will be described.

(In the formula, A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R ¹ is independently an unsubstituted or substituted 1 having 1 to 12 carbon atoms. A valent hydrocarbon group or an alkoxy group having 1 to 6 carbon atoms.)

（Ｒ^１は独立に非置換もしくは置換の炭素原子数１〜１２の、好ましくは１〜６の、１価炭化水素基又は炭素原子数１〜６のアルコキシ基である） <Raw material (a)>
(A-1) The reaction raw material of component (a) Two hydrogen atoms bonded to the silicon atom represented by the general formula (1) (hereinafter sometimes referred to as “SiH”) per molecule The compound (raw material (a)) is a compound represented by the following general formula (6) because A in the above general formula (1) is a divalent group represented by the above general formula (2). is there.

(R ¹ is independently an unsubstituted or substituted C 1-12, preferably 1-6 monovalent hydrocarbon group or C 1-6 alkoxy group)

In the general formula (6), when R ¹ is a monovalent hydrocarbon group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, an isopentyl group, Alkyl groups such as hexyl group and sec-hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, o-, m- and p-tolyl; benzyl group and 2-phenylethyl group An aralkyl group; an alkenyl group such as a vinyl group, an allyl group, a 1-butenyl group, or a 1-hexenyl group; an alkenyl aryl group such as a p-vinylphenyl group; and one or more hydrogen bonded to a carbon atom in these groups An atom is substituted with a halogen atom, a cyano group, an epoxy ring-containing group, etc., for example, chloromethyl group, 3-chloropropyl group, 3,3,3- A halogenated alkyl group such as a trifluoropropyl group; a 2-cyanoethyl group; a 3-glycidoxypropyl group;

Examples of the case where R ¹ is an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group.

Among these, as R ¹ , those other than alkenyl groups and alkenyl aryl groups are preferable, and those in which all R ^{1 in} one molecule are methyl groups are easy to industrially manufacture, It is preferable because it is easily available.

As the compound represented by the general formula (6), for example,
Structural _{formula: HMe 2 Si-p-C} 6 H 4 -SiMe 2 H
1,4-bis (dimethylsilyl) benzene represented by
Structural _{formula: HMe 2 Si-m-C} 6 H 4 -SiMe 2 H
1,3-bis (dimethylsilyl) benzene represented by
Structural formula: HMe ₂ Si—o—C ₆ H ₄ —SiMe ₂ H
And a silphenylene compound such as 1,2-bis (dimethylsilyl) benzene represented by the formula:

  In addition, the compound represented by the general formula (6) (the raw material (a) which is a reaction raw material of the component (A-1)) can be used alone or in combination of two or more. .

<Raw material (b)>
(B-1) In the polycyclic hydrocarbon (raw material (b)) having two addition-reactive carbon-carbon double bonds in one molecule, which is a reaction raw material of component (A-1), Means a property capable of undergoing the addition of a hydrogen atom bonded to a silicon atom (known as a hydrosilylation reaction).

  In addition, in the raw material (b), an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of (i) polycyclic hydrocarbon. (Ii) a hydrogen atom bonded to a carbon atom forming a polycyclic skeleton of a polycyclic hydrocarbon is substituted with an addition-reactive carbon-carbon double bond-containing group, or (Iii) Of the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon, an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and the polycyclic Any hydrogen atom bonded to the carbon atom forming the hydrocarbon polycyclic skeleton may be substituted with an addition-reactive carbon-carbon double bond-containing group. Here, examples of the addition-reactive carbon-carbon double bond-containing group include alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, norbornyl group, particularly those having 2 to 12 carbon atoms. Etc.

（式中、Ｒ^４は非置換又は置換の炭素原子数２〜１２のアルケニル基である。）

Examples of the raw material (b) include alkenyl norbornene compounds represented by the following general formula (4). Furthermore, specific examples of the compound represented by the following general formula (4) include 5-vinylbicyclo [2.2.1] hept-2-ene represented by the following structural formula (7), 6-vinylbicyclo [2.2.1] hept-2-ene represented by 8) and a combination of both. (Hereinafter, when it is not necessary to distinguish these three, they may be collectively referred to as “vinyl norbornene”).

(Wherein R ⁴ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)

  In addition, the substitution position of the vinyl group of the vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type), and the reaction of the raw material (b) depends on the difference in the arrangement. Since there is no particular difference in sex and the like, a combination of both isomers may be used.

<Preparation of component (A-1)>
The component (A-1) of the thermosetting silicone composition of the present invention has one addition-reactive carbon-carbon double bond per mole of the raw material (a) having two SiHs in one molecule. An addition reaction is carried out by subjecting an excess amount of more than 1 mole and not more than 10 moles, preferably more than 1 mole and not more than 5 moles of the raw material (b) having two in the molecule in the presence of a hydrosilylation reaction catalyst. It can be obtained as an addition reaction product having at least two functional carbon-carbon double bonds in one molecule and having no SiH.

The component (A-1) thus obtained is derived from the raw material (a) in addition to the addition-reactive carbon-carbon double bond derived from the raw material (b) (specifically, in the general formula (1) Since it can contain addition-reactive carbon-carbon double bonds (derived from R ¹ ), it contains at least two addition-reactive carbon-carbon double bonds in one molecule, but this number is preferably 2-6, More preferably, it is two. When the addition-reactive carbon-carbon double bond has such a number, the cured product obtained by curing the thermosetting silicone composition of the present invention does not become brittle.

  Any conventionally known hydrosilylation reaction catalyst can be used. For example, carbon powder supporting platinum metal, platinum black, platinous chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of platinum and vinylsiloxane such as divinyltetramethyldisiloxane; Examples include complexes of chloroplatinic acid and olefins, platinum catalysts such as platinum bisacetoacetate; platinum group metal catalysts such as palladium catalysts and rhodium catalysts. Moreover, about addition reaction conditions, use of a solvent, etc., it will not be specifically limited, What is necessary is just to be normal.

  As described above, the component (A-1) is prepared using an excess molar amount of the material (b) relative to the material (a). It has two addition-reactive carbon-carbon double bonds derived from the structure in one molecule. Further, the component (A-1) has a residue derived from the raw material (a), and the residue is derived from the structure of the raw material (b), but has an addition reactive carbon-carbon double bond. It may contain a structure bonded by a divalent residue of a polycyclic hydrocarbon that is not present.

（式中、Ｘは上記原料（ａ）の化合物の二価の残基であり、Ｙは上記原料（ｂ）の多環式炭化水素の一価の残基であり、Ｙ´は上記原料（ｂ）の二価の残基であり、ｍは０〜１０、好ましくは０〜５の整数である） That is, examples of the component (A-1) include compounds represented by the following general formula (9).

Wherein X is a divalent residue of the compound of the raw material (a), Y is a monovalent residue of the polycyclic hydrocarbon of the raw material (b), and Y ′ is the raw material ( b) a divalent residue, and m is an integer of 0 to 10, preferably 0 to 5.

  In addition, about the value of m which is the number of the repeating units represented by said (Y'-X), adjusting the excess molar amount of the said raw material (b) made to react with respect to 1 mol of said raw materials (a). It is possible to set by.

As Y in the general formula (9), specifically, for example, a monovalent residue represented by the following structural formula (hereinafter referred to as “NB” when it is not necessary to distinguish these six members) Generically referred to as “group”, and may be abbreviated as “NB” without distinguishing these six structures.)

Specific examples of Y ′ in the general formula (9) include a divalent residue represented by the following structural formula.

  However, the asymmetrical divalent residue represented by the above structural formula is not limited in the left-right direction as described above. It also includes a structure rotated 180 degrees.

  Although the preferable specific example of the (A-1) component represented by the said General formula (9) is shown below, it is not limited to this. (The meaning of “NB” is as described above.)

（式中、ｒは０〜１０の整数である。）

(In the formula, r is an integer of 0 to 10.)

  Furthermore, the component (A-1) of the present invention can be used singly or in combination of two or more.

[(A-2) component]
The component (A-2) is highly compatible with the component (A-1), and imparts heat resistance (thermal stability), particularly heat discoloration, without reducing the strength of the cured product after curing. It is.

  The component (A-2) is a linear organo group in which the main chain is composed of repeating diphenylsiloxane units, and both ends of the molecular chain are blocked with a triorganosiloxy group having an addition-reactive carbon-carbon double bond-containing group. Polysiloxane. The (A-2) component organopolysiloxane may be used alone or in combination of two or more different molecular weights, types of organic groups bonded to silicon atoms, and the like.

In the general formula (3), the addition-reactive carbon-carbon double bond-containing group as R ³ is the same as that described in the description of <Raw material (b)> above, and is the addition of a hydrogen atom bonded to a silicon atom. It is a group containing a carbon-carbon double bond having a property capable of undergoing (known as a hydrosilylation reaction).

  The said addition reactive carbon-carbon double bond containing group may be used individually by 1 type, or may be used in combination of 2 or more type.

Specific examples of the addition-reactive carbon-carbon double bond-containing group include alkenyl having 2 to 20, preferably 2 to 10, carbon atoms such as vinyl group, allyl group, 5-hexenyl group, propenyl group, and butenyl group. group; alkadienyl group having 4 to 10 carbon atoms such as 1,3-butadienyl group; acryloyloxy group _{(-O (O) CCH = CH} 2), methacryloyloxy group _{(-O (O) CC (CH} 3) = Combinations of the alkenyl group and carbonyloxy group such as CH ₂ ); and combinations of the alkenyl group and carbonylamino group such as acrylamide group (—NH (O) CCH═CH ₂ ).

  Among these, from the viewpoints of productivity and cost when obtaining the raw material of the component (A-2) and reactivity of the component (A-2), the addition reactive carbon-carbon double bond-containing group includes a vinyl group. , An allyl group and a 5-hexenyl group are preferable, and a vinyl group is particularly preferable.

R ² in the general formula (3) is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, alkyl groups such as tert-butyl group, pentyl group, isopentyl group, hexyl group and sec-hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, o-, m- and p-tolyl Aralkyl groups such as benzyl group and 2-phenylethyl group; alkenyl groups such as vinyl group, allyl group, 1-butenyl group and 1-hexenyl group; alkenyl aryl groups such as p-vinylphenyl group; and in these groups 1 or more hydrogen atoms bonded to carbon atoms of the above are substituted with halogen atoms, cyano groups, epoxy ring-containing groups, etc., for example, chloromethyl group, 3 -Halogenated alkyl groups such as chloropropyl group and 3,3,3-trifluoropropyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like.

Among these, R ² is particularly preferably a methyl group or a phenyl group because it is easy to produce industrially and is easily available.

  In the component (A-2), the polymerization degree n of the diphenylsiloxane unit is 1 to 20, preferably 1 to 15, and more preferably 2 to 10. When n is larger than 20, a decrease in fluidity and a decrease in compatibility with the component (A-1) occur, which is not preferable.

  The blending amount of the component (A-2) is 30 to 70 parts by weight, preferably 35 to 65 parts by weight, more preferably 100 parts by weight of the total of the components (A-1) and (A-2). Is 40-60 parts by mass. When the blending amount of the component (A-2) is less than 30 parts by mass, the heat discoloration is lowered, and when it exceeds 70 parts by mass, the gas barrier property is lowered.

  Component (A-2) contains, for example, an addition-reactive carbon-carbon double bond after hydrolysis / condensation of a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, or simultaneously with hydrolysis / condensation. It can be obtained by sealing the terminal with a terminal sealing agent having a group.

[Component (B)]
(B) component of the thermosetting silicone composition of this invention is an organosilicon compound which has 3 or more of SiH in 1 molecule. SiH in the component (B) is added by an addition reactive carbon-carbon double bond having at least two of the components (A-1) and (A-2) in one molecule and a hydrosilylation reaction, A cured product having a three-dimensional network structure is obtained.

（式中、Ｒ^５は独立に水素原子又はアルケニル基以外の非置換若しくは置換の炭素原子数１〜１２の一価炭化水素基であり、Ｒ^６はメチル基あるいは水素原子であり、ｐは１〜１０の整数、ｑは０〜７の整数である。ｐが付されたシロキサン単位とｑが付されたシロキサン単位とは互いにランダムに配列している。） As such (B) component, the siloxane compound represented by following General formula (5) is mentioned, for example.

(In the formula, R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, R ⁶ is a methyl group or a hydrogen atom, and p is 1 And an integer of 0 to 10 and q is an integer of 0 to 7. The siloxane units marked with p and the siloxane units marked with q are randomly arranged.

R ⁵ in the general formula (5) is, for example, alkyl such as methyl group, ethyl, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group and sec-hexyl group. A cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group, o-, m-, or p-tolyl; an aralkyl group such as a benzyl group or a 2-phenylethyl group; a p-vinylphenyl group; An alkenylaryl group; and one or more hydrogen atoms bonded to carbon atoms in these groups are substituted with a halogen atom, a cyano group, an epoxy ring-containing group, or the like, for example, a chloromethyl group, a 3-chloropropyl group Halogenated alkyl groups such as 3,3,3-trifluoropropyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like. I can get lost.

Among these, R ⁵ is particularly preferably a methyl group or a phenyl group because it is easy to produce industrially and is easily available.

  Although the preferable example of the said (B) component is shown below, it is not limited to this.

HMe ₂ SiO (HMeSiO) ₂ (Ph ₂ SiO) ₂ SiMe ₂ H
HMe ₂ SiO (HMeSiO) ₂ (Ph ₂ SiO) ₂ (Me ₂ SiO) ₂ SiMe ₂ H
HMe ₂ SiO (HMeSiO) ₁ (Ph ₂ SiO) ₁ (Me ₂ SiO) ₄ SiMe ₂ H
HMe ₂ SiO (HMeSiO) ₃ (Me ₂ SiO) ₅ SiMe ₂ H
Me ₃ SiO (HMeSiO) ₆ (Ph ₂ SiO) ₂ SiMe ₃

  The component (B) of the thermosetting silicone composition of the present invention can be used singly or in combination of two or more.

  The blending amount of component (B) is preferably set as follows. The thermosetting silicone composition of the present invention comprises a component having SiH other than the component (B) (for example, a component (G) described later) and a silicon atom other than the component (A-1) or (A-2). Any one of the components having an addition-reactive carbon-carbon double bond bonded to (for example, vinyl siloxane which can be contained in the present composition in the form of a complex with platinum as the component (C) described later) or Both can be included. Therefore, the amount of hydrogen atoms bonded to the silicon atom in the composition is preferably 0.5 to 3.3 with respect to 1 mole of the addition reactive carbon-carbon double bond bonded to the silicon atom in the composition. 0 mol, more preferably 0.8 to 2.0 mol. When the blending amount of the component (B) is an amount satisfying such conditions, a cured product having sufficient mechanical properties when used as a material for sealing an optical element is obtained from the thermosetting silicone composition of the present invention. be able to.

  In the case where only the components (A-1) and (A-2) have an addition reactive carbon-carbon double bond bonded to a silicon atom, and only the component (B) has SiH, The blending amount of the component (B) in the thermosetting silicone composition is preferably SiH in the component (B) with respect to 1 mol of the addition-reactive carbon-carbon double bond in the component (A). The amount may be 0.5 to 3.0 mol, more preferably 0.8 to 2.0 mol.

[Component (C)]
Any conventionally known hydrosilylation reaction catalyst that is the component (C) of the thermosetting silicone composition of the present invention can be used. For example, carbon powder supporting platinum metal, platinum black, platinous chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of platinum and vinylsiloxane such as divinyltetramethyldisiloxane; Examples include complexes of chloroplatinic acid and olefins, platinum catalysts such as platinum bisacetoacetate; platinum group metal catalysts such as palladium catalysts and rhodium catalysts.

  The blending amount of the component (C) in the thermosetting silicone composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but the above (A-1), (A-2) and (B The component (C) is preferably added in an amount of about 1 to 500 ppm, particularly preferably about 2 to 100 ppm as a platinum group metal atom, based on the total weight of the component and the component. By setting the blending amount within such a range, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.

  Component (C) can be used alone or in combination of two or more.

（式中、ｓは１〜３の整数であり、ｔは０〜３の整数であり、ｕは０〜３の整数であり、但しｓ＋ｔ＋ｕは４〜５の整数である。ｓが付されたシロキサン単位とｔが付されたシロキサン単位とｕが付されたシロキサン単位とは互いにランダムに配列している。） [(D) component]
Moreover, it is preferable to mix | blend an adhesive improvement agent as (D) component with the thermosetting silicone composition of this invention. Examples of the adhesion improver include silane coupling agents and oligomers thereof, and silicone having a reactive group similar to the silane coupling agent. Among these, as the component (D), a compound represented by the following general formula (11) is preferable.

(In the formula, s is an integer of 1 to 3, t is an integer of 0 to 3, u is an integer of 0 to 3, provided that s + t + u is an integer of 4 to 5. s is attached. (The siloxane unit, the siloxane unit to which t is attached, and the siloxane unit to which u is attached are randomly arranged to each other.)

  (D) component is an arbitrary component mix | blended with a composition in order to improve the adhesiveness with respect to the base material of the thermosetting silicone composition of this invention, and its hardened | cured material. Here, the base material refers to metal materials such as gold, silver, copper, and nickel, ceramic materials such as aluminum oxide, aluminum nitride, and titanium oxide, and polymer materials such as silicone resin and epoxy resin. Component (D) can be used alone or in combination of two or more.

  The blending amount of the component (D) is preferably 1 to 30 parts by mass, more preferably 1 to 100 parts by mass in total of the components (A-1), (A-2), and (B). -10 parts by mass. When the blending amount is 1 to 30 parts by mass, the thermosetting silicone composition of the present invention and the cured product thereof are effectively improved in adhesion to the substrate and are not easily colored.

Preferable specific examples of the component (D) include the following compounds, but the component (D) is not limited thereto.

[Other ingredients]
In addition to the above components, it is optional to add other components to the thermosetting silicone composition of the present invention. Examples of other components include those described below.

２−（ビシクロ［２．２．１］ヘプト−２−エン−５−イル）エチル基

２−（ビシクロ［２．２．１］ヘプト−２−エン−６−イル）エチル基 <Antioxidant>
In the cured product of the thermosetting silicone composition of the present invention, the addition-reactive carbon-carbon double bond in the component (A-1) may remain unreacted. 2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl group represented by the structural formula and 2- (bicyclo [2.2.1] heptated by the following structural formula 2-ene-6-yl) ethyl groups may contain carbon-carbon double bonds present in either or both. And when such a carbon-carbon double bond is contained, it will be oxidized by oxygen in air | atmosphere and will cause a hardened material to color. Then, coloring can be prevented beforehand by mix | blending antioxidant with the thermosetting silicone composition of this invention as needed.

2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl group

2- (bicyclo [2.2.1] hept-2-en-6-yl) ethyl group

  As the antioxidant, all conventionally known antioxidants can be used, and examples thereof include hindered amine compounds and hindered phenol compounds. Specifically, 2,6-di-t-butyl-4- Methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 1,3,5-tris [[3,5-bis (1,1-dimethylethyl ) -4-Hydroxyphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, N ′, N ′, N ″, N ′ ″-tetrakis [ , 6-Bis [(1,2,2,6,6-pentamethylpiperidin-4-yl) (butyl) amino] -1,3,5-triazin-2-yl] [N ′, N ″- Ethylenebis (propane-1,3-diamine)] and the like. These can be used singly or in combination of two or more.

  In addition, when using this antioxidant, the compounding quantity should just be an effective amount as an antioxidant, and although it does not restrict | limit in particular, the said (A-1), (A-2) and (B) component Preferably, about 10 to 10,000 ppm, particularly preferably about 100 to 1,000 ppm is blended on the mass basis. By setting the blending amount within such a range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent transparency without coloration or oxidative deterioration can be obtained.

<Others>
Moreover, in order to ensure pot life, addition reaction control agents, such as 1-ethynyl cyclohexanol and 3, 5- dimethyl- 1-hexyn-3-ol, can be mix | blended.
Furthermore, a light stabilizer can be used to impart resistance to light degradation caused by light energy such as light from the light emitting element and sunlight. As the light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidation degradation is suitable, and the antioxidant effect is further improved by using it together with the antioxidant. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like.

[Thermosetting silicone composition]
The thermosetting silicone composition of the present invention (transparent thermosetting silicone composition) is in a liquid state before being cured, and its viscosity at 25 ° C. is preferably 100 to 5000 mPa · s, more preferably 200 to 1000 mPa · s. s. When the viscosity is in the range of 100 to 5000 mPa · s, the resulting composition is likely to have good workability and handleability, and bubbles and air are less likely to be entrained during curing.

  The viscosity of the thermosetting silicone composition of the present invention is adjusted by the blending ratio of the components (A-1) (A-2) to (C) and other blending components, the viscosity of liquid components among these components, and the like. The

[Hardened silicone resin]
The thermosetting silicone composition of the present invention can be molded and cured by a known method under known curing conditions to obtain a cured silicone resin.
Specifically, the composition can be usually cured by heating at 80 to 200 ° C, preferably 100 to 160 ° C. The heating time may be about 0.5 minutes to 5 hours, particularly about 1 minute to 3 hours, but when reliability for LED sealing or the like is required, it is preferable to lengthen the curing time. The form of the obtained cured product is not particularly limited, and may be any of a gel cured product, an elastomer cured product, and a resin cured product, for example.

  In general, when the cured resin functions as an optical element sealing material, the transmittance of light having a wavelength of 400 nm is preferably 80% or more (that is, 80 to 100%), more preferably 85% or more (that is, 85-100%). When the light transmittance is 80% or more, when the cured product is used as an optical element sealing material for a light-emitting device such as a lighting fixture, the light extraction efficiency becomes higher, and sufficient brightness can be easily secured. . The light transmittance is preferably maintained at 70% or more not only at the initial stage of production of the cured product but also after the heat resistance test (performed by leaving the cured product to stand at 150 ° C. for 500 hours), It is more preferable to maintain 75% or more. The cured silicone resin obtained from the thermosetting silicone resin composition of the present invention has a light transmittance of 80% or more at a wavelength of 400 nm and a light transmittance of 70% or more after standing at 150 ° C. for 500 hours. The light transmittance sufficient as the optical element sealing material can be obtained. In this specification, the light transmittance means a numerical value measured by a spectrophotometer.

Further, the cured silicone resin of the present invention has a gas barrier property, and the water vapor permeability of the cured product having a thickness of 1 mm is preferably 7 g / m ² · day or less, more preferably 6 g / m ² · day or less at 40 ° C. It is. When the water vapor transmission rate is 7 g / m ² · day or less, the gas barrier property is lowered, and the silver electrode is not discolored by the invasion of corrosive gas from the outside. As a result, when the cured product is used as an optical element sealing material for a light-emitting device such as a lighting fixture, sufficient brightness can be ensured without lowering the light extraction efficiency. Therefore, the cured silicone resin obtained from the thermosetting silicone resin composition of the present invention can obtain gas barrier properties sufficient as an optical element sealing material.

  The cured product obtained by curing the thermosetting silicone composition of the present invention is excellent in transparency, heat discoloration, and gas barrier properties as described above, and is similar to a cured product of a normal thermosetting silicone composition. It also has excellent cold resistance and electrical insulation.

[Semiconductor device]
Examples of the optical element sealed with the cured silicone resin of the present invention include an LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, and a CCD. In such an optical element, the transparent thermosetting silicone composition of the present invention is applied to the optical element, and the applied composition is subjected to a known curing method under a known curing condition, specifically as described above. It can be sealed by curing. Any semiconductor device coated with such a cured product can be a semiconductor device with excellent reliability.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the viscosity is a value at 25 ° C. measured using a spiral viscometer (Malcom Co., Ltd., model: PC-1T) which is a rotational viscometer.

In the following examples, symbols indicating the composition of silicone oil or silicone resin are shown below. The number of moles of each silicone oil or each silicone resin indicates the number of moles of vinyl groups or silicon-bonded hydrogen atoms contained in each component.
^MH : (CH ₃ ) ₂ HSiO _1/2
M ^Vi : (CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2
M ^ViΦ : (CH ₂ ^═CH ) (C ₆ H ₅ ) (CH ₃ ) SiO _{1/2
^{D H: (CH 3) HSiO}} 2/2
_{^{D Φ: (C 6 H 5}} ) (CH 3) SiO 2/2
D ^2Φ : (C ₆ H ₅ ) ₂ SiO _2/2
M: (CH ₃ ) ₃ SiO _1/2

[Synthesis Example 1] Preparation of Component (A-1) Into a 5 L four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5- 1785 g (14.88 mol) of an approximately equimolar amount of an isomer mixture of vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene And 455g of toluene was added and it heated at 85 degreeC using the oil bath. To this, 3.6 g of carbon powder supporting 5 mass% platinum was added, and 1698 g (8.75 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 180 minutes while stirring. After completion of the dropwise addition, the mixture was further heated and stirred at 110 ° C. for 24 hours, and then cooled to room temperature. Thereafter, the platinum-supporting carbon was removed by filtration, and toluene and excess vinyl norbornene were distilled off under reduced pressure to obtain 3362 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 12820 mPa · s).

（２）ｐ−フェニレン基を３個有する化合物（下記に代表的な構造式の一例を示す）：約３２モル％

（３）ｐ−フェニレン基を４個以上有する化合物：約２７モル％
の混合物であることが判明した。また、混合物全体としての付加反応性炭素−炭素二重結合の含有割合は、０．３６モル／１００ｇであった。 As a result of analyzing the reaction product by FT-IR, NMR, GPC and the like,
(1) Compound having two p-phenylene groups (an example of a typical structural formula shown below): about 41 mol%,

(2) Compound having three p-phenylene groups (an example of a typical structural formula shown below): about 32 mol%

(3) Compound having 4 or more p-phenylene groups: about 27 mol%
It was found to be a mixture of Moreover, the content rate of the addition reactive carbon-carbon double bond as the whole mixture was 0.36 mol / 100g.

[Examples 1-4, Comparative Examples 1-3]
The following (A-1) to (G) components were blended in the blending amounts (unit: parts by mass) shown in Table 1, and compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were obtained. The viscosity of the obtained composition was measured. The results are shown in Table 1.

（Ｄ−２）下記式で表される化合物

（Ｅ）１−エチニル−１−シクロヘキサノールの５０質量％トルエン溶液（付加反応制御剤）
（Ｆ）酸化防止剤：ＢＡＳＦ社製 ＳＡＢＯＳＴＡＢ ＵＶ １１９
（Ｇ）酸化防止剤：チバ・スペシャリティ・ケミカルズ社製 ＩＲＧＡＮＯＸ ３１１４ (A-1) the reaction product obtained in Synthesis Example 1,
(A-2-1) Average molecular formula: Organopolysiloxane represented by M ^ViΦ ₂ D ^2Φ ₃ (A-2-2) Average molecular formula: Organopolysiloxane represented by M ^Vi ₂ D ^2Φ ₄ (A-3 ) average molecular ^{formula: M} _Vi organopolysiloxane represented by _{^{2 D Φ 6 (B-1}} ) the average molecular _{^{formula: M H 2 D H 2 D}} 2Φ 2, in the organopolysiloxane (B-2 represented) the average molecular formula: M ₃ ^DH ₆ D ^2Φ ₂ , organopolysiloxane (C) platinum-divinyltetramethyldisiloxane complex toluene solution (containing 1% by mass of platinum atom)
(D-1) Compound represented by the following formula

(D-2) Compound represented by the following formula

(E) 50 mass% toluene solution of 1-ethynyl-1-cyclohexanol (addition reaction control agent)
(F) Antioxidant: SABOSTAB UV 119 manufactured by BASF
(G) Antioxidant: IRGANOX 3114 manufactured by Ciba Specialty Chemicals

Next, about the composition obtained by each Example and the comparative example, hardened | cured material was produced according to the method of following (1)-(4) (each H1-H4 in Table 2, H5-H7), and performance evaluation Carried out. As curing conditions, heat curing was performed at 150 ° C. for 4 hours. The properties of the obtained cured product are shown in Table 2.
(1) Measurement of light transmittance A 2 mm thick spacer is mounted between two glass plates, the composition is placed in a 15 mm × 40 mm × 2 mm space, and the above heat curing is performed to obtain a 2 mm thick cured product. It was. The light transmittance of the obtained cured product was measured at 25 ° C. for a measurement wavelength of 400 nm (ultraviolet region) using a spectrophotometer.
(2) Measurement of hardness The hardness (Shore D) of each cured product was measured according to ASTM D 2240.
(3) Evaluation of gas barrier property (water vapor transmission rate) A cured product having an outer diameter of 100 mmΦ and a thickness of 1 mm was prepared and measured at 40 ° C. using a water vapor transmission rate measuring device (L80-5000 type) manufactured by Systec Illinois. Carried out. The lower the numerical value, the higher the gas barrier property.
(4) Evaluation of heat discoloration The cured products H1 to H7 obtained in the above (1) were left at 150 ° C. for 500 hours to conduct a heat resistance test. The heat resistance was evaluated by taking the difference between the initial light transmittance obtained in (1) above and the light transmittance after the test. The smaller the difference in light transmittance, the higher the heat resistance.

  As shown in Tables 1 and 2, in Examples 1 to 4 using the thermosetting silicone composition of the present invention, all the compositions had low viscosity and therefore excellent fluidity. The initial light transmittance was high and the transparency was excellent. Further, since the difference between the initial light transmittance and the light transmittance after heat deterioration was small, the heat resistance was excellent. Further, it was found that the water vapor transmission rate was small and the gas barrier property was excellent.

  On the other hand, in Comparative Example 1, heat resistance was poor because the light transmittance after heat deterioration was greatly reduced compared to the initial stage. In Comparative Example 2, it was found that the water vapor permeability was high and the gas barrier property was low. Also in Comparative Example 3, the water vapor transmission rate was high, and good gas barrier properties were not obtained.

  The above results show that the thermosetting silicone composition of the present invention has high fluidity at room temperature, and the cured product is excellent in transparency and heat resistance (thermal stability), in particular, heat discoloration resistance, and higher. It shows that it has gas barrier properties. Therefore, the hardened | cured material of the thermosetting silicone composition of this invention is useful as an optical element sealing material, especially a sealing material for white LED.

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

Claims (9)

(A-1) (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule; and (b) 1 addition-reactive carbon-carbon double bond. 30 to 70 parts by mass of an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, which is an addition reaction product with two polycyclic hydrocarbons in the molecule
(A-2) 30 to 70 parts by mass of a compound represented by the following general formula (3) (however, the sum of the component (A-1) and the component (A-2) is 100 parts by mass),
(B) an organosilicon compound having 3 or more hydrogen atoms bonded to silicon atoms in one molecule (the total amount of hydrogen atoms bonded to silicon atoms in the composition is the addition-reactive carbon-carbon 2 in the composition) And (C) a hydrosilylation reaction catalyst. A thermosetting silicone composition characterized by comprising a hydrosilylation reaction catalyst.

(In the formula, A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R ¹ is independently an unsubstituted or substituted monovalent carbon atom having 1 to 12 carbon atoms. It is a hydrogen group or an alkoxy group having 1 to 6 carbon atoms.)

(In the formula, Ph is a phenyl group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is an addition-reactive carbon-carbon double bond-containing group. And n is an integer from 1 to 20.) The thermosetting silicone composition according to claim 1, wherein (b) is an alkenyl norbornene compound represented by the following general formula (4).

(Wherein R ⁴ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)   The (b) is any one of 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene, and combinations thereof. The thermosetting silicone composition according to claim 1, wherein the thermosetting silicone composition is provided. The thermosetting silicone composition according to any one of claims 1 to 3, wherein the component (B) is a siloxane compound represented by the following general formula (5).

(In the formula, R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, R ⁶ is a methyl group or a hydrogen atom, and p is 1 And an integer of 0 to 10 and q is an integer of 0 to 7. The siloxane units marked with p and the siloxane units marked with q are randomly arranged.   A cured silicone resin, which is obtained by curing the thermosetting silicone composition according to any one of claims 1 to 4.   Immediately after curing, the transmittance of light at a wavelength of 400 nm is 80% or more, and the transmittance of light at a wavelength of 400 nm after exposure for 500 hours in an environment of 150 ° C. is maintained at 70% or more. The silicone resin cured product according to claim 5. The cured silicone resin according to claim 5 or 6, wherein the cured product having a gas barrier property and having a thickness of 1 mm has a water vapor transmission rate of 7 g / m ² · day or less at 40 ° C. object.   A semiconductor device, wherein an optical element is sealed with the cured silicone resin according to any one of claims 5 to 7.   The semiconductor device according to claim 8, wherein the optical element is an LED (light emitting diode).