JP6161252B2 - Modified polyorganosiloxane, composition containing the modified product, and cured product obtained by curing the composition - Google Patents

Description

  The present invention relates to a polyorganosiloxane composition having high heat resistance and light resistance, and excellent gas barrier properties and thermal shock resistance.

  Polyorganosiloxane composition is excellent in heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical properties, flame resistance, water resistance, transparency, colorability, non-adhesiveness, non-corrosion One of application examples is intended to be used as an optical semiconductor element sealant application. For example, in Patent Document 1, an organic compound having 2 to 6 carbon-carbon double bonds having reactivity with SiH groups in one molecule, a chain having at least two SiH groups in one molecule, and / or Cyclic polyorganosiloxane compound, organic compound having one carbon-carbon double bond having reactivity with at least one epoxy group or oxetanyl group and SiH group in the molecule, and reactivity with SiH group Although a polyorganosiloxane-based composition containing a compound having one carbon-carbon double bond having an oxygen atom is disclosed, since it has an oxetanyl group or an epoxy group, the heat resistance and light resistance are improved. There was room for.

  Patent Document 2 discloses an organohydrogensilicon compound containing at least one silicon-bonded hydrogen atom and one cyclosiloxane per molecule. While organohydrogensilicon compounds and polyorganosiloxane compositions have excellent characteristics, they generally have a problem of low gas barrier properties. Therefore, when used in an optical semiconductor element sealant application, there is a problem that the reflector is blackened by sulfide. For example, in Patent Document 3, a metal member is previously made of an acrylic resin having a high gas barrier property. The coating process is performed. However, after performing the coating treatment with an acrylic resin, it takes time and labor, such as sealing with a silicone resin separately, and there is a problem in productivity.

JP 2008-291137 A WO03 / 093349 JP 2009-206124 A

  It is an object of the present invention to provide a modified polyorganosiloxane having high heat resistance, light resistance, excellent thermal shock resistance and higher gas barrier properties, a composition containing the modified body, and curing the composition. The object is to provide a cured product.

As a result of intensive studies to solve the above problems, the present inventors have
Compound (α1) having at least one carbon-carbon double bond having reactivity with SiH group in one molecule and linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule A modified polyorganosiloxane characterized by having a structure derived from a silane compound (γ1) having one carbon-carbon double bond having a reactivity with SiH group in one molecule of the compound (β1), The present inventors have found that the above problems can be solved, and have reached the present invention.

That is, the present invention has the following configuration.
1) (α1) Compound having at least one carbon-carbon double bond having reactivity with SiH group in one molecule,
(Β1) a linear and / or cyclic polyorganosiloxane compound having at least two SiH groups in one molecule;
(Γ1) Hydrosilylation reaction product of a silane compound having one carbon-carbon double bond having reactivity with SiH group in one molecule, wherein the compound (α1) is
1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, 5- Vinylbicyclo [2.2.1] hept-2-ene, divinylbenzene, vinylcyclohexene, 1,2,4-trivinylcyclohexane, the following general formula (I)

(In the formula, R ¹ represents the same or different organic group having 1 to 20 carbon atoms or hydrogen atom, and at least one R ¹ represents a carbon-carbon double bond having reactivity with SiH group. An organic group having 2 to 20 carbon atoms which may have a substituent.

A modified polyorganosiloxane, which is at least one selected from the group consisting of:

  2) The compound represented by the general formula (I) is allyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, triallyl isocyanurate, allyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl isocyanurate, diallyl isocyanurate The modified polyorganosiloxane according to 1), which is at least one selected from the group consisting of:

  3) The compound (β1) is represented by the following general formula (II)

(Wherein R ² represents the same or different organic group having 1 to 6 carbon atoms, and m and n represent numbers satisfying 3 ≦ m + n ≦ 10 and 2 ≦ m ≦ 10). 1) and 2) modified polyorganosiloxane.

  4) The compound (γ1) is represented by the following general formula (III)

(In the formula, R ³ represents an organic group having 2 to 10 carbon atoms which may have a substituent having one carbon-carbon double bond having reactivity with the SiH group, and R ⁴ is the same or different. Represents an organic group having 1 to 10 carbon atoms that may be present.) The modified polyorganosiloxane according to 1) to 3).

5) The modified polyorganosiloxane according to 4), wherein at least one of R ⁴ has a phenyl skeleton.

  6) Compound (A) having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, Compound (B) having at least two SiH groups in one molecule, hydrosilylation catalyst ( A curable composition comprising C) as an essential component, the component (B) containing the modified polyorganosiloxane according to 1) to 5).

  7) Curability according to 1) to 6), wherein the compound (A) is at least one compound selected from the group consisting of triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate. Composition.

  8) A cured product obtained by curing the curable composition according to 6) and / or 7).

  A polyorganosiloxane modified product having high heat resistance, light resistance, excellent thermal shock resistance and higher gas barrier properties, a composition containing the modified product, and a cured product obtained by curing the composition Can be provided.

Hereinafter, the present invention will be described in detail.
<Compound (α1) having at least one carbon-carbon double bond having reactivity with SiH group in one molecule>
(Α1) is 1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, di Cyclopentadiene, 5-vinylbicyclo [2.2.1] hept-2-ene, divinylbenzene, vinylcyclohexene, 1,2,4-trivinylcyclohexane, the following general formula (I)

(In the formula, R ¹ represents the same or different organic group having 1 to 20 carbon atoms or hydrogen atom, and at least one R ¹ represents a carbon-carbon double bond having reactivity with SiH group. An organic group having 2 to 20 carbon atoms which may have a substituent.

Is at least one compound selected from the group consisting of

  From the viewpoint of the heat resistance of a cured product obtained by curing a composition comprising the polyorganosiloxane modified product and the compound (A) and hydrosilylation catalyst (C) described later as essential components, (α1) is allyl diglycidyl isocyanurate. It is preferably at least one selected from the group consisting of diallyl monoglycidyl isocyanurate, triallyl isocyanurate, allyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl isocyanurate and diallyl isocyanurate.

The various compounds (α1) described above can be used alone or in admixture of two or more.

<Linear and / or cyclic polyorganosiloxane compound (β1) having at least two SiH groups in one molecule>
Next, (β1) will be described. The compound (β1) is not particularly limited as long as it is a linear and / or cyclic organopolysiloxane compound having at least two SiH groups in one molecule. For example, the compound described in International Publication WO 96/15194, Those having at least two SiH groups in one molecule can be used.

  Among these, from the viewpoint of availability and reactivity with the compound (α1), the following general formula (II)

In the formula, R ² represents the same or different organic group having 1 to 6 carbon atoms, and m and n represent numbers satisfying 3 ≦ m + n ≦ 10 and 2 ≦ m ≦ 10. ) Is preferred.

The substituent R ² in the compound represented by the general formula (II) is preferably composed of C, H and O, more preferably a hydrocarbon group, and a methyl group. Further preferred.

The compound represented by the general formula (II) is 1 from the viewpoint of availability and reactivity.
3,5,7-tetramethylcyclotetrasiloxane is preferred.

The various compounds (β1) described above can be used alone or in admixture of two or more.

<Silane compound (γ1) having one carbon-carbon double bond having reactivity with SiH group in one molecule>
Next, a silane compound (γ1) having one carbon-carbon double bond having reactivity with a SiH group in one molecule will be described.

  The compound (γ1) is not particularly limited as long as it is a silane compound having one carbon-carbon double bond having reactivity with a SiH group in one molecule. However, availability, heat resistance, light resistance, gas barrier are not limited. General formula (III)

(In the formula, R ³ represents an organic group having 2 to 10 carbon atoms which may have a substituent having one carbon-carbon double bond having reactivity with the SiH group, and R ⁴ is the same or different. And a substituent having one carbon-carbon double bond having reactivity with the SiH group. Examples of the organic group having 2 to 10 carbon atoms may include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, but a vinyl group and an allyl group are preferable from the viewpoint of heat resistance and light resistance.

Examples of the organic group having 1 to 10 carbon atoms that may be the same or different for R ⁴ include a methyl group, an ethyl group, a propyl group, a cyclohexyl group, and a phenyl group, but the heat resistance, light resistance, From the viewpoint of combining gas barrier properties, at least one of R ⁴ is preferably a phenyl group.

  Specific examples of the compound (γ1) include vinyldiphenylmethylsilane, vinyldimethylphenylsilane, and vinyltriphenylsilane.

The various compounds (γ1) described above can be used alone or in admixture of two or more.

<Modified polyorganosiloxane>
The modified polyorganosiloxane of the present invention comprises a compound (α1) having at least one carbon-carbon double bond having reactivity with SiH group in one molecule and one molecule in the presence of a hydrosilylation catalyst described later. A linear and / or cyclic polyorganosiloxane compound (β1) having at least two SiH groups in one molecule of a silane compound (γ1) having one carbon-carbon double bond having reactivity with SiH groups. ) And a hydrosilylation reaction.

  The method for obtaining the modified polyorganosiloxane of the present invention is not particularly limited and can be variously set. However, after reacting the (α1) component and the (β1) component in advance, the (γ1) component may be reacted. The (γ1) component and the (β1) component may be reacted in advance, and then the (α1) component may be reacted, or the (α1) component and the (γ1) component may be allowed to coexist and react with the (β1) component. Also good. After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of a compound containing only the (γ1) component and the (β1) component and not containing the (α1) component, the (α1) component and the (β1) component are reacted, and the unreacted (β1) A method of reacting the (γ1) component after distilling off the component is preferred.

  In the modified polyorganosiloxane thus obtained, a part of the alkenyl group of the component (α1) used in the reaction may remain.

  The addition amount of the (β1) component is preferably used so that the number of hydrosilyl groups is 2.5 to 20 with respect to one alkenyl group of the (α1) component. When the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the handling property of the modified polyorganosiloxane may be inferior, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  The addition amount of the (γ1) component is preferably used so that the number of alkenyl groups is 0.01 to 0.6 with respect to one hydrosilyl group of the (β1) component. If the addition amount is small, the thermal shock resistance of the resulting cured product may be reduced, and if the addition amount is large, the heat resistance and light resistance of the resulting cured product may be reduced.

The addition amount of the hydrosilylation catalyst used in the synthesis of the modified polyorganosiloxane is not particularly limited, but is 10 ^-1 to 10 ^{-10 with} respect to 1 mole of the alkenyl group of the (α1) component and (γ1) component used in the reaction. It is good to use in the range of mole. Preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

The modified polyorganosiloxane thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and further has various alkenyl groups because hydrosilyl groups are introduced into the molecule. It becomes possible to react with a compound (compound (A) having at least two carbon-carbon double bonds having reactivity with SiH group in one molecule).
The compound (A) having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule is a polysiloxane having two or more alkenyl groups in one molecule described below and / or in one molecule. Can be classified into organic compounds having two or more alkenyl groups, polyorganosiloxane modified products, polysiloxanes having two or more alkenyl groups in one molecule, and / or two or more alkenyl groups in one molecule. A cured product can be obtained by reacting with an organic compound.

<Polysiloxane having two or more alkenyl groups in one molecule>
In the present invention, the number of polysiloxane siloxane units having two or more alkenyl groups in one molecule is not particularly limited, but is preferably 2 or more, and more preferably 2 to 10. When the number of siloxane units in one molecule is small, the composition tends to volatilize, and desired physical properties may not be obtained after curing. Moreover, when there are many siloxane units, the gas barrier property of the obtained hardened | cured material may fall.

  In the present invention, the polysiloxane having two or more alkenyl groups in one molecule preferably has an aryl group from the viewpoint of gas barrier properties. In addition, in the polysiloxane having two or more alkenyl groups in one molecule having an aryl group, the aryl group is preferably bonded directly to the Si atom from the viewpoint of heat resistance and light resistance. In addition, the aryl group may be present at either the side chain or the end of the molecule, and the molecular structure of such an aryl group-containing polysiloxane is not limited. For example, the aryl group-containing polysiloxane has a straight chain, branched chain, or partially branched chain. In addition to the chain shape, it may have a cyclic structure.

  Examples of such aryl groups include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, and 4-ethylphenyl. Group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, biphenyl group, 2,3,4-trimethyl Examples include phenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxyphenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group and the like. . Among these, a phenyl group is a preferred example from the viewpoint of heat resistance and light resistance. These may be used alone or in combination of two or more.

  The polysiloxane having two or more alkenyl groups in one molecule in the present invention is a linear polysiloxane having two or more alkenyl groups from the viewpoint of heat resistance and light resistance, and two or more alkenyl groups at the molecular ends. Preferred examples include polysiloxanes having a cyclic structure and cyclic siloxanes having two or more alkenyl groups.

  Specific examples of the linear polysiloxane having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer, methylphenylsiloxane unit, copolymer of methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane blocked with dimethylvinylsilyl group, endblocked with dimethylvinylsilyl group Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular terminals include polysiloxanes whose ends are blocked with dimethylvinylsilyl groups exemplified above, two or more dimethylvinylsiloxane units and SiO ₂ units, SiO _{3 /} Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

  Examples of the cyclic siloxane compound having two or more alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-vinyl-1-phenyl. -3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -Diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-tri Nyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11 -Hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane and the like are exemplified.

  These polysiloxanes having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

  The amount of polysiloxane having two or more alkenyl groups per molecule can be variously set, but hydrogen per one alkenyl group is directly bonded to Si atoms contained in the polyorganosiloxane-based modified product, which is a polyorganosiloxane-modified product. It is desirable to add at a rate of 0.3 to 5, preferably 0.5 to 3 atoms. When the proportion of alkenyl groups is small, appearance defects due to foaming or the like are likely to occur, and when the proportion of alkenyl groups is large, physical properties after curing may be adversely affected.

  A cured product can be obtained by hydrosilylating the hydrosilyl group of the modified polyorganosiloxane of the present invention and the alkenyl group of a polysiloxane having two or more alkenyl groups in one molecule. In the hydrosilylation reaction, it is preferable to use a hydrosilylation catalyst. As the hydrosilylation catalyst that can be used in this reaction, those described below can be used. In the hydrosilylation reaction between a polyorganosiloxane modified product and a polysiloxane having two or more alkenyl groups in one molecule, the hydrosilylation catalyst used in the synthesis of the polyorganosiloxane modified product is combined with the polyorganosiloxane modified product. Since it is carried in, it does not need to use a hydrosilylation catalyst separately.

<Organic compound having two or more alkenyl groups in one molecule>
The organic compound having two or more alkenyl groups in one molecule is not particularly limited as long as it is an organic compound having two or more carbon-carbon double bonds reactive with SiH group in one molecule. Organic compounds do not contain siloxane units (Si-O-Si) such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers, but only C, H, N, O, S, and halogen as constituent elements It is preferable that it contains. Those containing siloxane units have gas permeability and repelling problems.

The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

A group represented by the formula (wherein R ⁵ represents a direct bond or a divalent organic group having 1 to 18 carbon atoms and R ⁶ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of reactivity.

  The number of carbon-carbon double bonds reactive with the SiH group of an organic compound having two or more alkenyl groups in one molecule may be 2 to 6 per molecule, but the mechanical strength of the cured product can be increased. When it is desired to improve, the number is preferably more than 2, more preferably 3 or more. When the number of carbon-carbon double bonds reactive with the SiH group of an organic compound having two or more alkenyl groups in one molecule is one or less per molecule, even if it reacts with the compound (β1) It becomes only a graft structure, but not a crosslinked structure. On the other hand, when the number of carbon-carbon double bonds having reactivity with SiH groups of organic compounds having two or more alkenyl groups in one molecule is more than six per molecule, the resulting cured product becomes brittle. There is a tendency and it is not preferable.

  As an organic compound having two or more alkenyl groups in one molecule, it is preferable that three or more carbon-carbon double bonds are contained in one molecule from the viewpoint of good reactivity. Moreover, it is more preferable that 4 or less carbon-carbon double bonds are contained in 1 molecule from the viewpoint that the obtained cured product does not become brittle.

  As an organic compound having two or more alkenyl groups in one molecule, from the viewpoint of high mechanical heat resistance and from the viewpoint of low formability of raw material liquid, good moldability, handleability, and coating properties, The molecular weight is preferably less than 900, more preferably less than 700, and even more preferably less than 500.

  The organic compound having two or more alkenyl groups in one molecule preferably has a viscosity at 23 ° C. of less than 100 Pa · s, more preferably less than 30 Pa · s in order to obtain good workability. The viscosity can be measured with an E-type viscometer.

  As an organic compound having two or more alkenyl groups in one molecule, those having a small content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of coloration, particularly suppression of yellowing. Those not containing a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferred. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

  From the viewpoint that the obtained cured product is less colored and has high light resistance, the organic compounds having two or more alkenyl groups in one molecule are 1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy). Adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, 5-vinylbicyclo [2.2.1] hept-2-ene, divinylbenzene , Vinylcyclohexene and 1,2,4-trivinylcyclohexane are preferred, and allyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, triallyl isocyanurate, allyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl isocyanurate, diallyl isocyanurate Cyanurate is particularly preferred.

  An organic compound having two or more alkenyl groups in one molecule may have other reactive groups. Examples of the reactive group in this case include an epoxy group, an oxetanyl group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased.

  As the organic compound having two or more alkenyl groups in one molecule, triallyl isocyanurate represented by the following general formula (I) and derivatives thereof are particularly preferable from the viewpoint of high heat resistance and light resistance.

(In the formula, R ¹ represents the same or different organic group having 1 to 20 carbon atoms or hydrogen atom, and at least one R ¹ represents a carbon-carbon double bond having reactivity with SiH group. A compound having 2 to 20 carbon atoms which may have a substituent, which is preferable).

As R < ¹ > of the said general formula (I), it is preferable that it is a C1-C10 monovalent organic group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and C1-C1 4 is more preferably a monovalent organic group. Examples of these preferable R ¹ include methyl group, ethyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and the like.

R ^{1 in the} general formula (I) is a carbon in which at least one of the three R ^{1 s} contains one or more epoxy groups from the viewpoint that adhesion of the obtained cured product with various materials can be improved. It is preferable that it is a monovalent organic group of number 1-20. Examples of these preferable R ¹ include a glycidyl group,

Etc.

As R ¹ of the general formula (I), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it contains 2 or less oxygen atoms, and C, H, O as constituent elements It is preferably a monovalent organic group having 1 to 20 carbon atoms, and more preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of these preferable R ¹ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and the like.

As R ^{1 in the} general formula (I), from the viewpoint of improving the reactivity, three R 1
^At least one of 1 is represented by the following general formula (IV)

(Wherein R ⁵ represents a direct bond or a divalent organic group having 1 to 18 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group).

R ⁵ in the above general formula (IV) is a direct bond or a divalent organic group having 1 to 18 carbon atoms. From the viewpoint that the obtained cured product can have higher heat resistance, the direct bond or carbon A divalent organic group having 1 to 10 carbon atoms is preferable, and a direct bond or a divalent organic group having 1 to 4 carbon atoms is more preferable. Examples of these preferable R ⁸ include vinyl group, allyl group, propenyl group, butenyl group and the like.

R ^{6 in the} general formula (IV) is a hydrogen atom or a methyl group, but a hydrogen atom is preferable from the viewpoint of good reactivity.

  The organic compounds having two or more alkenyl groups in one molecule can be used alone or in combination of two or more.

<Hydrosilylation catalyst>
In the present invention, a hydrosilylation catalyst is used when the polyorganosiloxane modified product is synthesized and the composition containing the modified product is cured.

  As the hydrosilylation catalyst used in the present invention, a known hydrosilylation catalyst can be used, and there is no particular limitation.

Specifically, a platinum-olefin complex, chloroplatinic acid, platinum alone, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum, a platinum-vinylsiloxane complex, such as Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, such as Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer) , Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Patent Platinum is described in the 3220972 Pat Arcola - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

<Curing retarder>
The curing retarder is a component for improving the storage stability of the polyorganosiloxane composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process. In the present invention, as the retarder, known compounds used in addition-type curable compositions with hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organophosphorus compounds , Organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like. These may be used alone or in combination of two or more.

  Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1- Examples thereof include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like.

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, and N, N-dibutyl. -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

The addition amount of the curing retarder is not particularly limited, but is preferably used in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, with respect to 1 mol of the hydrosilylation catalyst. preferable. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

<Polyorganosiloxane composition>
The polyorganosiloxane-based composition of the present invention has a polyorganosiloxane-modified product having a polysiloxane having two or more alkenyl groups in one molecule and / or two or more alkenyl groups in one molecule, if necessary. It can be obtained by adding an organic compound, a hydrosilylation catalyst and a curing retarder. The polyorganosiloxane composition of the present invention can be handled as a liquid resin composition. By using a liquid resin composition, it is possible to easily obtain a molded body according to the application by injecting or applying to a mold, package, substrate or the like and curing.

  When adding temperature when making it harden | cure, Preferably it is 30-400 degreeC, More preferably, it is 50-250 degreeC. If the curing temperature is too high, the resulting cured product tends to have poor appearance, and if it is too low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.

  The curing time can be appropriately selected depending on the curing temperature, the amount of the hydrosilylation catalyst to be used and the amount of the reactive group, and other combinations of the composition of the present application. Preferably, a cured product can be obtained by performing the treatment for 10 minutes to 8 hours.

  The composition ratio of the modified polyorganosiloxane, polysiloxane having two or more alkenyl groups in one molecule and / or organic compound having two or more alkenyl groups in one molecule is the number of moles of alkenyl groups / number of moles of SiH groups. Is preferably in the range of 0.5 to 3, more preferably in the range of 0.7 to 1.5. When the composition ratio is small or large, physical properties such as heat resistance, light resistance and gas barrier properties may not be sufficient.

  In the polyorganosiloxane composition of the present invention, an adhesion-imparting agent can be added as necessary.

  The adhesion-imparting agent is used for the purpose of improving the adhesion between the polyorganosiloxane composition and the substrate in the present invention, and is not particularly limited as long as it has such an effect. The agent can be exemplified as a preferred example.

  The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysila Alkoxysilanes having a methacrylic group or an acrylic group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.

  The addition amount of the silane coupling agent is 100 parts by weight of a mixture of a modified polyorganosiloxane and a polysiloxane having two or more alkenyl groups in one molecule and / or an organic compound having two or more alkenyl groups in one molecule. It is preferable that it is 0.05-30 weight part with respect to this, More preferably, it is 0.1-10 weight part. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  In the present invention, a known adhesion promoter can be used to enhance the effect of the adhesion promoter. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic ester compounds, organoaluminum compounds, and organotitanium compounds.

  An inorganic filler can be added to the polyorganosiloxane composition of the present invention as necessary.

  By using an inorganic filler as the composition of the polyorganosiloxane-based composition of the present invention, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflection of the molded product obtained Various physical properties such as rate, flame retardancy, fire resistance, and gas barrier properties can be improved.

  The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, etc. Silica-based inorganic filler, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, Examples thereof include ferrite, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, and silver powder. These may be used alone or in combination of two or more.

  The inorganic filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.

As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape can be used. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but from the viewpoint of gas barrier properties, the average particle size is preferably 0.005 to 50 μm, more preferably 0.01 to 20 μm. More preferably. Similarly, the BET specific surface area, although not particularly limited, from the viewpoint of gas barrier properties, it is preferably 70m ² / g or more, more preferably 100 m ² / g or more, further 200 meters ² / It is especially preferable that it is g or more.

  The amount of the inorganic filler to be added is not particularly limited, but a polyorganosiloxane modified product and a polysiloxane having two or more alkenyl groups in one molecule and / or a mixture of organic compounds having two or more alkenyl groups in one molecule are 100 weights. It is 1-1000 weight part with respect to a part, More preferably, it is 3-500 weight part, More preferably, it is 5-300 weight part. When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.

  The order of mixing the inorganic filler is not particularly limited. However, in terms of easy storage stability, a polysiloxane having two or more alkenyl groups in one molecule and / or an alkenyl group in one molecule. A method of mixing the modified polyorganosiloxane after mixing with two or more organic compounds is desirable. In addition, a stable molded product in which a polyorganosiloxane modified substance as a reaction component, a polysiloxane having two or more alkenyl groups in a molecule, and / or an organic compound having two or more alkenyl groups in a molecule is well mixed. In terms of being easily obtained, a modified polyorganosiloxane, a polysiloxane having two or more alkenyl groups in one molecule and / or a mixture of organic compounds having two or more alkenyl groups in one molecule, inorganic It is preferable to mix a filler.

  The means for mixing these inorganic fillers is not particularly limited, but specifically, for example, a stirrer such as a two-roll or three-roll, a planetary stirring deaerator, a homogenizer, a dissolver, a planetary mixer, etc. And melt kneaders such as a plast mill. The mixing of the inorganic filler may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.

  In addition, the polyorganosiloxane composition of the present invention may optionally contain various additives such as phosphors, colorants, heat resistance improvers, reaction control agents, mold release agents, and dispersants for fillers. Can be added. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  In the polyorganosiloxane composition of the present invention, the above-described components are uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or using a planetary stirring deaerator, and heat-treated as necessary. You may give it.

  The polyorganosiloxane composition of the present invention can be used as a molded article. As a molding method, any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding can be used.

  Specific uses of the molded product obtained in the present invention include, for example, substrate materials in the field of liquid crystal displays, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, color filters, polarizers. Examples of the peripheral material of the liquid crystal display device such as a protective film and a film for liquid crystal such as a passivation film are exemplified. It is also used in PDP (plasma display) sealants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, color filters, passivation films, and LED display devices. LED element mold material, front glass protective film, front glass substitute material, adhesive, color filter, passivation film, substrate material for plasma addressed liquid crystal display, light guide plate, prism sheet, deflector plate, retardation plate, field of view Corner correction film, adhesive, color filter, polarizer protective film, passivation film, front glass protective film, front glass substitute material, color filter, adhesive, passivation film, and field emission in organic EL displays Various film substrate in Isupurei (FED), front glass protective films, front glass substitute material, adhesive, a color filter, a passivation film is exemplified.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives. More specifically, optical pickup members such as next-generation DVDs, such as pickup lenses, collimator lenses, objective lenses, sensor lenses, protective films, element sealants, sensor sealants, gratings, adhesives, prisms And a wave plate, a correction plate, a splitter, a hologram, a mirror, and the like.

  In the field of optical equipment, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

  In the field of optical components, fiber materials, lenses, waveguides, element sealants, adhesives and the like around optical switches in optical communication systems are exemplified. Examples include optical fiber materials, ferrules, sealants, adhesives and the like around the optical connector. Examples of optical passive components and optical circuit components include lenses, waveguides, LED element sealants, adhesives, and the like. Examples include substrate materials, fiber materials, element sealants, adhesives, and the like around an optoelectronic integrated circuit (OEIC).

  In the field of optical fibers, examples include sensors for industrial use such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in the home.

  Examples of the semiconductor integrated circuit peripheral material include an interlayer insulating film, a passivation film, an LSI, and a resist material for microlithography for an LSI material.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Examples include rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, and glass substitutes. Moreover, the multilayer glass for rail vehicles is illustrated. Further, examples thereof include a toughness imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating.

  In the construction field, interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials are exemplified. In agriculture, a house covering film is exemplified.

  Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.

  Next, although the composition of this invention is demonstrated in detail based on an Example, this invention is not limited only to these Examples.

(viscosity)
An E-type viscometer manufactured by Tokyo Keiki was used. Measurement was performed at a measurement temperature of 23.0 ° C. and an EHD type 48φ1 times cone.

(SiH value)
The following SiH value is obtained by making a mixture of the compound and dibromoethane, dissolving in deuterated chloroform, and performing NMR measurement using 400 MHz NMR manufactured by Bruker BioSpin Co., Ltd.
SiH value (mol / kg) = [integral value of peak attributed to SiH group of compound] / [integral value of peak attributed to methyl group of dibromoethane] × 4 × [weight of dibromoethane in mixture] / [Molecular weight of dibromoethane] / [weight of compound in mixture] (1)
Calculated using

(Preparation of samples for heat resistance test and light resistance test)
The composition was filled in a mold and thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours to prepare a sample having a thickness of 2 mm.

(Heat resistance test)
The sample prepared as described above was cured for 200 hours in a convection oven (in air) set at a temperature of 150 ° C., and visually observed. The case where no change in color due to coloring was observed was evaluated as ◎, the case where slight coloring was observed was evaluated as ◯, and the case where coloring was observed was evaluated as ×.

(Light resistance test)
A metering weather meter (model M6T) manufactured by Suga Test Instruments Co., Ltd. was used. The sample prepared as described above was irradiated with a black panel temperature of 120 ° C. and an irradiance of 0.53 kW / m ² to an integrated irradiance of 50 MJ / m ² and observed visually. The case where no change in color due to coloring was observed was evaluated as ◎, the case where slight coloring was observed was evaluated as ◯, and the case where coloring was observed was evaluated as ×.

(Creation of sample for cold thermal shock test)
Enomoto Co., Ltd. LED package (product name: TOP LED 1-IN-1), 0.4mm x 0.4mm x 0.2mm single crystal silicon chip, Henkel Japan Co., Ltd. epoxy adhesive (product name) : LOCITE 348) and fixed by heating in a convection oven set at 150 ° C. for 30 minutes. The composition was injected here, and a sample was prepared by thermosetting in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours.

(Cold thermal shock resistance test)
The sample prepared as described above was subjected to 1000 cycles of high temperature holding 100 ° C., 30 minutes, low temperature holding −40 ° C., 30 minutes using a thermal shock tester (TSA-71H-W manufactured by Espec). A sample was observed. After the test, make a visual check to mark the peeling between the resin and the package, the crack of the resin, and no coloration, and any one of the peeling between the resin and the package, the crack of the resin, or the coloring The case where it was recognized was set as x.

(Making samples for moisture permeability test)
(In the present invention, the moisture permeability of the cured product was used as an index of the gas barrier property of the obtained cured product. That is, a low moisture permeability is synonymous with a high gas barrier property.) The sample was filled and thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours to prepare a sample of 5 cm square and 2 mm thickness. This sample was cured for 24 hours in an environment of room temperature 60 ° C. and humidity 90% RH.

(Moisture permeability test)
A jig is prepared by fixing a 5 cm square polyisobutylene rubber sheet (3 mm thick, 3 cm square inside so as to be a square shape) on top of a 5 cm square plate glass (0.5 mm thick), 1 g of calcium chloride (for moisture measurement) manufactured by Wako Pure Chemical Industries, Ltd. is filled into a square shape. Furthermore, the above 5 cm square sample with a thickness of 2 mm is fixed to the upper part, and this is used as a test specimen. The test specimen is cured for 24 hours in a thermo-hygrostat (Espec SP-2KP) at a temperature of 60 ° C. and a humidity of 90% RH.
Moisture permeability (g / m ² / day) = [(total specimen weight after moisture permeability test (g)) − (total specimen weight before moisture permeability test (g))] × 10000/9 (2)
The moisture permeability (water vapor transmission rate) was calculated according to

(Hydrogen sulfide test)
Samples were injected into the LED package (product name: TOP LED 1-IN-1) manufactured by Enomoto Co., Ltd., and heat-cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours. It was created. This sample was put in a flow type gas corrosion tester (Factkey KG130S), and a hydrogen sulfide exposure test was performed for 96 hours under the conditions of 60 ° C., 80% RH, and hydrogen sulfide 3 ppm. After the test, ◎ if the lead frame portion of the package was not discolored, ◯ if slightly discolored, and × if it was black.

(Production Example 1)
71.80 g of diphenylmethylvinylsilane and 0.20 g of a toluene solution of 0.03% platinum vinylsiloxane complex were dissolved in 10 g of toluene. While stirring this solution in a temperature range of 100 to 110 ° C. in a nitrogen atmosphere, 48.08 g of 1,3,5,7-tetramethyl-1,3,5,7-tetramethylcyclosiloxane and 109.74 g of toluene were used. It was dripped at the liquid mixture of 2 over 2 hours. After completion of the dropwise addition, the mixture was stirred for 1 hour, and a solution obtained by dissolving 12.46 g of triallyl isocyanurate and 0.48 g of a toluene solution of 0.03% platinum vinylsiloxane complex in 12.43 g of toluene was heated to a temperature of 100 to 110 ° C. in a nitrogen atmosphere. Under the range, it was dripped over 2 hours, stirring. After stirring for 1 hour after completion of the dropping, the reaction solution was cooled to room temperature and the solvent was distilled off under reduced pressure with an evaporator to obtain 131.8 g of a modified polyorganosiloxane (SiH value 2.31 mol / kg).

(Production Comparative Example 1)
To a 2 L autoclave, 696 g of toluene, 556 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated so that the internal temperature became 104 ° C. Thereto, a mixture of 80 g of triallyl isocyanurate, 0.05 g of a 3% platinum-vinylsiloxane complex xylene solution (containing 3% by weight of platinum) and 60 g of toluene was dropped, and the mixture was heated and stirred for 7 hours. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a modified liquid polyorganosiloxane (SiH value: 9.2 mol / kg).

(Production Comparative Example 2)
A 2 L autoclave was charged with 600 g of toluene and 200 g of 1,3,5,7-tetramethylcyclotetrasiloxane, the gas phase portion was replaced with nitrogen, and then heated and stirred at a jacket temperature of 50 ° C. A mixed solution of 96 g of allyl glycidyl ether, 96 g of toluene and 0.027 g of a 3% platinum vinylsiloxane complex in xylene was added dropwise over 60 minutes. After completion of the dropping, the jacket temperature was raised to 60 ° C. and reacted for 40 minutes, then a mixed solution of 14 g of triallyl isocyanurate and 14 g of toluene was dropped, the jacket temperature was raised to 105 ° C., 56 g of triallyl isocyanurate, 56 g of toluene and 3 g of toluene. A mixed solution of 0.017 g of a xylene solution of% platinum vinylsiloxane complex was added dropwise over 30 minutes. Four hours after the completion of the dropping, the reaction solution was cooled to room temperature, and the solvent was distilled off under reduced pressure with an evaporator to obtain a liquid polyorganosiloxane modified product (SiH value 5.1 mol / kg).

Example 1
20.25 g of the modified polyorganosiloxane obtained in Production Example 1, 4.77 g of diallyl monomethyl isocyanurate, 2.1 μL of toluene solution of 3% platinum vinylsiloxane complex, 2.3 μL of 10% toluene solution of dimethyl maleate, γ -Glycidoxypropyltrimethoxysilane 0.125g, 1-ethynyl cyclohexanol 10% toluene solution 5.4microliter was added and stirred, and the composition was obtained. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 2)
17.66 g of the modified polyorganosiloxane obtained in Production Example 1, 7.34 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, 3% platinum vinylsiloxane complex 1.9 μL of toluene solution of 1.9 μL, 10% toluene solution of dimethyl maleate, 0.125 g of γ-glycidoxypropyltrimethoxysilane, and 5.4 μL of 10% toluene solution of 1-ethynylcyclohexanol were added and stirred. A composition was obtained. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 1)
12.00 g of the modified polyorganosiloxane obtained in Production Comparative Example 1, 8.00 g of triallyl isocyanurate, 0.02 g of toluene solution of 3% platinum vinylsiloxane complex, and 0.02 g of 1-ethynylcyclohexanol were added and stirred. And a composition was obtained. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 2)
18.76 g of the modified polyorganosiloxane obtained in Production Comparative Example 2, 6.24 g of diallyl monomethyl isocyanurate, 8.4 μL of a 3% platinum vinylsiloxane complex toluene solution, and 3.6 μL of dimethyl maleate were added and stirred. A composition was obtained. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 3)
Various evaluations described above were performed using SCR-1016 resin manufactured by Shin-Etsu Chemical Co., Ltd., and the results are shown in Table 1.

  As shown in Table 1, the polyorganosiloxane composition of the present invention has high heat resistance, light resistance and thermal shock resistance, and is more excellent in gas barrier properties.

Claims (8)

(Α1) a compound having at least one carbon-carbon double bond having reactivity with a SiH group in one molecule;
(Β1) a linear and / or cyclic polyorganosiloxane compound having at least two SiH groups in one molecule, and
(Γ1) A hydrosilylation reaction product of a silane compound (excluding a compound having a hydrolyzable group) having one carbon-carbon double bond having reactivity with a SiH group in one molecule. ,
The compound (α1) is 1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane , Dicyclopentadiene, 5-vinylbicyclo [2.2.1] hept-2-ene, divinylbenzene, vinylcyclohexene, 1,2,4-trivinylcyclohexane, the following general formula (I)

(In the formula, R ¹ represents the same or different organic group having 1 to 20 carbon atoms or a hydrogen atom, and at least one R ¹ represents a carbon-carbon double bond having reactivity with a SiH group. An organic group having 2 to 20 carbon atoms which may have a substituent.

A modified polyorganosiloxane, which is at least one selected from the group consisting of: The compound represented by the general formula (I) comprises allyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, triallyl isocyanurate, allyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl isocyanurate, diallyl isocyanurate. The modified polyorganosiloxane according to claim 1, which is at least one selected from the group. The compound (β1) is represented by the following general formula (II)

(Wherein R ² represents an organic group having 1 to 6 carbon atoms which may be the same or different, and m and n represent numbers satisfying 3 ≦ m + n ≦ 10 and 2 ≦ m ≦ 10). The modified polyorganosiloxane according to claim 1 or 2. The compound (γ1) is represented by the following general formula (III)

(Wherein R ³ represents an organic group having 2 to 10 carbon atoms which may have a substituent having one carbon-carbon double bond having reactivity with a SiH group, and R ⁴ is the same or different. 4. The modified polyorganosiloxane according to any one of claims 1 to 3, which is an organic group having 1 to 10 carbon atoms which may be present. The modified polyorganosiloxane according to claim 4, wherein at least one of R ⁴ has a phenyl skeleton. Compound (A) having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, Compound (B) having at least two SiH groups in one molecule, Hydrosilylation catalyst (C) A curable composition for encapsulating an optical semiconductor element, comprising the modified polyorganosiloxane according to any one of claims 1 to 5 in the component (B) . 7. The optical semiconductor element sealing according to claim 6, wherein the compound (A) is at least one compound selected from the group consisting of triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate. Curable composition. Hardened | cured material formed by hardening | curing the curable composition of Claim 6 or 7 .