JP5407615B2 - Organopolysiloxane, curable composition containing the same, and method for producing the same - Google Patents

Description

  The present invention relates to an organopolysiloxane, a curable composition containing the organopolysiloxane, and a method for producing the same. More specifically, the organopolysiloxane has excellent adhesion during heating, does not generate cracks, and can form a cured product having higher hardness. The present invention relates to siloxane, a curable composition containing the same, and a method for producing the same.

  Conventionally, an epoxy compound mainly composed of bisphenol A glycidyl ether has been generally used as a resin for encapsulating an optical semiconductor, but since such an epoxy compound has an aromatic ring, an optical semiconductor that emits blue or ultraviolet light. In order to perform sealing, durability against ultraviolet rays (UV durability) was insufficient.

Therefore, it has been proposed to use an alicyclic epoxy compound in order to improve the UV durability of the resin for encapsulating an optical semiconductor, but the UV durability has still not been sufficient.
On the other hand, it is known that a resin having a siloxane skeleton is excellent in weather resistance, and in recent years, studies using a resin having polydimethylsiloxane as a main skeleton as an optical semiconductor sealing material have been conducted.

  Patent Document 1 discloses a composition containing a linear siloxane having an epoxy group. However, when this composition is used for sealing an optical semiconductor, linear siloxane has a large coefficient of linear expansion, so that the cured product is inferior in adhesion during heating, or cracks are generated in the cured product, etc. There was a problem.

In this respect, polysiloxane based on a hydrolyzate (MQ) of a tetrafunctional silane compound (Q: Si (OR) ₄ ) and a monofunctional silane compound (M: SiR ₃ (OR)) has a linear expansion coefficient. Therefore, it is known that the cured product has excellent adhesion during heating, and cracks are hardly generated in the cured product.

  Patent Document 2 discloses a composition for an LED sealing material using MQ having a vinyl group and MQ having SiH. However, since this composition uses a white metal metal catalyst as a curing catalyst, there is a problem that the transparency of the cured product is low.

  Patent Document 3 describes a polysiloxane based on MQ having an epoxy group. However, when this polysiloxane is used for sealing an optical semiconductor, in the synthesis of this polysiloxane, after synthesizing MQ having Si—H, this is reacted with a compound having an epoxy group. Therefore, it was difficult to completely remove the catalyst from the catalyst, and there was a problem that the transparency of the sealing material was low. Moreover, the hardened | cured material obtained from this polysiloxane also had the problem that hardness was low.

JP-A-4-339816 JP 2004-186168 A Japanese Patent Laid-Open No. 5-105758

  The present invention provides a polysiloxane capable of forming a cured product that is excellent in adhesion during heating, hardly generates cracks, has high transparency, and has high hardness, and a curable composition containing the polysiloxane. With the goal.

The present invention for achieving the above object
An organopolysiloxane containing structural units represented by the following general formulas (1) to (3), having a silanol equivalent of 0 g / eq. Exceeding 500 g / eq. The organopolysiloxane is characterized by containing 10 to 70 mol% of a trifunctional siloxane unit when the total siloxane units constituting the organopolysiloxane are 100 mol%.

〔式中、Ｒ¹およびＲ³は、それぞれ独立に非置換もしくは置換の炭素数１〜３の１価の炭化水素基を示す。

[Wherein, R ¹ and R ³ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 3 carbon atoms.

R ^E represents an organic group having 3 to 20 carbon atoms having an epoxy group.
R ⁹ each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms.

a is 0 or 1; ]
In the organopolysiloxane, when the total siloxane unit constituting the organopolysiloxane is 100 mol%, the monofunctional siloxane unit is 20 to 80 mol% and the tetrafunctional siloxane unit is 10 to 60 mol%. It is preferable to contain,
It is preferable that R ^{E of the} formula (1) is represented by any one of the following general formulas (7) to (10).

〔一般式（７）中Ｒ⁵はメチレン基または２価の炭素数２〜１０の直鎖状アルキレン基または炭素数３〜１０の分岐鎖状アルキレン基を示す。〕

[R ^{5 in} General Formula (7) represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]

〔一般式（８）中Ｒ⁶はメチレン基または２価の炭素数２〜１０の直鎖状アルキレン基または炭素数３〜１０の分岐鎖状アルキレン基を示す。〕

[In General Formula (8), R ⁶ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]

〔一般式（９）中Ｒ⁷はメチレン基または２価の炭素数２〜１０の直鎖状アルキレン基または炭素数３〜１０の分岐鎖状アルキレン基を示す。〕

[In the general formula (9), R ⁷ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. ]

〔一般式（１０）中Ｒ⁸はメチレン基または２価の炭素数２〜１０の直鎖状アルキレン基または炭素数３〜１０の分岐鎖状アルキレン基を示す。〕
他の発明は、前記オルガノポリシロキサンとエポキシ用硬化剤とを含有することを特徴とする硬化性組成物である。

[In General Formula (10), R ⁸ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]
Another invention is a curable composition comprising the organopolysiloxane and an epoxy curing agent.

In the curable composition, the epoxy curing agent is preferably an acid anhydride.
Another invention is an optical semiconductor sealing composition comprising the curable composition,
It is a light emitting element using this composition for optical semiconductor sealing.

In addition, other inventions
A basic compound comprising a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), a siloxane compound (A) containing a silanol group and an alkoxysilane compound (B) having an epoxy group The process for producing an organopolysiloxane is characterized by comprising a step of reacting in the presence of.

〔式（２）中、Ｒ¹は、前記オルガノポリシロキサンに含まれる構成単位を表わす式（２）におけるＲ¹と同様である。〕

Wherein (2), R ¹ are the same as R ¹ in the formula (2) representing the structural unit contained in the organopolysiloxane. ]

In the method for producing the organopolysiloxane, the siloxane compound (A) is:
It is selected from the group consisting of a silane compound (A-1) represented by the following formula (4), a silane compound represented by the following formula (5), a condensate of the silane compound, and a hydrolyzate of the silane compound. It is preferably obtained by reacting with at least one (A-2),

〔式（４）中、Ｒ¹は、前記シロキサン化合物（Ａ）に含まれる構成単位を表わす式（２）におけるＲ¹と同様である。〕

[In Formula (4), R < ¹ > is the same as R < ¹ > in Formula ( 2 ) showing the structural unit contained in the said siloxane compound (A) . ]

〔式（５）中Ｒ²は非置換もしくは置換の１価の炭化水素基を示す。〕
前記アルコキシシラン化合物（Ｂ）が下記式（６）で表される化合物であることが好ましい。

[In formula (5), R ² represents an unsubstituted or substituted monovalent hydrocarbon group. ]
The alkoxysilane compound (B) is preferably a compound represented by the following formula (6).

〔式（６）中Ｒ^E、Ｒ³およびａは、それぞれ式（１）におけるＲ^E、Ｒ³およびａと同様である。Ｒ⁴はそれぞれ独立に非置換または置換の炭素数１〜３の炭化水素基を示す。〕

[Formula (6) was R ^E, R ³ and a are, R ^E in each formula (1) is the same as R ³ and a. R ⁴ each independently represents an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms. ]

  By using the polysiloxane according to the present invention, it is possible to produce a curable composition that is excellent in adhesion at the time of heating, hardly generates cracks, has high transparency, and can form a cured product with high hardness. Can do. Moreover, according to the manufacturing method of the polysiloxane which concerns on this invention, the said polysiloxane can be manufactured efficiently.

FIG. 1 is a schematic diagram of an LED. FIG. 2 is a schematic diagram of an LED having a fluorescent part.

<Curable composition>
The curable composition concerning this invention contains organopolysiloxane and the hardening | curing agent for epoxy, and can contain a silica particle etc. as needed. The curable composition concerning this invention can be used conveniently as a composition for optical semiconductor sealing.

Organopolysiloxane The organopolysiloxane contained in the curable composition contains structural units represented by the following general formulas (1) to (3) and has a silanol equivalent of 0 g / eq. Exceeding 500 g / eq. The organopolysiloxane is an organopolysiloxane having an epoxy group-containing organic group containing 10 to 70 mol% of a trifunctional siloxane unit when the total amount of siloxane units constituting the organopolysiloxane is 100 mol%.

〔式中、Ｒ¹およびＲ³は、それぞれ独立に非置換もしくは置換の炭素数１〜３の１価の炭化水素基を示す。
Ｒ^Eは、エポキシ基を有する炭素数３〜２０の有機基を示す。
Ｒ⁹は、それぞれ独立に水素原子または非置換もしくは置換の炭素数１〜３の炭化水素基を示す。
ａは０または１である。〕

[Wherein, R ¹ and R ³ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 3 carbon atoms.
R ^E represents an organic group having 3 to 20 carbon atoms having an epoxy group.
R ⁹ each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms.
a is 0 or 1; ]

  The organopolysiloxane can be cured by ring-opening polymerization of epoxy groups. The epoxy equivalent of the organopolysiloxane is 250 to 1000 g / eq. , Preferably 250 to 800 g / eq. , More preferably 300 to 800 g / eq. It is. The epoxy equivalent is 250 g / eq. If it is less than 1, the durability of the cured product to light and heat is inferior, and 1000 g / eq. If it exceeds, the hardness of the cured product tends to be insufficient and fragile.

R ^E is an organic group having 3 to 20 carbon atoms having an epoxy group. The organopolysiloxane preferably has at least one of the group represented by R ^E by the following general formula (7) to (10). When the organopolysiloxane has such a group, a cured product having excellent heat resistance, light resistance and dimensional stability can be obtained.

Specific examples of the group represented by the general formula (7) include 2- (3 ′, 4′-epoxycyclohexyl) ethyl group and the like.
Specific examples of the group represented by the general formula (8) include a 3-glycidyl group.

Specific examples of the group represented by the general formula (9) include a 3-glycidoxypropyl group.
Specific examples of the group represented by the general formula (10) include a 2- (4′-methyl-3 ′, 4′-epoxycyclohexyl) ethyl group and the like.

〔一般式（７）中Ｒ⁵はメチレン基または２価の炭素数２〜１０の直鎖状アルキレン基または炭素数３〜１０の分岐鎖状アルキレン基を示す。〕

[R ^{5 in} General Formula (7) represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]

〔一般式（８）中Ｒ⁶はメチレン基または２価の炭素数２〜１０の直鎖状アルキレン基または炭素数３〜１０の分岐鎖状アルキレン基を示す。〕

[In General Formula (8), R ⁶ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]

〔一般式（９）中Ｒ⁷はメチレン基または２価の炭素数２〜１０の直鎖状アルキレン基または炭素数３〜１０の分岐鎖状アルキレン基を示す。〕

[In the general formula (9), R ⁷ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. ]

〔一般式（１０）中Ｒ⁸はメチレン基または２価の炭素数２〜１０の直鎖状アルキレン基または炭素数３〜１０の分岐鎖状アルキレン基を示す。〕

[In General Formula (10), R ⁸ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]

The organopolysiloxane contains a silanol group together with an epoxy group. R ⁹ in Formula (1) is each independently a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms. In the formula (1), when R ⁹ is a hydrogen atom, OR ⁹ and Si bonded with OR ⁹ form a silanol group. Since a is 0 or 1, (OR ⁹ ) always exists in the formula (1). When organopolysiloxane contains a silanol group, when this composition is hardened | cured, the bridge | crosslinking by silanol groups will be formed and it will be thought that hardened | cured material with high hardness is obtained. The proportion of hydrogen atoms in the total R ⁹ is preferably 5 to 100 mol%, more preferably 10 to 80 mol%.

  The silanol equivalent of the organopolysiloxane is 0 g / eq. Exceeding 500 g / eq. The following is preferable in that a cured product having high hardness can be obtained. The silanol equivalent was 500 g / eq. If it is larger, the effect of improving the hardness due to the cross-linking may be hardly seen.

Specific examples of the hydrocarbon group represented by R ⁹ include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group is particularly preferable.
R ¹ and R ³ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 3 carbon atoms. Specific examples of R ¹ and R ³ include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group is particularly preferable.

  In the organopolysiloxane, it is preferable that the trifunctional siloxane unit is contained in an amount of 10 to 70 mol%, preferably 10 to 60%, based on 100 mol% of all siloxane units constituting the organopolysiloxane. More preferably. When the organopolysiloxane contains a trifunctional siloxane unit within the above range, a cured product having excellent heat resistance and light resistance and high hardness can be obtained.

  Moreover, in the said organopolysiloxane, when all the siloxane units which comprise the said organopolysiloxane are made into 100 mol%, it is preferable that 20-80 mol% of monofunctional siloxane units are contained, 20-70 mol. % Content is more preferable.

  The organopolysiloxane preferably contains 10 to 60 mol% of tetrafunctional siloxane units when the total siloxane units constituting the organopolysiloxane are 100 mol%. More preferably. When the organopolysiloxane contains a monofunctional siloxane unit and a tetrafunctional siloxane unit within the above range, a liquid polymer shape can be maintained without a solvent, and since the linear expansion coefficient is low, peeling and cracking are unlikely to occur. An LED encapsulant can be obtained.

  Here, the monofunctional siloxane unit refers to a unit in which one oxygen atom and three carbon atoms are bonded to one silicon atom. A trifunctional siloxane unit refers to a unit in which three oxygen atoms and one carbon atom are bonded to one silicon atom. The tetrafunctional siloxane unit refers to a unit in which four oxygen atoms are bonded to one silicon atom.

The organopolysiloxane preferably has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography in the range of 500 to 1000000, and more preferably in the range of 1000 to 30000. When the weight average molecular weight of the organopolysiloxane is within the above range, it is easy to handle when producing an optical semiconductor sealing material using the composition, and the cured product obtained from the composition is an optical semiconductor sealing material. Sufficient material strength and properties.
The organopolysiloxane is preferably contained in an amount of 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total mass of the composition.

[Method for producing organopolysiloxane]
Although there is no restriction | limiting in particular about the manufacturing method of the said organopolysiloxane, According to the manufacturing method shown below, the said organopolysiloxane can be manufactured efficiently.

The production method includes a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), and a siloxane compound (A) containing a silanol group (hereinafter referred to as “siloxane compound (A)”). And an alkoxysilane compound (B) having an epoxy group (hereinafter referred to as “alkoxysilane compound (B)”) in the presence of a basic compound (hereinafter referred to as step (i)). . This production method usually includes a step of reacting the product obtained in step (i) with water in the presence of a basic compound (hereinafter referred to as step (ii)).

〔式（２）中、Ｒ¹は、前記オルガノポリシロキサンに含まれる構成単位を表わす式（２）におけるＲ¹と同様である。〕

Wherein (2), R ¹ is the same as R ¹ in formula (2) representing the structural unit contained in the organopolysiloxane. ]

(Siloxane compound (A))
The siloxane compound (A) is, for example,
It is selected from the group consisting of a silane compound (A-1) represented by the following formula (4), a silane compound represented by the following formula (5), a condensate of the silane compound, and a hydrolyzate of the silane compound. It can be obtained by reacting with at least one (A-2).

〔式（４）中、Ｒ¹は、前記シロキサン化合物（Ａ）に含まれる構成単位を表わす式（２）におけるＲ¹と同様である。〕

[In Formula (4), R < ¹ > is the same as R < ¹ > in Formula ( 2 ) showing the structural unit contained in the said siloxane compound (A) . ]

〔式（５）中Ｒ²は非置換もしくは置換の１価の炭化水素基を示す。〕
上記式（４）において、Ｒ¹は、式（１）で挙げたＲ¹と同様の基である。

[In formula (5), R ² represents an unsubstituted or substituted monovalent hydrocarbon group. ]
In the above formula (4), R ¹ is the same group as R ¹ listed in the formula (1).

In the above formula (5), R ² is an unsubstituted or substituted monovalent hydrocarbon group. Specific examples of R ² include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group is particularly preferable.

  In the above reaction, the mixing ratio of the compound (A-1) and the compound (A-2) is a molar ratio of a monofunctional silicon atom and a tetrafunctional silicon atom, and is usually (monofunctional silicon atom): (tetrafunctional Of silicon atoms) = 1: 0.1 to 1: 2.5, preferably 1: 0.5 to 1: 2.0, more preferably 1: 0.7 to 1: 2.0. It is a range. If the monofunctional silicon molar ratio is larger than the above range, desired physical properties in terms of linear expansion coefficient and elastic modulus cannot be obtained, and if it is smaller than the above range, the liquid state in the absence of a solvent cannot often be maintained.

The reaction between the compound (A-1) and the compound (A-2) is performed, for example, by dropping the compound (A-2) into the mixed system of the hydrochloric acid aqueous solution and the compound (A-1) while stirring. Is called.
The hydrochloric acid aqueous solution usually contains 5% by mass or more, preferably 10% by mass or more of hydrogen chloride.

  In the mixed system of the hydrochloric acid aqueous solution and the compound (A-1), an organic solvent that does not directly participate in the reaction may coexist in order to dilute the reaction system or improve the mixing of the aqueous layer and the organic layer. it can. Examples of such an organic solvent include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, benzene, toluene, and xylene.

  1-90 mass% is preferable and, as for the density | concentration of the compound (A-1) in the said mixed system, 10-70 mass% is more preferable. The temperature of the mixed system when dropping the compound (A-2) is usually 0 to 90 ° C, preferably 0 to 40 ° C.

  By this reaction, a siloxane compound (A) having an MQ skeleton containing the structural unit represented by the above formula (2) and the structural unit represented by the above formula (3) is synthesized. This siloxane compound (A) has an OH group bonded to an Si atom forming the MQ skeleton, that is, a silanol group.

(Alkoxysilane compound (B))
The alkoxysilane compound (B) has an epoxy group and is represented, for example, by the following formula (6).

〔式（６）中Ｒ^E、Ｒ³およびａは、それぞれ式（１）におけるＲ^E、Ｒ³およびａと同様である。Ｒ⁴はそれぞれ独立に非置換または置換の炭素数１〜３の炭化水素基を示す。〕
上記式（６）において、Ｒ^EおよびＲ³は、それぞれ式（１）で挙げたＲ^EおよびＲ³と同様の基である。

[Formula (6) was R ^E, R ³ and a are, R ^E in each formula (1) is the same as R ³ and a. R ⁴ each independently represents an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms. ]
In the above formula (6), R ^E and R ³ are the same groups as R ^E and R ³ mentioned in the formula (1), respectively.

R ⁴ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 3 carbon atoms. Specific examples of R ⁴ include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group is particularly preferable.
a is 0 or 1;

  Examples of the alkoxysilane compound (B) include 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 2- (4′-methyl-3). '4'-epoxycyclohexyl) ethyltrimethoxysilane is preferred, and 2- (3', 4'-epoxycyclohexyl) ethyltrimethoxysilane is particularly preferred from the viewpoint of stability in step (ii) described later.

  In this reaction, an alkoxysilane other than the alkoxysilane compound (B) can be appropriately added to adjust the hardness of the cured product. Examples of such alkoxysilane include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, Examples thereof include ethyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane.

(Process (i))
In this step, the siloxane compound (A) and the alkoxysilane compound (B) are reacted in the presence of a basic compound as a catalyst to form a siloxane bond mainly by a dealcoholization coupling reaction. It is desirable to implement this process in a state where water is not present as much as possible. In the presence of water, the reaction process includes a hydrolysis / dehydration condensation process, which is an equilibrium reaction, making it difficult to increase the reaction rate of the entire system.

  In the above reaction, the mixing molar ratio of the siloxane compound (A) and the alkoxysilane compound (B) is usually in the range of 1: 0.01 to 1: 100, preferably 1: 0.02 to 1:50, More preferably, it is in the range of 1: 0.05 to 1:20. When the mixing molar ratio is in the above range, the reaction proceeds efficiently, the above-mentioned polymer for sealing an optical semiconductor within the epoxy equivalent range is obtained, and a cured product having excellent heat resistance can be obtained. The number of moles of the siloxane compound (A) is a value obtained by dividing the mass of the mixed siloxane compound (A) by the weight average molecular weight (Mw).

  The temperature of the reaction is preferably 10 to 100 ° C, more preferably 10 to 80 ° C, and particularly preferably 15 to 70 ° C. The reaction time is preferably 1 to 48 hours, more preferably 1 to 24 hours, and particularly preferably 2 to 12 hours. The reaction may be carried out by charging each component in a reaction vessel at once, or may be carried out while intermittently or continuously adding the other component to one component.

  An alkoxy group remains in the alkoxysilane residue contained in the polysiloxane produced by the above reaction (hereinafter, this polysiloxane is referred to as “alkoxy group-containing polysiloxane”).

(Basic compound)
Examples of the basic compound include ammonia (including aqueous ammonia), organic amines, nitrogen-containing compounds other than organic amines, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, and sodium methoxide. And alkali metal alkoxides such as sodium ethoxide. Among these, ammonia and nitrogen-containing compounds other than organic amines and organic amines are preferable.

Examples of the organic amine include alkylamine, alkoxyamine, alkanolamine, and arylamine.
Alkylamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine , Alkylamines having an alkyl group having 1 to 4 carbon atoms, such as triethylamine, tripropylamine, and tributylamine.

  Alkoxyamines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine , Alkoxyamines having 1 to 4 carbon atoms such as butoxyethylamine, butoxypropylamine, and butoxybutylamine.

  As alkanolamine, methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethyl Ethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine Alkanolamine having an alkyl group having 1 to 4 carbon atoms such as alkanolamine and derivatives thereof.

Examples of the arylamine include aniline and N-methylaniline.
Further, as other organic amines and nitrogen-containing compounds other than organic amines, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc. Side: Tetraalkylethylenediamine such as tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine; Alkylaminoalkylamine such as methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine, ethylaminomethylamine Pyridine, pyrrole, piperazine, pyrrolidine, piperidine Picoline, morpholine, methylmorpholine, diazabicyclooctane okra down, diazabicyclononane, and also such as diazabicycloundecene.

Such basic compounds may be used alone or in combination of two or more.
Of these, triethylamine, pyrrolidine, tetramethylammonium hydroxide, pyridine, diazabicyclononane and diazabicycloundecene are particularly preferable.

  In the said process (i), a basic compound is 1-50 weight part normally with respect to a total of 100 weight part of a siloxane compound (A) and an alkoxysilane compound (B), Preferably it is 2-30 weight part. Preferably 2 to 20 parts by weight are added.

(Organic solvent)
In the step (i), an organic solvent can also be used.
Examples of the organic solvent include alcohols, aromatic hydrocarbons, ethers, ketones, esters, and the like. Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, Examples include ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol. Aromatic hydrocarbons include benzene, toluene, xylene, etc., ethers include tetrahydrofuran, dioxane, etc., and ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like. . These organic solvents may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among these organic solvents, from the viewpoint of promoting the reaction, it is preferable to use an organic solvent other than alcohol, for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and the like.

  The organic solvent can be appropriately used for the purpose of controlling the reaction. When an organic solvent is used, the amount used can be appropriately set according to desired conditions.

(Step (ii))
In this step, the product obtained in the step (i) is reacted with water in the presence of a basic compound. By this reaction, it is considered that the alkoxy group contained in the alkoxy group-containing polysiloxane is converted to a hydroxyl group and a silanol group is generated, and as a result, the organopolysiloxane is generated (hereinafter referred to as this reaction). The obtained organopolysiloxane is also referred to as “silanol group epoxy group-containing polysiloxane”). In this reaction, not all of the alkoxy groups are converted to silanol groups, but some of them remain as alkoxy groups. Moreover, a part of silanol group of the silanol group epoxy group-containing polysiloxane may be condensed.

  This reaction is preferably performed in an organic solvent in the presence of a basic compound as a catalyst. As the catalyst used at this time, the basic compound used in the step (i) may be used continuously, or the same or different basic compound may be newly added.

  The amount of water added in the step (ii) is usually 10 to 500 weights when the total weight of the siloxane compound (A) and the alkoxysilane compound (B) in the step (i) is 100 parts by weight. Parts, preferably 20 to 200 parts by weight, more preferably 30 to 100 parts by weight. It is preferable for the amount of water added to be in the above range because step (ii) proceeds sufficiently and the amount of water removed after the reaction is small.

  The temperature in the step (ii) is preferably 10 to 100 ° C, more preferably 10 to 80 ° C, and particularly preferably 15 to 70 ° C. The reaction time is preferably 0.3 to 48 hours, more preferably 0.5 to 24 hours, and particularly preferably 1 to 12 hours.

  The amount of the basic compound used in the above step (ii) is usually 0.01 to 50 parts by weight, preferably 0. 0 parts by weight with respect to 100 parts by weight as the total of the siloxane compound (A) and the alkoxysilane compound (B). 1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight.

  When the step (ii) is subsequently performed after the step (i), the specific compound used in the step (i) may be used as it is, or the same or different specific compound is newly added. You may do it.

Examples of the organic solvent used in the step (ii) include the organic solvents mentioned in the step (i).
From the viewpoint of the storage stability of the silanol group epoxy group-containing polysiloxane obtained above, it is preferable to perform water washing as a despecification compound step after step (ii). In particular, when a basic compound is used as the specific compound, it is more preferable to perform water washing after neutralization with an acidic compound after the reaction.

  Examples of the acidic compound used for neutralization include organic acids and inorganic acids. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, methylmalonic acid, adipic acid, Sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfone Examples include acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, methanesulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

  The amount of the acidic compound used is usually 0.5 to 2 N, preferably 0.8 to 1.5 N, more preferably 0.9 to 1 N of the basic compound used in the dealcoholization reaction and hydrolysis reaction. 1.3. The acidic compound is preferably a water-soluble acidic compound from the viewpoint that it can be easily extracted into the aqueous layer at the time of washing with water. When used by dissolving in water, the acidic compound is usually added in an amount of 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of water.

After neutralization, the mixture is sufficiently stirred and allowed to stand, and after confirming phase separation between the aqueous phase and the organic solvent phase, the lower layer moisture is removed.
The water used for the water washing after neutralization is usually 10 to 500 parts by weight, preferably 20 to 300 parts, more preferably 100 parts by weight in total of the siloxane compound (A) and the alkoxysilane compound (B). 30 to 200 parts.

Washing with water is performed by adding water and stirring sufficiently, and then allowing to stand, and after confirming phase separation between the aqueous phase and the organic solvent phase, removing the lower layer moisture. The number of washings is preferably 1 or more times, more preferably 2 or more times.
Moreover, you may extract with an organic solvent for the purpose of the removal of an impurity after water washing. As the organic solvent necessary for extraction, the above organic solvents can be used. The kind of organic solvent and its compounding quantity can be selected suitably.

Epoxy Curing Agent The epoxy curing agent is a substance that cures the organopolysiloxane.
Examples of the epoxy curing agent (B) include acid anhydrides, amine compounds, and mercapto compounds. Of these, acid anhydrides are particularly preferred.

[Acid anhydride]
Although it does not specifically limit as an acid anhydride, An alicyclic carboxylic acid anhydride is preferable.
Examples of the alicyclic carboxylic acid anhydride include compounds represented by the following formulas (11) to (21).

や、４−メチルテトラヒドロフタル酸無水物、メチルナジック酸無水物、ドデセニルコハク酸無水物のほか、α−テルピネン、アロオシメン等の共役二重結合を有する脂環式化合物と無水マレイン酸とのディールス・アルダー反応生成物やこれらの水素添加物等を挙げることができる。なお、前記ディールス・アルダー反応生成物やこれらの水素添加物としては、任意の構造異性体および任意の幾何異性体を使用することができる。

And Diels-Alder of maleic anhydride and alicyclic compounds having conjugated double bonds such as α-terpinene and alloocimene in addition to 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, dodecenyl succinic anhydride Reaction products and hydrogenated products thereof can be exemplified. In addition, arbitrary structural isomers and arbitrary geometric isomers can be used as the Diels-Alder reaction product and hydrogenated products thereof.

In addition, the alicyclic carboxylic acid anhydride can be used after being appropriately chemically modified as long as the curing reaction is not substantially hindered.
Among these alicyclic carboxylic acid anhydrides, from the viewpoint of fluidity and transparency of the composition, the formula (11), the formula (13), the formula (15), the formula (16), the formula (17) or the formula A compound represented by (21) is preferred. Particularly preferred are compounds represented by formula (11), formula (13), formula (16) or formula (21).

In this invention, an alicyclic carboxylic acid anhydride can be used individually or in mixture of 2 or more types.
In addition, one or more aliphatic acid anhydrides or aromatic acid anhydrides can be used as the acid anhydride. These are preferably used in combination with an alicyclic acid anhydride.

The aliphatic acid anhydride and aromatic acid anhydride can also be used after being appropriately chemically modified as long as they do not substantially interfere with the curing reaction.
The total use ratio of the aliphatic acid anhydride and the aromatic acid anhydride is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount with the alicyclic acid anhydride.

  When an acid anhydride is used as a curing agent for epoxy, the amount used is 0.2 to 1.7, preferably 0.3 as an equivalent ratio of acid anhydride groups to 1 mol of epoxy groups in the organopolysiloxane. To 1.5, more preferably 0.5 to 1.3, and most preferably 0.6 to 0.8. In this case, even if the corresponding amount ratio is less than 0.2 or exceeds 1.7, there is a possibility that inconveniences such as a decrease in the glass transition point (Tg) and coloring of the obtained cured product may occur.

Curing accelerator The curable composition according to the present invention may contain a curing accelerator. The curing accelerator is a component that accelerates the curing reaction between the organopolysiloxane and the epoxy curing agent.

Such a curing accelerator is not particularly limited, but for example,
Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine; special amines such as UCAT410 (San Apro Corporation);
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s- Imidazoles such as isocyanuric acid adducts of triazines;
Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;
Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide , Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetraphenylphosphonium tetraphenylborate, triphenylbenzylphosphonium tetraphenylborate, tetra-n-butylphosphonium tetrafluoroborate Quaternary phosphonium salt;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Tetraethylammonium bromide, tetra-n-butylammonium bromide, UCAT18X (San Apro Co., Ltd.) or the following formula (22)

の如き４級アンモニウム塩；
三フッ化ホウ素、ホウ酸トリフェニルの如きホウ素化合物；塩化亜鉛、塩化第二錫の如き金属ハロゲン化合物、
ジシアンジアミドやアミンとエポキシ樹脂との付加物等のアミン付加型促進剤等の高融点分散型潜在性硬化促進剤；前記イミダゾール類、有機リン化合物や４級フォスフォニウム塩等の硬化促進剤の表面をポリマーで被覆したマイクロカプセル型潜在性硬化促進剤；アミン塩型潜在性硬化剤促進剤；ルイス酸塩、ブレンステッド酸塩等の高温解離型の熱カチオン重合型潜在性硬化促進剤等の潜在性硬化促進剤
等を挙げることができる。

A quaternary ammonium salt such as
Boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannic chloride,
High melting point dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide and adducts of amine and epoxy resin; surfaces of curing accelerators such as imidazoles, organophosphorus compounds and quaternary phosphonium salts Microcapsule-type latent curing accelerator coated with polymer; amine salt-type latent curing accelerator; high-temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt and Bronsted acid salt Can be mentioned.

  Among these curing accelerators, imidazoles, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, and quaternary ammonium salts are colorless and transparent, and cured products that are difficult to discolor even when heated for a long time are obtained. This is preferable.

The said hardening accelerator can be used individually or in mixture of 2 or more types.
In the curable composition according to the present invention, the content of the curing accelerator is 0.005 to 6 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0 to 100 parts by mass of the organopolysiloxane. 0.05 to 4 parts by mass. When the content of the curing accelerator is less than 0.005 parts by mass, the effect of promoting the curing reaction tends to be reduced. On the other hand, when the content exceeds 6 parts by mass, the obtained cured product may be disadvantageous such as coloring. is there.

Other components The curable composition of the present invention further includes inorganic particles such as silica particles, epoxy group-containing polysiloxanes other than the organopolysiloxane as adhesion assistants, or oxetane compounds, thiol compounds, and compounds having an isocyanuric ring structure. , Alkoxysilane or a hydrolyzate or condensate thereof may be contained. Moreover, the curable composition of this invention can contain fluorescent substance further, and the hardening body of the curable composition containing fluorescent substance can be used as LED sealing material.

[Inorganic particles]
When the curable composition of the present invention contains silica particles as inorganic particles, it is preferable in that the strength of the cured product is improved.

  When silica particles are blended as inorganic particles, they can also be used in the form of powder or a solvent-based sol or colloid dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. In the case of a solvent-based sol or colloid, the solvent may be distilled off after compounding. In order to improve the dispersibility of the silica particles, surface-treated silica particles may be used.

The primary particle diameter of these silica particles is usually 0.0001 to 1 μm, more preferably 0.001 to 0.5 μm, and particularly preferably 0.002 to 0.2 μm.
In the case of a silica particle solvent-based sol or colloid, the solid content concentration usually exceeds 0% by mass and is 50% by mass or less, preferably 0.01% by mass or more and 40% by mass or less.

  In the present invention, as surface-treated untreated powdered silica, OX50, # 50, # 150, # 200, # 300 manufactured by Nippon Aerosil Co., Ltd., and R972 manufactured by Nippon Aerosil Co., Ltd. as hydrophobized powdered silica. R974, R976, RX50, RX200, RX300, RY50, RY200S, RY300, R106, SS50A and SS30V manufactured by Tosoh Corporation, Silo Hovic 100 and Silo Hovic 200 manufactured by Fuji Silysia Chemical Ltd., and the like.

  Examples of the solvent-dispersed colloidal silica include alcohol-based solvent-dispersed colloidal silica such as isopropyl alcohol manufactured by Nissan Chemical Industries, ketone-based solvent-dispersed colloidal silica such as methylisobutyl, and nonpolar solvent-dispersed colloidal silica such as toluene. It is done. Silica particles may be added during the preparation of the curable composition, or may be added after the preparation of the curable composition.

  The amount of the inorganic particles used is usually more than 0% by mass and 80% by mass or less, preferably 5% by mass or more and 50% by mass or less in terms of solid content with respect to the organopolysiloxane.

[Adhesion aid]
The curable composition of the present invention can also contain the following substances as adhesion assistants.
Examples of the epoxy group-containing polysiloxane other than the organopolysiloxane include an epoxy group-containing alkoxysilane represented by the above formula (1) and the following formula (III):

（式（III）中、Ｒ⁵およびＲ⁶はそれぞれ独立に非置換または置換の１価の炭化水素基を示し、ｐは０〜２の整数である）
で表されるアルコキシシランとの加水分解縮合物や、シラノール基を含有しないエポキシ基含有ポリジメチルシロキサンなどが挙げられる。

(In Formula (III), R ⁵ and R ⁶ each independently represents an unsubstituted or substituted monovalent hydrocarbon group, and p is an integer of 0 to 2)
And hydrolyzed condensates with alkoxysilanes, and epoxy group-containing polydimethylsiloxanes that do not contain silanol groups.

Specific examples of the alkoxysilane represented by the above formula (III) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane. Tetraalkoxysilanes (p = 0 in formula (III));
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxy Silane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3 Trialkoxysilanes such as (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane (p = 1 in formula (III)); dimethyldimethoxysilane, dimethyldiethoxysilane Diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxy Silane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n- Heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. Alkoxysilanes (p = 2 in formula (III));
Is mentioned.

  Examples of the oxetane compound include compounds represented by the following formulas (O-1) to (O-10).

チオール化合物としては、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルトリ−ｎ−プロポキシシラン、３−メルカプトプロピルトリ−ｉ−プロポキシシラン、３−メルカプトプロピルトリ−ｎ−ブトキシシラン、３−メルカプトプロピルトリ−ｓｅｃ−ブトキシシランなどが挙げられる。

Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, and 3-mercaptopropyltri-n. -Butoxysilane, 3-mercaptopropyltri-sec-butoxysilane and the like.

  Examples of the compound having an isocyanuric ring structure include isocyanuric acid tris (3-trimethoxysilyl-n-propyl), isocyanuric acid tris (2-hydroxyethyl), isocyanuric acid triglycidyl, isocyanuric acid tris (2-carboxyethyl) and the like. Can be mentioned.

  Moreover, as alkoxysilane, its hydrolyzate, or its condensate, the alkoxysilane represented by Formula (III) mentioned above, its hydrolyzate, or its condensate is mentioned. Examples of the condensate of formula (III) include a single condensate of alkoxysilane exemplified above and a condensate of two or more alkoxysilanes, such as tetramethoxysilane oligomer, tetraethoxysilane oligomer, methyltrimethoxysilane oligomer, methyltrimethoxysilane. Examples include condensates of methoxysilane and dimethyldimethoxysilane. When using a condensate of alkoxysilane, it is preferable that Mw is 3000 or less from the viewpoint of compatibility with polysiloxane (A).

  These silica particles, epoxy group-containing polysiloxanes other than the organopolysiloxane, oxetane compounds, thiol compounds, compounds having an isocyanuric ring structure, alkoxysilanes and hydrolysates or condensates thereof are synthesized from the organopolysiloxanes. Sometimes it may be added, or it may be added when forming a cured product. In order to improve the compatibility with the organopolysiloxane, it is more preferable to add at the time of synthesis.

[Operation of the curable composition according to the present invention]
When using organopolysiloxane, an MQ polymer with silanol groups and epoxy groups, in addition to the formation of a dense polymer skeleton derived from tetrafunctional components, crosslinking reactions between epoxy groups and acid anhydrides, and condensation reactions between silanol groups occur. . As a result, the thermal shock resistance is improved by reducing the thermal stress during temperature change due to a decrease in the linear expansion coefficient of the polymer and improving the strength of the polymer itself. Further, since no transition metal catalyst or the like is used in the synthesis, a polymer excellent in light resistance can be obtained.

<Light emitting element>
The light emitting element according to the present invention is obtained by sealing an optical semiconductor using the optical semiconductor sealing composition. When sealing an optical semiconductor using the composition, the composition can be cured by a known method. For example, after apply | coating this composition, it hardens | cures by heating at 100-180 degreeC for 3 to 13 hours, and can form a hardening body. Curing may be performed in a process of stepwise temperature rise (step cure). Examples of the light emitting element include an LED (Light Emitting Diode) and an LD (Laser Diode).

  1 and 2 are schematic diagrams of LEDs. In FIG. 1 and FIG. 2, a light emitting element portion 50 that is an optical semiconductor is sealed with a sealing material 51. In FIG. 1, the light emitting element portion 50 is sealed with a sealing material 51 in which a phosphor 54 is dispersed. The light emitting element part 50 may have the fluorescent part 52 containing the binder 53 and the fluorescent substance 54 like FIG. The sealing material 51 in the LED shown in FIG. 1 and FIG. 2 can be formed with the composition for optical semiconductor sealing according to the present invention.

  Moreover, a light-emitting device can be obtained by sealing and curing a light-emitting element such as an LED element with the composition for encapsulating an optical semiconductor. As the LED element, a blue LED element, an ultraviolet LED element, or the like can be used. Furthermore, the fluorescent substance can be contained in the cured body, and the light emitted from the LED element can be converted.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples and comparative examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified.
Various measurements in Examples and Comparative Examples were performed by the following methods.

(1) GPC measurement The weight average molecular weight of the silanol group epoxy group-containing polysiloxane was measured by gel permeation chromatography under the following conditions, and was shown as a polystyrene equivalent value.
Apparatus: HLC-8120C (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore H _XL- M (manufactured by Tosoh Corporation)
Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL
(2) Epoxy equivalent Based on JIS C2105, the epoxy equivalent of silanol group epoxy group containing polysiloxane was measured.

(3) Silanol equivalent The silanol equivalent in the resulting silanol group epoxy group-containing polysiloxane was determined by the following method.
100 g of silanol group epoxy group-containing polysiloxane to be measured was weighed. 49.2 g of 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane, 10% by weight of diazabicycloundecene was added, and the mixture was stirred at 50 ° C. The consumption of 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane was monitored by gas chromatography, and the reaction was terminated when the consumption ceased. When 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane is completely consumed at the end of the reaction, the silanol equivalent is 500 g / eq. Hereinafter, when complete consumption of 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane was not observed, the silanol equivalent was determined to be greater than 500 g / eq.

(4) Identification method of monofunctional siloxane unit / bifunctional siloxane unit / trifunctional siloxane unit / tetrafunctional siloxane unit in silanol group epoxy group-containing polysiloxane In the obtained silanol group epoxy group-containing polysiloxane The ratio of monofunctional siloxane unit / bifunctional siloxane unit / trifunctional siloxane unit / tetrafunctional siloxane unit, that is, monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon ratio was determined by the following method. .
A solution in which 100 parts by weight of deuterated chloroform was added to 100 parts by weight of the composition was prepared, and 29Si-NMR was measured. The integrated values of a peak around 10 to 0 ppm, a peak around -10 to -30 ppm, a peak between -40 to -70 ppm, and a peak between -80 to -120 ppm of the obtained chart were obtained. From these integrated values, (monofunctional silicon) / (bifunctional silicon) / (trifunctional silicon) / (tetrafunctional silicon) = (peak integrated value near 10 to 0 ppm) / (peak integrated value of −10 to −30 ppm) ) / (Peak integration value from -40 to -70 ppm) / (peak integration value from -80 to -120 ppm).

(5) Linear expansion coefficient The obtained composition was put into a petri dish so that the film thickness was 1 mm, dried and cured at 100 ° C for 1 hour, and then dried and cured at 150 ° C for 5 hours to prepare a cured product. The cured product was measured for linear expansion coefficient at −50 ° C. to 300 ° C. using a heat / stress / strain measuring apparatus (manufactured by SII Nanotechnology Co., Ltd .: TMA / SS6100).

(6) Hardness The obtained composition was placed in a petri dish so that the film thickness was 1 mm, dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 5 hours to produce a cured product. The hardness of this cured product was measured by a type A durometer and a type D durometer according to JIS K6253.

(7) Heat resistance After the obtained composition was applied on quartz glass so that the dry film thickness was 1 mm, it was dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 5 hours to obtain a cured product. Produced. This cured body was stored at 150 ° C. for 500 hours, and the appearance of the cured body after storage was visually observed and evaluated according to the following criteria.
(Color change)
A: No change B: Slight discoloration C: Yellowish

(8) Light resistance After applying the obtained composition on quartz glass so that the dry film thickness is 1 mm, it is dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 5 hours to obtain a cured product. Produced. The cured product was irradiated with ultraviolet rays having an illuminance of 5000 mW / cm ² for 500 hours using a spot UV irradiation device (USHIO Corp .: SP-VII) in which light having a wavelength of 350 nm or less was cut. The appearance of the cured product after ultraviolet irradiation was visually observed and evaluated according to the following criteria.
A: No change B: Yellowed C: Black burnt

(9) Peeling resistance during moisture absorption and reflow The obtained composition is poured into an LED package (surface mount type, top view type), dried and cured at 100 ° C. for 1 hour, and then dried and cured at 150 ° C. for 5 hours. Thus, a cured body sample was prepared. The obtained sample was stored for 5 hours at 85 ° C. and 85% RH in a constant temperature and humidity chamber (PL-3KP manufactured by ESPEC), and then MAX260 using a desktop solder reflow device (STR-2010 manufactured by Senju Metal Industry Co., Ltd.). The reflow process at 10 ° C. for 10 seconds was performed twice. Separation between the cured product in the package after reflow treatment and the package resin was observed with an optical microscope. Ten samples were carried out for each sample.
Peel resistance and crack resistance were evaluated according to the following criteria.
(Peeling resistance)
AA: No peeling even after 8 hours storage A: No peeling after 5 hours storage, peeling after 8 hours storage B: 1 to 2 peeling after 5 hours storage C: peeling after 5 hours storage 3 or more occurrences

(10) Thermal shock resistance evaluation method The obtained composition is applied in a surface mount type (top view) package, and a sample for evaluation is prepared by heating at 100 ° C for 1 hour and then at 150 ° C for 3 hours. Went.
The above-mentioned sample for evaluation was cooled in a thermal shock test apparatus (TOM17 manufactured by ESPEC) at a rate of 1 ° C./min, from -40 ° C. to 100 ° C. and from 100 ° C. to −40 ° C. as one cycle. The impact test was performed 1000 cycles. After completion of the test, peeling between the package and the resin and cracks inside the resin were visually observed using an optical microscope. The same test was conducted 10 times per sample, and evaluation was performed according to the following criteria.
(Peeling)
A: No peeling
B: Peeling occurred between the package and the resin 1 to 4 times out of 10 times
C: Separation occurred between the package and the resin 1 to 5 times or more out of 10 times (crack)
A: No cracking
B: Cracks occurred inside the resin 1 to 4 times out of 10 times
C: Cracks occurred in the resin from 1 to 5 times out of 10 times

[Synthesis example of silanol group epoxy group-containing polysiloxane]
(Synthesis of siloxane compound (A1) obtained by hydrolytic condensation of monofunctional silicon compound and tetrafunctional silicon compound)
In a reactor equipped with a stirrer, water 22.6 parts, 37% hydrochloric acid aqueous solution 15.1 parts, ethanol 11.3 parts, hexamethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96L-0) .65cs) 21.5 parts was added and stirred at room temperature. To this solution, 78.5 parts of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-04) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solution was heated to 75 ° C. and then stirred at 75 ° C. for 1 hour. After completion of the stirring, the upper aqueous layer was removed from the cooled solution, and after adding 150 parts of toluene, the solution was transferred to a separatory funnel and washed with water until the aqueous layer became neutral. By concentrating the obtained organic layer, a siloxane compound (A1) obtained by hydrolytic condensation of a monofunctional silicon compound and a tetrafunctional silicon compound was obtained as a 70 wt% toluene solution.

(Synthesis of siloxane compound (A2) obtained by hydrolytic condensation of monofunctional silicon compound and tetrafunctional silicon compound)
In a reactor equipped with a stirrer, water 22.6 parts, 37% hydrochloric acid aqueous solution 15.1 parts, ethanol 11.3 parts, hexamethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96L-0) .65cs) 21.5 parts was added and stirred at room temperature. To this solution, 11.0 parts of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-04) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solution was heated to 75 ° C. and then stirred at 75 ° C. for 1 hour. After completion of the stirring, the upper aqueous layer was removed from the cooled solution, and after adding 150 parts of toluene, the solution was transferred to a separatory funnel and washed with water until the aqueous layer became neutral. By concentrating the obtained organic layer, a siloxane compound (A2) obtained by hydrolytic condensation of a monofunctional silicon compound and a tetrafunctional silicon compound was obtained as a 70 wt% toluene solution.

(Synthesis of siloxane compound (A3) obtained by hydrolytic condensation of monofunctional silicon compound and tetrafunctional silicon compound)
In a reactor equipped with a stirrer, water 22.6 parts, 37% hydrochloric acid aqueous solution 15.1 parts, ethanol 11.3 parts, hexamethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96L-0) .65cs) 21.5 parts was added and stirred at room temperature. To this solution, 276 parts of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-04) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solution was heated to 75 ° C. and then stirred at 75 ° C. for 1 hour. After completion of the stirring, the upper aqueous layer was removed from the cooled solution, and after adding 150 parts of toluene, the solution was transferred to a separatory funnel and washed with water until the aqueous layer became neutral. By concentrating the obtained organic layer, a siloxane compound (A3) obtained by hydrolytic condensation of a monofunctional silicon compound and a tetrafunctional silicon compound was obtained as a 70 wt% toluene solution.

(Synthesis of a siloxane compound (A4) obtained by hydrolytic condensation of a monofunctional silicon compound and a tetrafunctional silicon compound)
In a reactor equipped with a stirrer, water 22.6 parts, 37% hydrochloric acid aqueous solution 15.1 parts, ethanol 11.3 parts, hexamethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96L-0) .65cs) 21.5 parts was added and stirred at room temperature. To this solution, 5.5 parts of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-04) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solution was heated to 75 ° C. and then stirred at 75 ° C. for 1 hour. After completion of the stirring, the upper aqueous layer was removed from the cooled solution, and after adding 150 parts of toluene, the solution was transferred to a separatory funnel and washed with water until the aqueous layer became neutral. By concentrating the obtained organic layer, a siloxane compound (A4) obtained by hydrolytic condensation of a monofunctional silicon compound and a tetrafunctional silicon compound was obtained as a 70 wt% toluene solution.

(Synthesis Example 1: Synthesis of Silanol Group Epoxy Group-Containing Polysiloxane (B1))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A1) obtained by hydrolysis and condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethyltri 84.4 parts of methoxysilane and 15.7 parts of diazabicycloundecene were added as a catalyst and stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B1) having Mw = 2500. It was 440 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B1) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was the following. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 32/0/26/42.

(Synthesis Example 2: Synthesis of silanol group epoxy group-containing polysiloxane (B2))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A1) obtained by hydrolysis and condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethyltri 30 parts of methoxysilane and 15.7 parts of diazabicycloundecene as a catalyst were added and stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B2) having Mw = 3000. It was 860 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B2) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was the following. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 36/0/10/54.

(Synthesis Example 3: Synthesis of epoxy group-containing siloxane compound (B3))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A1) obtained by hydrolysis and condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethyltri 500 parts of methoxysilane and 15.7 parts of diazabicycloundecene as a catalyst were added and stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B3) having Mw = 2000. It was 280 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B3) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was the following. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 15/0/65/20.

(Synthesis Example 4: Synthesis of Epoxy Group-Containing Siloxane Compound (B4))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A2) obtained by hydrolytic condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethyltri 102 parts of methoxysilane and 15.7 parts of diazabicycloundecene as a catalyst were added and stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B4) having Mw = 3000. It was 420 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B4) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was the following. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 58/0/30/12.

(Synthesis Example 5: Synthesis of epoxy group-containing siloxane compound (B5))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A3) obtained by hydrolytic condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethyltri 124 parts of methoxysilane and 15.7 parts of diazabicycloundecene as a catalyst were added and stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B5) having Mw = 3500. It was 390 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B5) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was the following. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 12/0/30/58.

(Synthesis Example 6: Synthesis of epoxy group-containing siloxane compound (B6))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A4) obtained by hydrolytic condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethyltri 100 parts of methoxysilane and 15.7 parts of diazabicycloundecene as a catalyst were added and stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B6) having Mw = 3500. It was 430 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B6) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was the following. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 64/0/30/6.

(Synthesis Example 7: Synthesis of Silanol Group Epoxy Group-Containing Polysiloxane (B7))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A1) obtained by hydrolytic condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyl 84.0 parts of dimethoxysilane and 15.7 parts of diazabicycloundecene were added as a catalyst and stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this water washing operation 3 times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B7) having Mw = 2400. It was 440 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B7) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was the following. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 32/26/0/42.

(Synthesis Example 8: Synthesis of epoxy group-containing siloxane compound (B8))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A1) obtained by hydrolysis and condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethyltri After adding 8.3 parts of methoxysilane and 15.7 parts of diazabicycloundecene as a catalyst, the mixture was stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B8) having Mw = 3000. It was 2500 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B8) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was bigger. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 42/0/3/55.

(Synthesis Example 9: Synthesis of Epoxy Group-Containing Siloxane Compound (B9))
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of siloxane compound (A1) obtained by hydrolysis and condensation of the above monofunctional silicon compound and tetrafunctional silicon compound and 2- (3 ′, 4′-epoxycyclohexyl) ethyltri 2430 parts of methoxysilane and 15.7 parts of diazabicycloundecene were added as a catalyst, and the mixture was stirred at 50 ° C. for 24 hours. To this reaction product, 300 parts of methyl isobutyl ketone, 100 parts of methanol and 100 parts of water were added and subjected to a hydrolysis reaction at 25 ° C. for 1 hour, followed by addition of 189 parts of a 6% aqueous oxalic acid solution at room temperature for 1 hour. A sum reaction was performed. Thereafter, the aqueous layer was separated and the organic phase was washed with 100 parts of water. After performing this water washing operation 3 times, the solvent was distilled off to obtain a silanol group epoxy group-containing polysiloxane (B9) having Mw = 3000. It was 240 when the epoxy equivalent of this silanol group epoxy group containing polysiloxane (B9) was evaluated by the said method. When the silanol equivalent was evaluated, it was 500 g / eq. It was the following. The ratio of silicon atoms was monofunctional silicon / bifunctional silicon / trifunctional silicon / tetrafunctional silicon = 4/0/90/6.

(Synthesis Example 10: Synthesis of Epoxy Group-Containing Siloxane Compound (C1) Synthesized Using Platinum Catalyst Hydrosilylation)
(Synthesis of a siloxane compound having a hydrogen atom bonded to a silicon atom obtained by hydrolytic condensation of a monofunctional silicon compound and a tetrafunctional silicon compound)
In a reactor equipped with a stirrer, 24.0 parts of water, 16.0 parts of 37% aqueous hydrochloric acid, 12.0 parts of ethanol, 1,1,3,3, -tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) And 23.9 parts of reagent name: LS-7040) and stirred at room temperature. To this solution, 76.1 parts of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-04) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solution was stirred at room temperature for 3 hours. After the stirring, the upper aqueous layer was removed, 150 parts of toluene was added, and the mixture was transferred to a separatory funnel and washed with water until the aqueous layer became neutral. By concentrating the obtained organic layer, a siloxane compound obtained by hydrolysis condensation of a monofunctional silicon compound containing a hydrogen atom bonded to a silicon atom and a tetrafunctional silicon compound was obtained as a 70 wt% toluene solution.

(Synthesis of epoxy group-containing siloxane compounds by hydrosilylation using platinum catalyst)
In a reactor equipped with a stirrer, 100 parts of a 70 wt% toluene solution of a siloxane compound having a hydrogen atom bonded to a silicon atom obtained by hydrolysis condensation of the monofunctional silicon compound and the tetrafunctional silicon compound, and 1,2-epoxy-4 -55.9 parts of vinylcyclohexane, chloroplatinic acid was added as a catalyst so that the platinum concentration was 10 ppm, and the mixture was stirred at 120 ° C for 1 hour and cooled. The solvent was distilled off from the obtained solution to obtain an epoxy group-containing siloxane compound (C1), and yellow coloring was observed in this compound.
The epoxy equivalent of this epoxy group-containing siloxane compound (C1) was 360. When the silanol equivalent was evaluated, it was 500 g / eq. It was bigger.

(Synthesis Example 11: Synthesis of epoxy group-containing siloxane compound (D1) having bifunctional silicon compound as main skeleton)
In a reactor equipped with a stirrer, 30 parts of 1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.), α-vinyldimethylsilyloxy containing 1.64 mmol of vinyl group in 1 g -Ω-vinyldimethylsilyl-polydimethylsiloxane [average degree of polymerization of dimethylsiloxane units is 14. ] 152.4 parts, 35.65 parts of 4-vinylcyclohexene oxide (manufactured by Daicel Chemical Industries, Ltd .: Celoxide 2000), and 855 parts of 1,4-dioxane (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) are charged under nitrogen. Thereafter, the temperature was raised to 60 ° C. with stirring. To this was added 1.7 parts of a 1,4-dioxane solution of a platinum divinyltetramethyldisiloxane complex containing 1,000 ppm of platinum in terms of platinum element, and the reaction was continued for 4 hours. After completion of the reaction, the temperature of the reaction solution was lowered to 30 ° C., and 300 g of activated carbon (manufactured by Wako Pure Chemicals: Granular Special Grade) heated and dried at 120 ° C. for 3 hours under a dry nitrogen stream was added to the reaction solution, After continuing the stirring treatment at a temperature of 30 ° C. to 40 ° C. for 24 hours, the activated carbon was filtered. The obtained treatment liquid was heated using an evaporator under conditions of a heating temperature of 45 ° C. and a pressure of 10 kPa for 1.5 hours, the pressure was sequentially reduced, and finally the pressure was reduced to 30 Pa. The compound having a bond was distilled off to obtain an epoxy group-containing siloxane compound (D1). The epoxy equivalent of the epoxy group-containing siloxane compound (D1) was 900, the transition metal component contained was only platinum, and the content of the component was 3 ppm in terms of platinum element. When the silanol equivalent was evaluated, it was 500 g / eq. It was bigger.

Example 1
26 parts of acid anhydride (manufactured by Nippon Nippon Chemical Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (B1) obtained in Synthesis Example 1 and U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “composition (1)”. Composition (1) was subjected to linear expansion coefficient, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, The peel / crack resistance upon impact was evaluated, and the evaluation results are shown in Table 1. In Table 1, M and Q represent a monofunctional silane compound and a tetrafunctional silane compound, respectively, and Si (1), Si (2), Si (3) and Si (4) mean monofunctional silicon, bifunctional silicon, trifunctional silicon and tetrafunctional silicon, respectively.

(Example 2)
13 parts of an acid anhydride (manufactured by Nippon Nippon Chemical Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (B2) obtained in Synthesis Example 2 above, U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator 0.07 part was added and sufficiently stirred (hereinafter referred to as “composition (2)”. Composition (2) was subjected to the above-described methods for the linear expansion coefficient, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, cold heat. The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

(Example 3)
41 parts of acid anhydride (manufactured by Nippon Kayaku Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (B3) obtained in Synthesis Example 3 above, U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “composition (3)”) About composition (3), the coefficient of linear expansion, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, cold heat The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

Example 4
27 parts of acid anhydride (manufactured by Shin Nippon Rika Co., Ltd .: MH700G) and 100 parts of epoxy group-containing siloxane compound (B4) obtained in Synthesis Example 4 above, U-CAT18X made by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “composition (4)”) About the composition (4), the coefficient of linear expansion, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, cold heat The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

(Example 5)
29 parts of acid anhydride (manufactured by Shin Nippon Rika Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (B5) obtained in Synthesis Example 5 and U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “composition (5)”) About the composition (5), the coefficient of linear expansion, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, cold heat The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

(Example 6)
27 parts of an acid anhydride (manufactured by Shin Nippon Rika Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (B6) obtained in Synthesis Example 6 above, U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “composition (6).” About composition (6), the linear expansion coefficient, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

(Comparative Example 1)
5 parts of acid anhydride (manufactured by Shin Nippon Rika Co., Ltd .: MH700G) per 100 parts of the epoxy group-containing siloxane compound (B8) obtained in Synthesis Example 8 above, and U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator 0.02 part was added and sufficiently stirred (hereinafter referred to as “composition (8)”. The composition (8) was not cured under the above conditions, and a sample for measurement could not be obtained. The linear expansion coefficient, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, and peeling / crack resistance during cold shock could not be evaluated.

(Comparative Example 2)
48 parts of an acid anhydride (manufactured by Shin Nippon Rika Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (B9) obtained in Synthesis Example 9 and U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “composition (9)”) About the composition (9), the coefficient of linear expansion, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, cold heat The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

(Comparative Example 3)
32 parts of an acid anhydride (manufactured by Shin Nippon Rika Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (C1) obtained in Synthesis Example 10 above, U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “composition (10)”) About composition (10), the coefficient of linear expansion, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, cold heat The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

(Comparative Example 4)
13 parts of acid anhydride (manufactured by Nippon Nippon Chemical Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (D1) obtained in Synthesis Example 11 above, U-CAT18X manufactured by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “Composition (11)”) About the composition (11), the coefficient of linear expansion, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, cold heat The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

(Comparative Example 5)
26 parts of an acid anhydride (manufactured by Shin Nippon Rika Co., Ltd .: MH700G) with respect to 100 parts of the epoxy group-containing siloxane compound (B7) obtained in Synthesis Example 7 above, U-CAT18X made by San Apro Co., Ltd. as a curing accelerator (Hereinafter referred to as “composition (7).” About the composition (7), the linear expansion coefficient, hardness, heat resistance, light resistance, moisture absorption / reflow resistance, The peel / crack resistance during impact was evaluated and the evaluation results are shown in Table 1.

50 light emitting element part 51 sealing material 52 fluorescent part 53 binder 54 phosphor

Claims (10)

An organopolysiloxane containing structural units represented by the following general formulas (1) to (3),
Silanol equivalent is 0 g / eq. Exceeding 500 g / eq. And
An organopolysiloxane comprising 10 to 70 mol% of a trifunctional siloxane unit when the total amount of siloxane units constituting the organopolysiloxane is 100 mol%.

[Wherein, R ¹ and R ³ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 3 carbon atoms.
R ^E represents an organic group having 3 to 20 carbon atoms having an epoxy group.
R ⁹ each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms.
a is 0 or 1 ; ]   The monofunctional siloxane unit is contained in an amount of 20 to 80 mol% and the tetrafunctional siloxane unit is contained in an amount of 10 to 60 mol% when the total amount of siloxane units constituting the organopolysiloxane is 100 mol%. Item 3. The organopolysiloxane according to Item 1. 3. The organopolysiloxane according to claim 1, wherein R ^{E of the} formula (1) is represented by any one of the following general formulas (7) to (10).

[R ^{5 in} General Formula (7) represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]

[In General Formula (8), R ⁶ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]

[In the general formula (9), R ⁷ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. ]

[In General Formula (10), R ⁸ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms. ]   A curable composition comprising the organopolysiloxane according to claim 1 and an epoxy curing agent.   The curable composition according to claim 4, wherein the epoxy curing agent is an acid anhydride.   The composition for optical semiconductor sealing which consists of a curable composition of Claim 4 or 5.   The light emitting element using the composition for optical semiconductor sealing of Claim 6. A basic compound comprising a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), a siloxane compound (A) containing a silanol group and an alkoxysilane compound (B) having an epoxy group The method for producing an organopolysiloxane according to claim 1, further comprising a step of reacting in the presence of.

[In formula (2), R ¹ is the same as R ¹ in formula (2) according to claim 1. ] The siloxane compound (A) is
It is selected from the group consisting of a silane compound (A-1) represented by the following formula (4), a silane compound represented by the following formula (5), a condensate of the silane compound, and a hydrolyzate of the silane compound. The method for producing an organopolysiloxane according to claim 8, wherein the organopolysiloxane is obtained by reacting at least one (A-2).

[In formula (4), R ¹ is the same as R ¹ in formula (2) according to claim 8. ]

[In formula (5), R ² represents an unsubstituted or substituted monovalent hydrocarbon group. ] The method for producing an organopolysiloxane according to claim 8 or 9, wherein the alkoxysilane compound (B) is a compound represented by the following formula (6).

[Formula (6) was R ^E, R ³ and a are, R ^E in each formula (1) is the same as R ³ and a. R ⁴ each independently represents an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms. ]

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