JP5943104B2 - Curable composition, cured film, polysiloxane, and optical semiconductor device - Google Patents

Description

  The present invention relates to a curable composition, a cured film, polysiloxane, and an optical semiconductor device.

  Hydrosilylation reaction-curable polysiloxane compositions (hereinafter also referred to as hydrosilyl-based polysiloxane compositions) used in semiconductor light emitting device (LED) encapsulants and the like increase adhesion to LED packages and the like. Technology is required.

  As a technique for improving the adhesion of the hydrosilyl polysiloxane composition, a technique of adding an adhesion promoter such as an epoxy group-containing polysiloxane to the hydrosilyl polysiloxane composition is known.

  Patent Document 1 discloses a hydrosilyl polysiloxane composition containing 0.01 to 50 parts by weight of an epoxy group-containing polysiloxane having an alkenyl group, which is an adhesion promoter, with respect to 100 parts by weight of an organopolysiloxane as a main agent. Have been described.

  In Patent Document 2, an epoxy group-containing polysiloxane as an adhesion promoter is contained in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of an organopolysiloxane resin containing alkenyl groups and phenyl groups as main components. A polysiloxane composition is described.

  Patent Document 3 discloses a hydrosilyl system containing 0.01 to 10 parts by mass of an epoxy group-containing polysiloxane having an alkenyl group, which is an adhesion promoter, with respect to 100 parts by mass of an organopolysiloxane component containing an alkenyl group as a main component. A polysiloxane composition is described.

JP 2007-327019 A JP 2007-008996 A JP 2010-229402 A

  A cured product formed from a conventional hydrosilyl polysiloxane composition has a problem of insufficient adhesion to an LED substrate or a wiring metal made of gallium nitride (GaN), silicon nitride (SiN), or the like. For this reason, epoxy group-containing polysiloxanes have been used to improve the adhesion.

  In the synthesis of an epoxy group-containing polysiloxane, a base is usually used for the reaction of introducing an epoxy group into the polysiloxane. However, there is a possibility that the polysiloxane may be altered by the base during the reaction, and there is a problem that the cured product obtained from the cured composition containing the altered polysiloxane is colored.

  An object of this invention is to provide the curable composition which can form hardened | cured material with high adhesiveness with LED board | substrates, such as a gallium nitride and silicon nitride, a wiring metal, etc., and without coloring.

The present invention for achieving the above object is as follows.
[1] At least one group selected from a group having a structure represented by the following formula (1) and a group having a structure represented by the following formula (2) (hereinafter also referred to as “adhesive group (A)”) A curable composition comprising polysiloxane (A) having a crosslinking agent (B).

（（１）式中、Ｘは、脂環式炭化水素基を表わす。（１）中、−［ＣＨ₂］−ＯＨおよび−ＯＨは、前記脂環式炭化水素基を構成する異なる炭素原子に結合し、該２つの炭素原子は単結合で結合され、前記２つの炭素原子にはそれぞれ水素原子が結合している。ｎは０〜６の整数を示す。＊は結合手を示す。）

(In the formula (1), X represents an alicyclic hydrocarbon group. In (1), — [CH ₂ ] —OH and —OH represent different carbon atoms constituting the alicyclic hydrocarbon group. The two carbon atoms are bonded by a single bond, and a hydrogen atom is bonded to each of the two carbon atoms, n represents an integer of 0 to 6, and * represents a bond.)

（（２）式中、Ｒ¹は炭素数１〜８のアルキル基または水素原子を示す。ｍは０〜６の整数を示す。＊は結合手を示す。）

(In the formula (2), R ¹ represents an alkyl group having 1 to 8 carbon atoms or a hydrogen atom. M represents an integer of 0 to 6. * represents a bond.)

[2] The curable composition according to [1], wherein the polysiloxane (A) has a group having a structure represented by the formula (1).
[3] The curable composition according to [1] or [2], wherein the polysiloxane (A) is a polysiloxane (A1) having at least two alkenyl groups in one molecule.
[4] The above-mentioned [3], wherein the crosslinking agent (B) is a compound (B1) having at least two silicon-bonded hydrogen atoms in one molecule, and further contains a hydrosilylation catalyst (C). The curable composition according to 1.
[5] When the content ratio of all Si atoms contained in the polysiloxane (A) is 100 mol%, the polysiloxane (A) has a group having the structure represented by the formula (1) and a structure represented by the formula (2). The curable composition according to any one of [1] to [4], wherein the content of at least one group selected from the group is 0.1 to 10 mol%.

[6] A polysiloxane having at least one group selected from a group having the structure represented by the formula (1) and a group having a structure represented by the formula (2) and an alkenyl group.
[7] A polysiloxane having a group having the structure represented by the formula (1) and an alkenyl group.
[8] A cured product obtained by curing the curable composition according to any one of [1] to [5].
[9] An optical semiconductor device comprising: a semiconductor light emitting element; and the cured product according to [8], which covers the semiconductor light emitting element.

  Since the curable composition of the present invention has high adhesion to LED substrates and wiring metals such as gallium nitride and silicon nitride, and can form a cured product having no color, LED such as gallium nitride and silicon nitride It can be suitably used as a sealant for an LED having a substrate.

FIG. 1 is a schematic diagram showing a specific example of an optical semiconductor device. FIG. 2 is a ¹ H NMR spectrum of polysiloxane (A-1) obtained in Example 1.

<Curable composition>
The curable composition of the present invention includes a polysiloxane (A) having at least one group selected from a group having a structure represented by the following formula (1) and a group having a structure represented by the following formula (2), and a crosslink It contains an agent (B).

（（１）式中、Ｘは、脂環式炭化水素基を表わす。（１）中、−［ＣＨ₂］−ＯＨおよび−ＯＨは、前記脂環式炭化水素基を構成する異なる炭素原子に結合し、該２つの炭素原子は単結合で結合され、前記２つの炭素原子にはそれぞれ水素原子が結合している。ｎは０〜６の整数を示す。＊は結合手を示す。）

(In the formula (1), X represents an alicyclic hydrocarbon group. In (1), — [CH ₂ ] —OH and —OH represent different carbon atoms constituting the alicyclic hydrocarbon group. The two carbon atoms are bonded by a single bond, and a hydrogen atom is bonded to each of the two carbon atoms, n represents an integer of 0 to 6, and * represents a bond.)

（（２）式中、Ｒ¹は炭素数１〜８のアルキル基または水素原子を示す。ｍは０〜６の整数を示す。＊は結合手を示す。）
なお、本発明において「ポリシロキサン」とは、シロキサン単位 (Ｓｉ−Ｏ)が２個以上結合した分子骨格を有するシロキサンを意味する。

(In the formula (2), R ¹ represents an alkyl group having 1 to 8 carbon atoms or a hydrogen atom. M represents an integer of 0 to 6. * represents a bond.)
In the present invention, “polysiloxane” means a siloxane having a molecular skeleton in which two or more siloxane units (Si—O) are bonded.

Polysiloxane (A)
The polysiloxane (A) is a polysiloxane having at least one group selected from a group having a structure represented by the above formula (1) and a group having a structure represented by the above formula (2). Polysiloxane (A) is the main component of the present composition, and is crosslinked and cured by the action of the crosslinking agent (B) to become the main component of the cured product.

In the above formula (1), X represents an alicyclic hydrocarbon group. (1) in the - [CH _2] -OH and -OH, said cycloaliphatically bound different carbon atoms constituting the hydrocarbon group, the two carbon atoms are bonded by a single bond, the two carbon A hydrogen atom is bonded to each atom. Polysiloxane (A) can also be represented, for example, by the following formula (3).

（３）式において、点線および単結合を示す実線とこれらによって結ばれる３つの炭素原子とで表わされる環状部分は脂環式炭化水素基を表わし、Ｚは、該脂環式炭化水素基を前記３つの炭素原子とともに形成する、前記脂環式炭化水素基を完成するのに必要な個数の炭素原子を示す。ｎは０〜６の整数を示す。＊は結合手を示す。

In the formula (3), a cyclic portion represented by a dotted line and a solid line showing a single bond and three carbon atoms connected by these represents an alicyclic hydrocarbon group, and Z represents the alicyclic hydrocarbon group as described above. The number of carbon atoms necessary to complete the alicyclic hydrocarbon group formed with three carbon atoms is shown. n shows the integer of 0-6. * Indicates a bond.

The number of carbon atoms constituting the alicyclic hydrocarbon group is usually 3 to 30, preferably 4 to 20, and more preferably 4 to 10.
For example, when the number of carbons constituting the alicyclic hydrocarbon group is 6, the above formulas (1) and (3) can be represented by the following formula (4).

（４）式において、ｎは０〜６の整数を示す。

In the formula (4), n represents an integer of 0-6.

The alicyclic hydrocarbon group may have a carbon-carbon unsaturated bond.
A chain hydrocarbon group or the like may be bonded to carbon constituting the alicyclic hydrocarbon group.
In the formulas (1) and (3), n represents an integer of 0 to 6, preferably 0.
In the formula (2), R ¹ is an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, preferably a hydrogen atom or an alkyl group having 1 carbon atom (methyl group). In the formula (2), m represents an integer of 0 to 6, and is preferably 0.

  The group having the structure represented by the above formula (1) and the group having the structure represented by the formula (2) may be directly bonded to the silicon atom constituting the polysiloxane chain in the polysiloxane (A) molecule. In addition, it may be bonded to the silicon atom via a linking group such as a hydrocarbon group such as a methylene group or an alkylene group or an oxycarbonyl group.

  The polysiloxane (A) has at least one group selected from a group having a structure represented by the formula (1) and a group having a structure represented by the formula (2), and thus has a diol group. In the cured product obtained from the present curable composition, the diol group of the polysiloxane (A) functions as an adhesive group, and has an adhesive property with an LED substrate such as gallium nitride or silicon nitride, a wiring metal, or the like. It is thought to improve. The adhesive group means a group having adhesiveness to a metal or an organic resin that is a material of a substrate such as a semiconductor device.

  The polysiloxane (A) may have only a group having the structure represented by the formula (1), or may have only a group having the structure represented by the formula (2). You may have both groups. The polysiloxane (A) preferably has a group having a structure represented by the formula (1). When the polysiloxane (A) has a group having the structure represented by the formula (1), the obtained cured film has an effect of having high adhesiveness with an LED substrate such as gallium nitride or silicon nitride, a wiring metal, or the like. .

  In polysiloxane (A), the content of at least one group selected from the group having the structure represented by formula (1) and the group having the structure represented by formula (2) is included in polysiloxane (A). When the content ratio of all Si atoms is 100 mol%, it is preferably 0.1 to 10 mol%, more preferably 0.5 to 8 mol%, and 1 to 5 mol%. Is more preferable. When the content ratio of at least one group selected from the group having the structure represented by the formula (1) and the group having the structure represented by the formula (2) is within the above range, the resulting cured film may be formed of gallium nitride or There is an effect of having high adhesiveness with LED substrates such as silicon nitride and wiring metals.

  The polysiloxane (A) may have other groups besides the adhesive group (A). Other groups include hydrogen atom; silanol group; polar group such as halogen atom, nitro group, carboxyl group, carbonyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, Groups having an alkenyl group such as heptenyl, hexenyl and cyclohexenyl; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl Group, cyclooctyl group, bornyl group, norbornyl group, adamantyl group and other alkyl groups; phenyl group, tolyl group, xylyl group, naphthyl group and other aryl groups; benzyl group, phenethyl group and other aralkyl groups; cyclic ether group, thionyl Group, isocyanate group and triallyl Groups having and the polar group and bonding group; other adhesive base such as a cyanate group and the like.

  The polysiloxane (A) is preferably a polysiloxane (A1) having at least two alkenyl groups in one molecule. When the polysiloxane (A) has at least two alkenyl groups, a hydrosilylation reaction with a cross-linking agent (B1) having at least two silicon atom-bonded hydrogen atoms in one molecule, which will be described later, becomes possible, and the curing is strong. A thing is obtained.

The above-mentioned group is mentioned as an alkenyl group which polysiloxane (A) has. Among these, a vinyl group, an allyl group, and a hexenyl group are preferable.
The alkenyl group content in the polysiloxane (A) is preferably 3 to 50 mol%, more preferably 5 when the number of all Si atoms contained in the polysiloxane (A) is 100 mol%. It is -40 mol%, More preferably, it is 10-30 mol%. When the content of the alkenyl group is within the above range, the hydrosilylation reaction between the polysiloxane (A) and the crosslinking agent (B1) having at least two silicon-bonded hydrogen atoms occurs in a suitable range, and the cured product has high strength. Is obtained.

  Polysiloxane (A) preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 100 to 50000, and more preferably in the range of 500 to 5000. When the weight average molecular weight of the polysiloxane (A) is within the above range, it is easy to handle when producing a sealing material using the composition, and the cured product obtained from the composition is used as an optical semiconductor sealing material. Has sufficient material strength and properties.

[Production Method of Polysiloxane (A)]
The polysiloxane (A) having the adhesive group (A) can be produced by opening a cyclic ether group. Examples of the method for opening the cyclic ether group include a method of treating the cyclic ether group with a strong acid in the presence of water. For example, a polysiloxane having a cyclic ether group is treated with a strong acid in the presence of water (Method 1), or a chlorosilane or an alkoxysilane having a cyclic ether group serving as each unit source when synthesizing a polysiloxane is obtained. It can be produced by treating with a strong acid in the presence of water (Method 2). Among these, Method 2: A method in which a chlorosilane or alkoxysilane having a cyclic ether group serving as a unit source in the synthesis of polysiloxane is treated with a strong acid in the presence of water is included in polysiloxane. It is preferable because the content ratio of the contained adhesive group (A) can be easily controlled.

  Examples of the cyclic ether group include an epoxy group (ethylene oxide group), a trimethylene oxide group (oxetane group), and a tetramethylene oxide group (tetrahydrofuran group). When the cyclic ether group is an epoxy group, a polysiloxane (A) having a group having a structure of m = 0 in the above formula (2) can be produced. When the cyclic ether group is a trimethylene oxide group, the polysiloxane (A) having a group having a structure of m = 1 in the above formula (2) can be produced. When the cyclic ether group is a tetramethylene oxide group, the polysiloxane (A) having a group having a structure of m = 2 in the above formula (2) can be produced.

  The cyclic ether group includes, for example, a ring containing two carbon atoms adjacent to each other constituting an alicyclic hydrocarbon group and an oxygen atom bonded to at least one of the two carbon atoms. And a group containing an atomic group constituted by: Examples of such a cyclic ether group include a group represented by the following formula (5) (epoxycyclohexyl group), a group represented by the following formula (6), and a group represented by the following formula (7). it can.

  When the cyclic ether group is a group represented by the formula (5), a polysiloxane (A) having a group having a structure of n = 0 in the above formula (3) can be produced. When the cyclic ether group is a group represented by the formula (6), a polysiloxane (A) having a group having a structure of n = 1 in the above formula (3) can be produced. When the cyclic ether group is a group represented by the formula (5), a polysiloxane (A) having a group having a structure of n = 2 in the formula (3) can be produced.

  Polysiloxane (A) can be produced by combining one or more known methods. Examples of the known methods include JP-A-6-9659, JP-A-2003-183582, JP-A-2007-008996, JP-A-2007-106798, JP-A-2007-169427, and JP-A-2010. The methods described in JP-A-059359 and the like, for example, a method of cohydrolyzing chlorosilane and alkoxysilane serving as each unit source, a method of equilibrating the cohydrolyzed product with an alkali metal catalyst, and the like.

  Examples of the unit chlorosilane and alkoxysilane include the following. Examples of the unit source having a cyclic ether group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) di Ethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (Ethyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) Til] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycidoxypropyl) ) (Methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy ) Dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3,4- Epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, 2- (3,4-epoxycyclohexane) Epoxy group-containing alkoxysilanes such as xyl) propyltrimethoxysilane; γ-glycidoxypropyltrichlorosilane, (γ-glycidoxypropyl) (methyl) dichlorosilane, 2- (3,4-epoxycyclohexyl) propyltrichlorosilane Such as epoxy group-containing chlorosilanes; oxetanyl group-containing alkoxysilanes such as 3-oxetanylpropyltrimethoxysilane; oxetanyl group-containing chlorosilanes such as 3-oxetanylpropyltrichlorosilane; Among these, since reaction control is easy and coloring of the cured film obtained is suppressed, an epoxy group-containing alkoxysilane is preferable, and an alicyclic such as 2- (3,4-epoxycyclohexyl) propyltrimethoxysilane. An epoxy group-containing alkoxysilane having a hydrocarbon group is more preferred.

  As the unit source having an alkenyl group, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclo Tetrasiloxane, alkenyl siloxane in which a part of methyl groups of these alkenyl siloxanes are substituted with groups such as ethyl group, phenyl group, alkenyl siloxane in which vinyl groups of these alkenyl siloxanes are substituted with groups such as allyl group, hexenyl group, etc. Is mentioned.

  Other unit sources include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, trimethoxy Silane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, JP2007-106798A, and JP2009-24077A Examples thereof include unit sources described in Japanese Patent Laid-Open No. 2009-215377.

  For example, in the case of the method 1, a unit source having a cyclic ether group is used as an essential component, a polysiloxane having a cyclic ether group is synthesized using a base catalyst or the like, and then a cyclic ether group is obtained using a strong acid and water. Polysiloxane (A) can be produced by opening the ring. Moreover, in the case of the said method 2, polysiloxane (A) can be manufactured by making it react using a strong acid and water, using the unit source which has a cyclic ether group as an essential component.

  In order to produce the polysiloxane (A1) having at least two alkenyl groups in one molecule, the polysiloxane can be prepared by the above-described method using a unit source having a cyclic ether group and a unit source having an alkenyl group as essential components. What is necessary is just to manufacture (A1). Examples of the strong acid used for opening the cyclic ether group include trifluoromethanesulfonic acid, sulfuric acid, nitric acid, sulfuric anhydride, and trifluoroacetic acid. In addition, acidic clay such as activated clay obtained by heat treatment of acidic clay containing montmorillonite as a main component with sulfuric acid or hydrochloric acid can be used.

The amount of the strong acid used is appropriately determined depending on the amount of the cyclic ether group, and is usually 0.01 to 20 g per 1 mol of the cyclic ether group.
The amount of water added when treating with a strong acid is appropriately determined depending on the amount of cyclic ether groups, and is usually 1 g to 150 g per mole of cyclic ether groups.

The temperature at the time of processing with a strong acid is 23 to 100 degreeC normally.
The treatment time when treating with a strong acid is usually 0.2 hours to 5 hours.
After completion of the reaction, excess water can be removed from the reaction solution by azeotropic dehydration or the like, or the reaction solution can be neutralized with potassium hydroxide or the like.

Cross-linking agent (B)
The crosslinking agent (B) is a crosslinking agent for the polysiloxane (A), and forms a cured product by a crosslinking reaction with the polysiloxane (A).
As a crosslinking agent (B), the crosslinking agent normally used for a polysiloxane composition can be mentioned. For example, when the polysiloxane (A) is a polysiloxane having an alkenyl group, a crosslinking agent that acts on the alkenyl group as a crosslinking agent: a compound having Si—H (hydrosilyl group), or Japanese Patent Application Laid-Open No. 2005-112925. A polyfunctional monomer having a plurality of the acrylic groups described can be used. Further, when the polysiloxane (A) is a polysiloxane having an epoxy group, as a crosslinking agent, acid anhydrides described in WO05 / 100445, amine compounds, mercapto compounds, phenols, dicyandiamides, adipic acid hydrazide, Organic hydrazides such as phthalic hydrazide can be used.

  Among these, the crosslinking agent (B) is preferably a compound (B1) having at least two silicon-bonded hydrogen atoms per molecule, that is, at least two Si—H groups (hydrosilyl groups) per molecule. When the crosslinking agent (B) has at least two silicon-bonded hydrogen atoms, a crosslink by hydrosilylation reaction may be formed with the polysiloxane (A1) having at least two alkenyl groups in one molecule. And a cured product having high strength can be obtained.

  Examples of the compound (B1) include polysiloxanes having at least two silicon atom-bonded hydrogen atoms per molecule, which are used as crosslinking agents in conventional hydrosilyl polysiloxane compositions.

Specific examples of the compound (B1) include organohydrogenpolysiloxanes described in Patent Documents 1 to 3.
Compound (B1) is obtained, for example, by reacting an alkoxysilane such as phenyltrimethoxysilane or diphenyldimethoxysilane with a hydrogensiloxane such as 1,1,3,3-tetramethyldisiloxane by a known method. be able to.

As content of the crosslinking agent (B) in the curable composition of this invention, 1-300 mass parts is normally used with respect to 100 mass parts of polysiloxane (A).
When the crosslinking agent (B) is the compound (B1), the content of the compound (B1) in the curable composition of the present invention is silicon in the compound (B1) relative to the alkenyl group amount in the polysiloxane (A). It is preferable that the molar ratio of the atomic bond hydrogen atom amount is 0.1 to 5, more preferably 0.5 to 2, and still more preferably 0.7 to 1.4. When the content of the compound (B1) is within the above range, the composition is sufficiently cured, and sufficient heat resistance is obtained for the obtained cured product.

Catalyst for hydrosilylation reaction (C)
The catalyst for hydrosilylation reaction (C) is a catalyst for hydrosilylation reaction between a polysiloxane (A1) having at least two alkenyl groups in one molecule and a compound (B1) having a hydrosilyl group.

  The hydrosilylation reaction catalyst (C) can be used without any particular limitation as long as it is a catalyst used as a hydrosilylation reaction catalyst in a conventional hydrosilyl polysiloxane composition.

  Specific examples of the hydrosilylation catalyst (C) include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Among these, a platinum-based catalyst is preferable from the viewpoint of promoting the curing of the present composition. Examples of the platinum-based catalyst include a platinum-alkenylsiloxane complex. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Etc. In particular, from the viewpoint of the stability of the complex, 1,3-divinyl-1,1,3,3-toteramethyldisiloxane is preferable.

The hydrosilylation reaction catalyst (C) in the curable composition of the present invention is used in such an amount that the hydrosilylation reaction of the polysiloxane (A) and the polysiloxane (B) can actually proceed.
As long as the object of the present invention is achieved, the curable composition of the present invention includes, in addition to the above components, as necessary, for example, polysiloxanes other than polysiloxane (A), fumed silica, quartz powder, etc. Inorganic fillers such as fine particle silica, titanium oxide and zinc oxide, retarders such as cyclo-tetramethyltetravinyltetrasiloxane, diluents such as diphenylbis (dimethylvinylsiloxy) silane, phenyltris (dimethylvinylsiloxy) silane, A pigment, a flame retardant, a heat-resistant agent, an antioxidant and the like can be contained.

The curable composition of this invention can be prepared by mixing each said component uniformly by well-known methods, such as a mixer.
The viscosity at 25 ° of the curable composition of the present invention is preferably 1 to 1000000 mPa · s, more preferably 10 to 10000 mPa · s. When the viscosity is within this range, the operability of the composition is improved.

  The curable composition of the present invention can be prepared as one liquid, or can be prepared by dividing into two liquids, and the two liquids can be mixed and used at the time of use. If necessary, a small amount of a curing inhibitor such as acetylene alcohol may be added.

<Hardened product>
A cured product is obtained by curing the curable composition of the present invention. If a semiconductor element is sealed with the curable composition of the present invention and cured, a cured product as a sealing material is obtained.
Examples of the method for curing the curable composition of the present invention include a method in which the curable composition is applied on a substrate and then heated at 100 to 180 ° C. for 1 to 13 hours. In addition, you may perform manufacture of the said cured film in the process (step cure) which heats up in steps.

  As described above, the cured product obtained by curing the curable composition of the present invention is a cured film that has high adhesion to LED substrates such as gallium nitride and silicon nitride, metal wiring, and the like, and is not colored.

<Optical semiconductor device>
The optical semiconductor device of the present invention includes a semiconductor light emitting element and the cured product that covers the semiconductor light emitting element. The optical semiconductor device of the present invention is obtained by coating a semiconductor light emitting element with the curable composition and curing the composition. The method for curing the curable composition is as described above.

Examples of the optical semiconductor device include an LED (Light Emitting Diode) and an LD (Laser Diode).
FIG. 1 is a schematic view of a specific example of the optical semiconductor device of the present invention. The optical semiconductor device 1 includes an electrode 6, a semiconductor light emitting element 2 that is installed on the electrode 6 and electrically connected to the electrode 6 through a wire 7, and a reflector 3 that is disposed so as to accommodate the semiconductor light emitting element 2. The sealing material 4 is filled in the reflector 3 and seals the semiconductor light emitting element 2. The sealing material 4 is obtained by curing the curable composition of the present invention. In the sealing material 4, particles 5 such as silica and phosphor are dispersed.

(1) Synthesis of polysiloxane
(1-1) Synthesis of polysiloxane
Example 1 Synthesis of Polysiloxane (A-1) 20 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added to a four-necked flask equipped with a stirrer, reflux condenser, inlet, and thermometer. 120 g of phenyltrimethoxysilane, 6 g of 2- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 15 g of water, 0.1 g of trifluoromethanesulfonic acid and 500 g of toluene were mixed and heated to reflux for 1 hour. After cooling, 2.5 g of a 0.5 wt% potassium hydroxide aqueous solution was added to the reaction solution, and the mixture was heated to reflux for 4 hours, and then excess water was removed by azeotropic dehydration. After cooling, the reaction solution was neutralized with acetic acid and washed with water. Polysiloxane (A-1) was obtained by removing the solvent from the reaction solution.

^From the results of ¹ H NMR measurement, it was confirmed that polysiloxane (A-1) had a group represented by the following formula (8). ^{The 1} H NMR spectrum is shown in FIG.
^{From 1} H NMR measurement, the polysiloxane (A-1) contains 3 mol% of the group represented by the following formula (8) when the total Si atoms contained in the polysiloxane (A-1) is 100 mol%. It was confirmed that
When the weight average molecular weight of resiloxane (A-1) was measured by gel permeation chromatography, it was 2000 in terms of polystyrene.

（式（８）中、「＊」は結合手を示す）

(In formula (8), “*” represents a bond)

[Synthesis Example 1] Synthesis of polysiloxane (D-1) A stirrer, a reflux condenser, an inlet, and a four-neck flask with a thermometer, 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 525 g of phenyltrimethoxysilane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, and the mixture was heated to reflux for 1 hour. After cooling, the lower layer of the reaction solution was separated and removed, and the upper toluene solution layer was washed with water. To the toluene solution layer washed with water, 0.4 g of potassium hydroxide was added and refluxed while removing water from the water separation tube. After the removal of water was completed, the solution was concentrated until the solid concentration became 75% by mass, and further refluxed for 5 hours. After cooling, 0.6 g of acetic acid was added to neutralize, and the toluene solution layer was washed with water. Then, it concentrated under reduced pressure and obtained polysiloxane (D-1).
It was 2000 when the polystyrene conversion weight average molecular weight of polysiloxane (D-1) was measured by the gel permeation chromatography.

[Synthesis Example 2] Synthesis of polysiloxane (B-1) 195 g of phenyltrimethoxysilane and 0.2 g of trifluoromethanesulfonic acid were added to and mixed with a stirrer, a reflux condenser, an inlet, and a four-neck flask with a thermometer, While stirring, 13 g of water was added dropwise over 15 minutes, and after completion of the addition, the mixture was heated to reflux for 1 hour. After cooling the reaction solution to room temperature, 119 g of 1,1,3,3-tetramethyldisiloxane was added, and 88 g of acetic acid was added dropwise while stirring. After completion of dropping, the reaction solution was heated to 50 ° C. while stirring and reacted for 3 hours. After cooling the reaction solution to room temperature, toluene and water were added, mixed well and allowed to stand, and the aqueous layer was separated and removed. The upper toluene solution layer was washed with water and then concentrated under reduced pressure to obtain polysiloxane (B-1).
It was 330 when the polystyrene conversion weight average molecular weight of polysiloxane (B-1) was measured by the gel permeation chromatography.

(2) Preparation of curable composition [Example 2, Example 3 and Comparative Example 1]
The components shown in Table 1 below were mixed in the blending amounts shown in Table 1 to obtain curable compositions of Example 2, Example 3, and Comparative Example 1. “Parts” in Table 1 indicates parts by mass. The details of each component in Table 1 are as follows.

Ｃ−１：白金と１，３−ジビニル−１，１，３，３−テトラメチルジシロキサンとの錯体(白金金属量４質量％)
Ｄ−２：フェニルトリス（ジメチルビニルシロキシ）シラン

C-1: Complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum metal amount 4% by mass)
D-2: Phenyltris (dimethylvinylsiloxy) silane

(3) Evaluation of curable composition About the curable composition of Example 2, Example 3, and the comparative example 1, it evaluated by the method of the following (3-1)-(3-3). The evaluation results are shown in Table 1.

(3-1) A 2 mm thick frame is applied to a Teflon (registered trademark) flat plate with a hardness- curable composition, applied to the height of the frame, and heated in a hot air circulation oven at 150 ° C. for 5 hours. Thus, a cured product of 50 mm × 50 mm × 1 mm was produced. The hardness of the cured product was measured with a type D durometer defined in JIS K6253.

(3-2) A curable composition was applied onto a SiN substrate having an adhesive force of 4 inches by spin coating, and heated at 170 ° C. for 120 minutes to form a cured film having a thickness of 100 μm. The adhesive strength of the cured film was measured by a pull-down breaking point test (a tensile tester manufactured by Quad Group).

(3-3) Transparency A curable composition was applied onto a 4-inch SiN substrate by spin coating, and heated at 170 ° C. for 120 minutes to form a cured film having a thickness of 100 μm. The cured film heated at 150 ° C. for 2000 hours was measured for spectral transmittance at a wavelength of 400 to 700 nm with an ultraviolet-visible spectrophotometer. Regarding the transparency of the cured film, the spectral transmittance is “A” (good) when the spectral transmittance is 90% or more, “B” (slightly good) when the spectral transmittance is 70% or more and less than 90%, and the spectral transmittance is The case of less than 70% was evaluated as “C” (defective).

Claims (2)

A polysiloxane having a group and the alkenyl group having the structure shown below following formula (1), when the content ratio of the total Si atoms contained in the polysiloxane (A) and 100 mol%, wherein (1 ) Is a polysiloxane having a group content of 0.1 to 10 mol%.

(In the formula (1), X represents an alicyclic hydrocarbon group. In (1), — [CH ₂ ] _n —OH and —OH represent different carbon atoms constituting the alicyclic hydrocarbon group. And the two carbon atoms are bonded by a single bond, and each of the two carbon atoms has a hydrogen atom bonded thereto, n represents an integer of 0 to 6, and * represents a bond.) Wherein when 100 mol% of the content of the total Si atoms contained in the polysiloxane (A), a polysiloxane according to claim 1, wherein the content ratio of the alkenyl group is 3 to 50 mol%.

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