JP2011252070A - Deairing method of volatile matter contained in compound having reactive functional group, and curable composition for optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deairing method of a curing composition for an optical material, in which a volatile matter contained in a compound having a reactive functional group is removed to thereby control poor molding by a void, a crack or the like.SOLUTION: The deairing method of a volatile matter contained in a curing composition includes a step which introduces a gas and deairs a mixture obtained by independent one or combinations of each of: a compound (A) having at least two carbon-carbon double bond parts having reactivity with an SiH group in one molecule; a compound (B) having at least two SiH groups in one molecule; and a hydrosilylation catalyst (C) at 0-100°C, thereby controls polymerization and/or crosslinking of the compound containing a reactive functional group, and removes a volatile matter in the mixture for a short time. The curing composition for an optical material has very high transparency.

Description

The present invention relates to a method for devolatilizing a compound having at least one reactive double bond in one molecule, and a carbon-carbon double bond site having reactivity with a SiH group obtained by the devolatilization method. The present invention relates to a curable composition for optical materials using a compound having at least two per molecule, an optical material, and a method for producing the same.

  Conventionally, a curable composition comprising a compound having a carbon-carbon double bond, a compound having a SiH group, and a hydrosilylation catalyst has been proposed. For example, the present applicant has proposed a curable composition of a compound having triallyl isocyanurate and SiH group in Japanese Patent Application Laid-Open No. 2003-73551, and the volatile component contained in the composition is a void or crack at the time of molding. There is room for improvement because it causes molding defects.

  In order to solve these problems, it is conceivable that each component of the curable composition is devolatilized at a high temperature and under reduced pressure. However, when a high temperature is applied to a compound having a reactive double bond, the polymerization reaction proceeds. However, the color tone and haze of the blended composition may be deteriorated. Moreover, the low-pressure devolatilization at low temperature has a problem that not only the productivity is inferior because devolatilization takes a long time, but also volatile components cannot be completely removed. In addition, the proposal which prevents the gelatinization of resin by performing radical polymerization of acrylic resin in molecular oxygen presence is made (patent document 2). However, no technical description has been made regarding devolatilization.

JP 2003-73551 A JP-A-9-48821

The object of the present invention is to introduce a gas under reduced pressure and devolatilize so that polymerization of the volatile component contained in the compound having at least one reactive double bond in one molecule does not occur. The effective removal at temperature. Further, among compounds obtained by the devolatilization method of the present invention, a compound having at least two reactive double bonds in one molecule is used to suppress molding defects such as voids and cracks during molding. It is to provide a curable composition for optical materials.

（式中、それぞれのＲ^８、Ｒ^９は、水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^８、Ｒ^９は異なっていても同一であってもよいが、１分子中に少なくとも２個のアルケニル基を有し、ｎは１〜１０００の数である。）で表される鎖状ポリオルガノシロキサンであることを特徴とする上記１１）または２２）に記載の硬化性組成物。
２４）一般式（I）に記載の（Ａ）成分が、２５℃における粘度が０．００１〜１００Ｐａ・ｓの鎖状ポリオルガノシロキサンであることを特徴とする上記１１）、２２）または２３）に記載の硬化性組成物。
２５）一般式（I）に記載の（Ａ）成分が、２５℃における粘度が０．００１〜１０Ｐａ・ｓの鎖状ポリオルガノシロキサンであることを特徴とする上記１１）、２２）、２３）または２４）に記載の硬化性組成物。
２６）（Ａ）成分が、１，３−ジビニルテトラメチルジシロキサン、１，３−ジビニルテトラフェニルジシロキサン、１，３−ジビニル−１，３−ジフェニル−１，３−ジメチルジシロキサン、１，３−ジビニル−テトラエトキシジシロキサン、ジビニルテトラキス(トリメチルシロキシ)ジシロキサン、１，３−ジビニル−１，３−ジメチル−１，３−ジクロロジシロキサン、１，１，３，３−テトラビニルジメチルジシロキサン１，３−ジアリルテトラキス（トリメチルシロキシ）ジシロキサン、ヘキサビニルジシロキサン、１，３−ジアリルテトラメチルジシロキサン、１，５−ジビニル−ヘキサメチルトリシロキサン、１，５−ジビニル−３−フェニル−ペンタメチルトリシロキサン、１，５−ジビニル−３，３−ジフェニル−１，１，５，５−テトラメチルトリシロキサン、１,３,５−トリビニル−１，１，３，５，５−ペンタメチルトリシロキサン、トリス(ビニルジメチルシロキシ)メチルシラン、トリス(ビニルジメチルシロキシ)フェニルシランおよびテトラキス(ビニルジメチルシロキシ)シランからなる群より選択されるものであることを特徴とする上記１１）、２２）、２３）、２４）または２５）に記載の硬化性組成物。
２７）（Ａ）成分が、下記一般式（II）

（式中、Ｒ^１０は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１０は異なっていても同一であってもよいが、少なくとも２個はアルケニル基であり、ｎは３〜１０の数である。）で表される環状ポリオルガノシロキサンであることを特徴とする上記１１）または２０）に記載の硬化性組成物。
２８）一般式（II）に記載の（Ａ）成分が、２５℃における粘度が０．００１〜１００Ｐａ・ｓの環状ポリオルガノシロキサンであることを特徴とする上記１１）、２２）または２７）に記載の硬化性組成物。
２９）一般式（II）に記載の（Ａ）成分が、２５℃における粘度が０．００１〜１０Ｐａ・ｓの環状ポリオルガノシロキサンであることを特徴とする上記１１）、２２）、２７）または２８）に記載の硬化性組成物。
３０）（Ａ）成分が、１，３，５，７−テトラビニル−１，３，５，７−テトラメチルシクロテトラシロキサン、１−メチル−３，５，７−トリビニル−１，３，５，７−テトラメチルシクロテトラシロキサンおよび１，５−ジビニル−３，７−ジメチル−１，３，５，７−テトラメチルシクロテトラシロキサンからなる群より選択されるものであることを特徴とする上記１１）、２２）、２７）、２８）または２９）に記載の硬化性組成物。
３１）（Ａ）成分が、下記一般式（III）〜（VI）

（式中、Ｒ^１１は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１１は異なっていても同一であってもよい。）で表される分岐状及び／又は三次元網目状ポリオルガノシロキサンであり１分子中少なくとも２個のアルケニル基を有する化合物であることを特徴とする上記１１）または２２）に記載の硬化性組成物。
３２）一般式（III）〜（VI）に記載の（Ａ）成分が、２５℃における粘度が０．００１〜１００Ｐａ・ｓの分岐状及び／又は三次元網目状ポリオルガノシロキサンであることを特徴とする上記１１、２２または３１に記載の硬化性組成物。
３３）一般式（III）〜（VI）に記載の（Ａ）成分が、２５℃における粘度が０．００１〜１０Ｐａ・ｓの分岐状及び／又は三次元網目状ポリオルガノシロキサンであることを特徴とする上記１１）、２２）、３１）または３２）に記載の硬化性組成物。
３４）（Ｂ）成分が、下記一般式（VII）

（式中、それぞれのＲ^１２、Ｒ^１３は、水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１２、Ｒ^１３は異なっていても同一であってもよいが、一分子中少なくとも２個のＳｉＨ基を有し、ｎは１〜１０００の数である。）で表される鎖状ポリオルガノシロキサンであることを特徴とする上記１１）に記載の硬化性組成物。
３５）一般式（VII）に記載の（Ｂ）成分が、２５℃における粘度が０．００１〜１００Ｐａ・ｓの鎖状ポリオルガノシロキサンであることを特徴とする上記１１）または３４）に記載の硬化性組成物。
３６）一般式（XIV）に記載の（Ｂ）成分が、２５℃における粘度が０．００１〜１０Ｐａ・ｓの鎖状ポリオルガノシロキサンであることを特徴とする上記１１）、３４）または３５）に記載の硬化性組成物。
３７）（Ｂ）成分が、１，１，３，３−テトラメチルジシロキサン、１，１，３，３−テトライソプロピルジシロキサン、１，３−ビス（トリメチルシロキシ）−１，３−ジメチルジシロキサン、１，３−ジフェニルテトラキス(ジメチルシロキシ)ジシロキサン、１，１，３，３，５，５−ヘキサメチルトリシロキサン、１，１，１，５，５，５−ヘキサメチルトリシロキサン、３−フェニル−１，１，３，５，５−ペンタメチルトリシロキサン、１，１，３，３，５，５，７，７−オクタメチルテトラシロキサン、トリフルオロプロピルトリス(ジメチルシロキシ)シラン、メチルトリス(ジメチルシロキシ)シラン、フェニルトリス(ジメチルシロキシ)シラン、ビニルトリス(ジメチルシロキシ)シランおよびテトラキス(ジメチルシロキシ)シランからなる群より選択されるものであることを特徴とする上記１１）、３４）、３５）または３６）に記載の硬化性組成物。
３８）（Ｂ）成分が、下記一般式（VIII）

（式中、Ｒ^１４は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１４は異なっていても同一であってもよいが、一分子中少なくとも２個のＳｉＨ基を有し、ｎは３〜１０の数である。）で表される環状ポリオルガノシロキサンであることを特徴とする上記１１）に記載の硬化性組成物。
３９）一般式（VIII）に記載の（Ｂ）成分が、２５℃における粘度が０．００１〜１００Ｐａ・ｓの環状ポリオルガノシロキサンであることを特徴とする上記１１）または３８）に記載の硬化性組成物。
４０）一般式（VIII）に記載の（Ｂ）成分が、２５℃における粘度が０．００１〜１０Ｐａ・ｓの環状ポリオルガノシロキサンであることを特徴とする上記１１）、３８）または３９）に記載の硬化性組成物。
４１）（Ｂ）成分が、１，３，５−トリメチルシクロトリシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサンまたは１，３，５，７，９−ペンタメチルシクロペンタシロキサンであることを特徴とする上記１１）、３８）、３９）または４０）に記載の硬化性組成物。
４２）（Ｂ）成分が、下記一般式（IX）〜（XII）

（式中、Ｒ^１５は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１５は異なっていても同一であってもよい。）で表される分岐状及び／又は三次元網目状ポリオルガノシロキサンであり１分子中少なくとも２個のＳｉＨ基を有する化合物であることを特徴とする上記１１）に記載の硬化性組成物。
４３）一般式（IX）〜（XII）に記載の（Ｂ）成分が、２５℃における粘度が０．００１〜１００Ｐａ・ｓの分岐状及び／又は三次元網目状ポリオルガノシロキサンであることを特徴とする上記１１）または４２）に記載の硬化性組成物。
４４）一般式（IX）〜（XII）に記載の（Ｂ）成分が、２５℃における粘度が０．００１〜１０Ｐａ・ｓの分岐状及び／又は三次元網目状ポリオルガノシロキサンであることを特徴とする上記１１）、４２）または４３）のいずれかに記載の硬化性組成物。
４５）（Ｂ）成分が、ＳｉＨ基と反応性を有する炭素−炭素二重結合部位を１分子中に少なくとも２個有する有機骨格部分（Ａ）と、１分子中に少なくとも２個のＳｉＨ基を有する、直鎖状、環状、分岐状または三次元網目状構造を有するポリオルガノシロキサン（Ｂ）とを、ヒドロシリル化反応して得ることができる変性体（Ｂ１）であり、１分子中に少なくとも２個のＳｉＨ基を有する化合物であることを特徴とする上記１１）に記載の硬化性組成物。
４６）（Ｂ）成分が、イソシアヌル酸誘導体と、環状ポリオルガノシロキサンとを、ヒドロシリル化反応して得ることができる変性体であり、１分子中に少なくとも２個のＳｉＨ基を有する化合物であることを特徴とする上記１１）または４５）に記載の硬化性組成物。
４７）（Ｂ）成分が、トリアリルイソシアヌレートと１，３，５，７−テトラメチルシクロテトラシロキサンの変性体、ジアリルモノグリシジルイソシアヌレートと１，３，５，７−テトラメチルシクロテトラシロキサンの変性体、モノアリルジグリシジルイソシアヌレートと１，３，５，７−テトラメチルシクロテトラシロキサンの変性体、ジビニルベンゼンと１，３，５，７−テトラメチルシクロテトラシロキサンの変性体、ビスフェノールＡジアリルエーテルと１，３，５，７−テトラメチルシクロテトラシロキサンの変性体、およびビス〔４−（２−アリルオキシ）フェニル〕スルホンと１，３，５，７−テトラメチルシクロテトラシロキサンの変性体からなる群より選択されるものであることを特徴とする上記１１）、４５）または４６）に記載の硬化性組成物。
４８）ヘーズメーターを用いて１０ｍｍの光路長のセルに硬化性組成物を入れて測定した液のヘーズが１０％以下であることを特徴とする上記１１）〜４７）のいずれかに記載の硬化性組成物。
４９）上記１１）〜４８）のいずれかに記載の硬化性組成物を硬化させてなる硬化物。
５０）上記１１）〜４９）のいずれかに記載の硬化性組成物の硬化物を使用した光学部材。
５１）上記１１）〜５０）のいずれかに記載の光学部材を使用した光学モジュール。 As a result of diligent research, the inventors of the present invention applied a compound having at least one reactive double bond in one molecule under reduced pressure conditions to air, oxygen-containing nitrogen, and an inert gas such as nitrogen, argon, helium, or neon. It was found that by introducing any of these gases and devolatilizing, the volatile component contained can be efficiently removed while preventing polymerization of the compound, and the present invention has been achieved. Details are described below.
1) A devolatilization method comprising removing a volatile component contained in a compound having at least one reactive double bond in one molecule under reduced pressure.
2) The devolatilization method according to 1) above, wherein a devolatilizer equipped with a vacuum decompressor, a stirrer, a gas blowing tube, and a heating jacket is used.
3) The devolatilization method according to 1) or 2) above, wherein a gas is introduced under reduced pressure conditions.
4) The devolatilization method according to any one of the above 1) to 3), wherein the gas introduction method is carried out by an intermittent pressurization method to the gas phase portion.
5) The devolatilization method according to any one of 1) to 3) above, wherein the gas introduction method is performed by a bubbling method to the liquid phase part.
6) The devolatilization method according to any one of 1) to 5) above, wherein the gas used for devolatilization is air or oxygen-containing nitrogen.
7) The devolatilization method according to any one of 1) to 5) above, wherein the gas used for devolatilization is an inert gas.
8) The devolatilization method according to any one of 1) to 7) above, wherein the inert gas is selected from the group consisting of nitrogen, argon, helium and neon.
9) The devolatilization method according to any one of 1) to 8) above, which is performed at 500 Torr or less.
10) The devolatilization method according to any one of 1) to 9) above, which is performed at a temperature of 0 to 100 ° C.
11) The following component (A) is a compound obtained by the devolatilization method according to any one of 1) to 10) above, and a carbon-carbon double bond site having reactivity with SiH groups A compound (A) having at least 2 per molecule, a compound (B) having at least 2 SiH groups per molecule, and a hydrosilylation catalyst (C) as essential components.
12) The curable composition as described in 11) above, wherein the component (A) is an aliphatic chain diene having 20 or less carbon atoms.
13) The component (A) is 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene and The curable composition as described in 11) or 12) above, which is selected from the group consisting of 1,9-decadiene.
14) The curable composition as described in 11) above, wherein the component (A) is an aliphatic cyclic diene having 20 or less carbon atoms.
15) The curable composition as described in 11) or 14) above, wherein the component (A) is 1,3-cyclohexadiene, 1,4-cyclohexadiene or 2,5-norbornadiene.
16) The curable composition as described in 11) above, wherein the component (A) is an alkenyl group-substituted alicyclic compound having 20 or less carbon atoms.
17) The component (A) is selected from the group consisting of 1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, 5-vinyl-2-norbornene and 4-vinylcyclohexene. The curable composition as described in 11) or 16) above.
18) The curable composition as described in 11) above, wherein the component (A) is an alkenyl group-substituted aromatic compound having 20 or less carbon atoms.
19) The component (A) is selected from the group consisting of divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, diallyl phthalate and triallyl trimellitate. The curable composition as described in 11) or 18) above, wherein
20) The curable composition as described in 11) above, wherein the component (A) is an alkenyl group-substituted isocyanurate.
21) The curable composition as described in 11) or 20) above, wherein the component (A) is triallyl isocyanurate, diallyl monoglycidyl isocyanurate or tris (2-acryloyloxyethyl) isocyanurate.
22) The (A) component is a polyorganosiloxane having at least two carbon-carbon double bond sites reactive with SiH groups in one molecule, which is linear, cyclic, branched, or three-dimensional The curable composition as described in 11) above, which has a network structure.
23) The component (A) is represented by the following general formula (I)

(In the formula, each R ⁸ and R ⁹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ⁸ and R ⁹ may be different or the same, It is a chain polyorganosiloxane having at least two alkenyl groups in one molecule, and n is a number from 1 to 1000.) Curable composition.
24) The above-mentioned 11), 22) or 23), wherein the component (A) described in the general formula (I) is a linear polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s. The curable composition according to 1.
25) The above-mentioned 11), 22), 23), wherein the component (A) described in the general formula (I) is a linear polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. Or the curable composition as described in 24).
26) The component (A) is 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 3-divinyl-tetraethoxydisiloxane, divinyltetrakis (trimethylsiloxy) disiloxane, 1,3-divinyl-1,3-dimethyl-1,3-dichlorodisiloxane, 1,1,3,3-tetravinyldimethyldi Siloxane 1,3-diallyltetrakis (trimethylsiloxy) disiloxane, hexavinyldisiloxane, 1,3-diallyltetramethyldisiloxane, 1,5-divinyl-hexamethyltrisiloxane, 1,5-divinyl-3-phenyl- Pentamethyltrisiloxane, 1,5-divinyl-3,3-diphenyl-1,1 5,5-tetramethyltrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, tris (vinyldimethylsiloxy) methylsilane, tris (vinyldimethylsiloxy) phenylsilane and tetrakis The curable composition according to 11), 22), 23), 24) or 25) above, which is selected from the group consisting of (vinyldimethylsiloxy) silane.
27) The component (A) is represented by the following general formula (II)

(Wherein R ¹⁰ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁰ may be different or the same, but at least two are alkenyl groups; n is a number of 3 to 10.) The curable composition as described in 11) or 20) above, which is a cyclic polyorganosiloxane.
28) In the above 11), 22) or 27), wherein the component (A) described in the general formula (II) is a cyclic polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s. The curable composition as described.
29) The above-mentioned 11), 22), 27) or (9), wherein the component (A) described in the general formula (II) is a cyclic polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. 28) The curable composition described in 28).
30) The component (A) is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-methyl-3,5,7-trivinyl-1,3,5 , 7-tetramethylcyclotetrasiloxane and 1,5-divinyl-3,7-dimethyl-1,3,5,7-tetramethylcyclotetrasiloxane The curable composition according to 11), 22), 27), 28) or 29).
31) The component (A) is represented by the following general formulas (III) to (VI)

(Wherein R ¹¹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹¹ may be different or the same) and / or The curable composition as described in 11) or 22) above, which is a three-dimensional network polyorganosiloxane and is a compound having at least two alkenyl groups in one molecule.
32) The component (A) described in the general formulas (III) to (VI) is a branched and / or three-dimensional network polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s. The curable composition according to the above 11, 22, or 31.
33) The component (A) described in the general formulas (III) to (VI) is a branched and / or three-dimensional network polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. The curable composition according to 11), 22), 31) or 32).
34) The component (B) is represented by the following general formula (VII)

(In the formula, each of R ¹² and R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each of R ¹² and R ¹³ may be different or the same, The curable composition as described in 11) above, which has a chain polyorganosiloxane having at least two SiH groups in one molecule, and n is a number from 1 to 1000. .
35) The component (B) described in the general formula (VII) is a linear polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s, as described in 11) or 34) above Curable composition.
36) The above-mentioned 11), 34) or 35), wherein the component (B) described in the general formula (XIV) is a linear polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. The curable composition according to 1.
37) The component (B) is 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,3-bis (trimethylsiloxy) -1,3-dimethyldi Siloxane, 1,3-diphenyltetrakis (dimethylsiloxy) disiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane, 3 -Phenyl-1,1,3,5,5-pentamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, trifluoropropyltris (dimethylsiloxy) silane, methyltris (Dimethylsiloxy) silane, phenyltris (dimethylsiloxy) silane, vinyltris (dimethylsiloxy) silane and tetrakis (dimethylsiloxy) silane Above 11), characterized in that those selected from Ranaru group, 34), 35) or 36 curable composition according to).
38) The component (B) is represented by the following general formula (VIII)

(In the formula, R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁴ may be different or the same, but at least two SiH groups in one molecule. And n is a number of 3 to 10.) The curable composition as described in 11) above, which is a cyclic polyorganosiloxane represented by the following formula.
39) The curing according to 11) or 38) above, wherein the component (B) described in the general formula (VIII) is a cyclic polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s. Sex composition.
40) In the above 11), 38) or 39), the component (B) described in the general formula (VIII) is a cyclic polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. The curable composition as described.
41) The component (B) is 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane or 1,3,5,7,9-pentamethylcyclopentasiloxane. The curable composition as described in 11), 38), 39) or 40) above.
42) The component (B) is represented by the following general formulas (IX) to (XII)

(Wherein R ¹⁵ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁵ may be different or the same) and / or 11. The curable composition as described in 11) above, which is a three-dimensional network polyorganosiloxane and is a compound having at least two SiH groups in one molecule.
43) The component (B) described in the general formulas (IX) to (XII) is a branched and / or three-dimensional network polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s. The curable composition as described in 11) or 42) above.
44) The component (B) described in the general formulas (IX) to (XII) is a branched and / or three-dimensional network polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. The curable composition according to any one of 11), 42) or 43).
45) The component (B) comprises an organic skeleton part (A) having at least two carbon-carbon double bond sites reactive with SiH groups in one molecule, and at least two SiH groups in one molecule. A modified product (B1) obtainable by hydrosilylation reaction with a polyorganosiloxane (B) having a linear, cyclic, branched or three-dimensional network structure, and having at least 2 per molecule The curable composition as described in 11) above, which is a compound having a single SiH group.
46) The component (B) is a modified product obtained by hydrosilylation reaction of an isocyanuric acid derivative and a cyclic polyorganosiloxane, and is a compound having at least two SiH groups in one molecule. The curable composition as described in 11) or 45) above, wherein
47) Component (B) is a modified form of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane. Modified product, modified product of monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, modified product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, bisphenol A diallyl From a modified product of ether and 1,3,5,7-tetramethylcyclotetrasiloxane, and a modified product of bis [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetramethylcyclotetrasiloxane 11), 45) above, characterized in that it is selected from the group consisting of The curable composition according to 46).
48) The curing according to any one of 11) to 47) above, wherein the haze of the liquid measured by putting the curable composition into a cell having an optical path length of 10 mm using a haze meter is 10% or less. Sex composition.
49) A cured product obtained by curing the curable composition according to any one of 11) to 48).
50) An optical member using a cured product of the curable composition according to any one of 11) to 49) above.
51) An optical module using the optical member according to any one of 11) to 50) above.

The hardened | cured material of this invention hardens the said hardening composition for optical materials, and is suitable for an optical member or a semiconductor module.

It has high transparency that suppresses molding defects such as voids and cracks during molding by effectively removing volatile components contained in compounds having reactive double bonds at a temperature at which polymerization of the compound does not occur. It is to provide a composition for optical materials.

The devolatilization method of the present invention can be used for compounds having at least one reactive double bond in one molecule.

  First, the compound which has at least 1 reactive double bond in 1 molecule in this invention is demonstrated. The compound having at least one reactive double bond in one molecule is not particularly limited, and various compounds can be used. Illustrative examples include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, vinylpyridine, diallylphthalate, diallylbenzenephosphonate, hexene, heptene, dimethylbutene, octadiene, decadiene. Aliphatic chain olefins such as cyclohexadiene, cyclooctadiene, norbornadiene, vinylcyclopentene, vinylcyclohexene, trivinylcyclohexane, vinylnorbornene and other alicyclic compounds, vinyl chloride, vinylidene chloride, vinyl bromide and other halogenated vinyl , Isallyurates such as triallyl isocyanurate, diallyl monoglycidyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, (meth) acrylic acid, Methyl) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid tert-butyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, Benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate , 2-aminoethyl (meth) acrylate, ethyl of (meth) acrylic acid (Meth) acrylic monomers such as oxide adducts, acetic acid, propanoic acid, crotonic acid, itaconic acid, maleic acid, phthalic acid and other (un) saturated carboxylic acid ester derivatives, styrene sulfonic acid and other unsaturated sulfonic acid esters , Unsaturated aldehydes such as (meth) acrolein, crotonaldehyde, (meth) acrylamide, N, N-dimethylacrylamide, N-isopropyl (meth) acrylamide, N-vinylformamide, N-acryloyl-N′-biotinyl- Macromonomers such as unsaturated amides such as 3,6-dioxaoctane-1,9-diamine, unsaturated nitriles such as acrylonitrile and methacrylonitrile, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate N- Heterocyclic vinyl monomers such as vinylpyrrolidone and N- (meth) acryloylmorpholine, vinyl trichloride silane, fluorinated dimethylvinylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethylsilane, vinyltriethylsilane, vinyltriphenylsilane, etc. Vinyl silane monomers, vinyl tetramethyldisiloxane, linear polyorganosiloxanes such as vinylpentamethyldisiloxane, vinyl substitution such as tetravinyltetramethylcyclotetrasiloxane, trivinylpentamethylcyclotetrasiloxane, divinylhexamethylcyclotetrasiloxane Examples include cyclic siloxanes.

  Next, the devolatilization conditions for a compound having at least one reactive double bond in one molecule will be described. In a reduced pressure state, gas such as nitrogen and air dissolved in the component is rapidly volatilized, and the gas-liquid interface is increased, so that the removal efficiency of the remaining volatile component from the component can be increased. The higher the degree of reduced pressure during devolatilization, the higher the removal rate of the remaining volatile matter, so that it is preferably 500 Torr or less, and more preferably 100 Torr or less. If it is larger than 500 Torr, it takes a long time to sufficiently remove volatile components, and therefore, polymerization of a compound having a reactive double bond may occur.

The shape of the devolatilizer is not particularly limited, but examples thereof include a stirring tank and an extruder. On the other hand, well-known stirring blades such as paddle blades, turbine blades, propeller blades, lattice blades, fiddler blades, gate blades, helical ribbon blades and anchor blades are used as the stirring blades, and one or more of these blades are used. Can also be used in combination. The blade configuration may be a single-stage blade or a multi-stage blade. As the extruder, a known extruder such as a single screw extruder or a twin screw extruder is used. The rotation speed of the stirring blade varies depending on the volume of the reaction vessel, the viscosity of the polymerization solution, the required shearing force, and the like, but is usually adjusted so that the power required for stirring is 0.20 to 20 kW / m ³ . If stirring is not sufficient, it takes a long time for devolatilization, which is not preferable. Moreover, when stirring is too intense, the compound which has a reactive double bond may superpose | polymerize by the uniform heat insulation by stirring.

  The method for introducing gas into the devolatilizer is not particularly limited, but a method of intermittently pressurizing the gas phase portion of the reaction tank and a bubbling continuously using a nozzle or the like in the liquid phase portion. The method is used. When introducing gas, the amount of gas introduced is preferably 1.0 to 300 L / h · kg. Less than 1.0 L / h · kg is not preferable because it takes a long time for devolatilization. Moreover, when more than 300 L / h * kg, it is unpreferable from an economical viewpoint. In addition, when oxygen is introduced, it is preferable to adjust the oxygen concentration so as not to enter the explosion range of the composition.

  The devolatilization temperature in the above method is preferably as high as possible for devolatilization in a short time. However, if the temperature is too high, the monomer may be polymerized, and white turbidity may be observed in the curable composition. Therefore, the temperature can be set in the range of 0 to 100 ° C. depending on the type of the monomer. A temperature lower than 0 ° C. is not preferable from an economical viewpoint.

  The total residual volatile content in the double bond compound having a reactive functional group subjected to devolatilization is preferably 1500 ppm or less, and more preferably 1000 ppm or less. If the total concentration of residual volatile components is more than 1500 ppm, molding defects such as voids and cracks may occur when processing the curable composition for optical materials.

The devolatilization of the present invention can be suitably used even under conditions where the hydrosilylation catalyst (C) is added to the compound (α) having at least one reactive double bond in one molecule.

Further, the devolatilization of the present invention can be performed by coloring a compound having at least one reactive double bond in one molecule, a co-catalyst, a storage stabilizer, an anti-aging agent, a radical inhibitor, an ultraviolet absorber, an inorganic filler, and others. Agents, mold release agents, flame retardants, flame retardant aids, surfactants, emulsifiers, leveling agents, repellent agents, ion trapping agents such as antimony-bismuth, thixotropic agents, tackifiers, storage stability improvers , Antiozonants, light stabilizers, thickeners, antifoaming agents, plasticizers, reactive diluents, antioxidants, thermal stabilizers, conductivity enhancers, antistatic agents, radiation blockers, nucleating agents , A composition containing a single or a combination of two or more selected from the group consisting of a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity-imparting agent and a physical property modifier It can also be suitably used for the devolatilization.

The curable composition for optical materials in the present invention is a compound obtained by the devolatilization method according to any one of claims 1 to 6, wherein 1 is a carbon-carbon double bond site having reactivity with SiH groups. It is a composition containing a compound (A) having at least two in the molecule, a compound (B) having at least two SiH groups in the molecule, and a hydrosilylation catalyst (C) as essential components. Hereinafter, each component (A), (B), (C) will be described in detail.

((A) component)
The component (A) is a compound composed of a skeleton portion and a carbon-carbon double bond site having reactivity with at least two SiH groups. Here, the carbon-carbon double bond site may be covalently bonded to any site of the skeleton. The skeleton portion is an organic skeleton (A1) composed of an organic polymer skeleton and / or an organic monomer skeleton, or silicon composed of a chain and / or cyclic and / or branched and / or three-dimensional network polyorganosiloxane. And a skeleton (A2).

First, the carbon-carbon double bond site having reactivity with the SiH group will be described. The carbon-carbon double bond site of the component (A) is not particularly limited as long as it has reactivity with the SiH group, but the following general formula (XIII)

（式中Ｒ^１は水素原子あるいはメチル基を表す。）で示される炭素−炭素二重結合が反応性の点から好適であり、原料の入手の容易さからは、Ｒ^１は水素原子であることがより好ましい。

A carbon-carbon double bond represented by the formula (wherein R ¹ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of reactivity, and R ¹ is a hydrogen atom from the viewpoint of availability of raw materials. It is more preferable.

In recent years, lead-free solder is often used for mounting optical components, and further heat resistance is required for optical components. Therefore, from the point of high heat resistance of the cured product, the general formula (XIV)

（式中Ｒ^２は水素原子あるいはメチル基を表し、それぞれのＲ^２は異なっていても同一であってもよい。）が好適であり、原料の入手の容易さからは、Ｒ^２は水素原子であることがより好ましい。

(Wherein R ² represents a hydrogen atom or a methyl group, and each R ² may be different or the same). From the viewpoint of availability of raw materials, R ² is a hydrogen atom. It is more preferable that

The carbon-carbon double bond site may be covalently bonded to the skeleton of the component (A) via a substituent, and the substituent is selected from C, H, N, O, S and halogen as constituent elements. That contain only atoms that are preferred. The following are mentioned as an example of a substituent.

Two or more of these substituents may be connected by a covalent bond to form a substituent.

Examples of carbon-carbon double bonds that are covalently bonded to the substituents as described above and reactive with the SiH group include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (Allyloxy) propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- Examples include (allyloxy) ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group.

Next, the skeleton part will be described. The organic skeleton (A1) is not particularly limited, and an organic polymer skeleton or an organic monomer skeleton may be used.

Examples of organic polymer backbones include polyethers, polyesters, polyarylates, polycarbonates, saturated hydrocarbons, unsaturated hydrocarbons, poly (meth) acrylates, polyamides, phenol-formaldehydes (Phenolic resins), polyimides and the like.

In particular, polyesters, polycarbonates, and poly (meth) acrylic acid esters are preferable from the viewpoint of heat resistance and transparency.

Examples of organic monomer skeletons include aliphatic chain compounds such as ethane, propane, and isobutane, aliphatic cyclic compounds such as cyclopentane, dicyclopentane, and norbornane, or epoxies, oxetanes, furans, and thiophenes. Pyrroles, oxazoles, isoxazoles, thiazoles, imidazoles, pyrazoles, furazanes, triazoles, tetrazoles, pyrans, thiines, pyridines, oxazines, thiazines, pyridazines, pyrimidines, There are heterocyclic compounds such as pyrazines, piperazines and isocyanurates. Here, the heterocyclic ring is not particularly limited as long as it is a cyclic compound having a hetero element in a cyclic skeleton. The number of atoms forming the ring is not particularly limited and may be 3 or more. From availability, it is preferable that it is 10 or less.

Specific examples of (A1) comprising an organic monomer include 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4-hexadiene, 1,6-heptadiene, 1,7-octadiene, Aliphatic chain diolefins having 20 or less carbon atoms such as 1,8-nonadiene, 1,9-decadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, norbornadiene, 5-vinyl-2-norbornene, Alkenyl group-containing alicyclic such as 4-vinylcyclohexene having 20 or less carbon atoms such as alicyclic (di) olefin, 1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, etc. Compound, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, diallyl Alkenyl group-containing aromatic compounds having 20 or less carbon atoms such as tarate and triallyl trimellitate, isocyanurate derivatives such as triallyl isocyanurate, diallyl monoglycidyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, etc. Can be mentioned.
Moreover, the compound shown below is mentioned as a suitable example.

(A) As a component, from a viewpoint that heat resistance can be improved more, what contains 0.1 mmol or more of carbon-carbon double bonds reactive with SiH group per 1 g of (A) component is preferable. Those containing 0.5 mmol or more per gram are preferred, and those containing 1 mmol or more are particularly preferred.

The number of carbon-carbon double bonds having reactivity with the SiH group of component (A) should be on average at least two per molecule, but may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it is 3 or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of component (A) is 1 or less per molecule, only a graft structure is formed even if it reacts with component (B). Because it does not become hardened.

Further, as the component (A), those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of suppressing coloring, particularly yellowing, and the phenolic hydroxyl group and / or phenolic hydroxyl group is preferable. Those not containing a compound having a derivative of In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acetoxy group, or the like.

In particular, as the component (A), the general formula (XV) described above from the viewpoint of high heat resistance and light resistance.

（式中Ｒ^３は炭素数１〜３０の一価の有機基を表し、それぞれのＲ^３は異なっていても同一であってもよいが、少なくとも二つはアルケニル基である。）で表されるイソシアヌル酸誘導体が好ましい。

(Wherein R ³ represents a monovalent organic group having 1 to 30 carbon atoms, and each R ³ may be different or the same, but at least two are alkenyl groups). Isocyanuric acid derivatives are preferred.

R ^{3 in the} general formula (XV) is preferably a monovalent organic group having 1 to 30 carbon atoms from the viewpoint that the heat resistance of the resulting cured product can be further increased, and the availability of raw materials is easy. Are monovalent organic groups having 1 to 10 carbon atoms, such as the following methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and the like. preferable.

  Preferable specific examples of the isocyanurate compound represented by the general formula (XV) include triallyl isocyanurate, trimethallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoisocyanate as described below. Examples include phenyl isocyanurate and tris (2-acryloyloxyethyl) isocyanurate.

In addition, from the viewpoint of high heat resistance, the component (A) is the general formula (XVI) described above.

（式中、Ｒ^４は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^４は異なっていても同一であってもよいが、少なくとも２個がアルケニル基である。）で表される化合物が好ましい。

(Wherein R ⁴ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ⁴ may be different or the same, but at least two are alkenyl groups. ) Is preferred.

R ^{4 in the} general formula (XVI) is preferably a monovalent organic group having 1 to 30 carbon atoms from the viewpoint that the heat resistance of the resulting cured product can be further increased, and is easy to obtain raw materials. Is more preferably a monovalent organic group having 1 to 10 carbon atoms. Examples of R ⁴ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and the like.

Preferable specific examples of the substituted phenylene compound represented by the general formula (XVI) include divinylbenzene, divinylbiphenyl, 1,4-diisopropenylbenzene, oligomers thereof, and bisphenol A diallyl ether.

R ^{4 in the} general formula (XVI) preferably has a plurality of aromatic rings in the skeleton from the viewpoint that the resulting cured product can have higher heat resistance.

In addition, as the component (A), from the viewpoint of heat resistance and transparency of the cured product, the general formula (XVII)

（式中、Ｒ^５は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^５は異なっていても同一であってもよいが、少なくとも２個がアルケニル基である。）で表される多置換シクロヘキサン化合物が挙げられる。

(Wherein R ⁵ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ⁵ may be different or the same, but at least two are alkenyl groups. And a polysubstituted cyclohexane compound represented by

Specific examples of the polysubstituted cyclohexane compound represented by the general formula (XVII) include 1,2,4-trivinylcyclohexane.

In addition, general formula (XVIII)

（式中Ｒ^６は水素原子あるいは炭素数１〜３０の一価のアルケニル基を表し、それぞれのＲ^６は異なっていても同一であってもよいが、少なくとも２個がアルケニル基である。）で表されるアダマンタン誘導体が挙げられる。

(Wherein R ⁶ represents a hydrogen atom or a monovalent alkenyl group having 1 to 30 carbon atoms, and each R ⁶ may be different or the same, but at least two are alkenyl groups.) An adamantane derivative represented by the formula:

Specific examples of the adamantane derivative represented by the general formula (XVIII) include bisstyryl adamantane, 2- (1-adamantyl) propane-1,3-diylbis (meth) acrylate, and the like.

The following general formula (XIX)

（式中Ｒ^７は炭素数１〜３０の一価のアルケニル基である。）で表されるノルボルネン誘導体なども挙げられる。

And a norbornene derivative represented by the formula (wherein R ⁷ is a monovalent alkenyl group having 1 to 30 carbon atoms).

Specific examples of the norbornene derivative represented by the general formula (XIX) include 5-vinyl-2-norbornene.

Further, as the component (A), a silicon compound (A2) having at least two carbon-carbon double bond sites reactive with SiH groups in one molecule can also be used. Here, the silicon compound represents a linear and / or cyclic and / or three-dimensional network polyorganosiloxane.

As the chain polyorganosiloxane of (A2), for example, the following general formula (I)

（式中、それぞれのＲ^８、Ｒ^９は、水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^８、Ｒ^９は異なっていても同一であってもよいが、１分子中に少なくとも２個のアルケニル基を有し、ｎは１〜１０００の数である。）で表されるものが挙げられる。

(In the formula, each R ⁸ and R ⁹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ⁸ and R ⁹ may be different or the same, Having at least two alkenyl groups in one molecule, and n is a number from 1 to 1000).

In the general formula (I), examples of the monovalent organic group having 1 to 30 carbon atoms represented by R ⁸ and R ⁹ include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, Branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl An alkenyl group such as a group, an aryl group such as a phenyl group and a tolyl group, an aralkyl group such as a benzyl group and a phenylethyl group, and at least one of the hydrogen atoms of the hydrocarbon group is a halogen, a carboxyl group, The thing substituted by the hydroxyl group, the alkoxy group, and the siloxy group is also mentioned.

The component (A) described in the general formula (I) is a linear polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s, preferably 0.001 to 10 Pa · s, for ease of handling. Specific examples include 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3 -Divinyl-tetraethoxydisiloxane, divinyltetrakis (trimethylsiloxy) disiloxane, 1,3-divinyl-1,3-dimethyl-1,3-dichlorodisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane 1,3-diallyltetrakis (trimethylsiloxy) disiloxane, hexavinyldisiloxane, 1,3-diallyltetra Tildisiloxane, 1,5-divinyl-hexamethyltrisiloxane, 1,5-divinyl-3-phenyl-pentamethyltrisiloxane, 1,5-divinyl-3,3-diphenyl-1,1,5,5- Tetramethyltrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, tris (vinyldimethylsiloxy) methylsilane, tris (vinyldimethylsiloxy) phenylsilane, tetrakis (vinyldimethylsiloxy) ) Silane and the like.

Examples of the cyclic polyorganosiloxane (A2) include the following general formula (II):

（式中、Ｒ^１０は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１０は異なっていても同一であってもよいが、１分子中に少なくとも２個のアルケニル基を有し、ｎは３〜１０の数である。）で表されるものが挙げられる。

(Wherein R ¹⁰ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁰ may be different or the same, but at least two alkenyl groups in one molecule) And n is a number of 3 to 10.).

Examples of the monovalent organic group having 1 to 30 carbon atoms represented by R ¹⁰ in the general formula (II) include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an isopropyl group, and an isobutyl group. Group, branched alkyl group such as tert-butyl group, cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, alkenyl such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group Group, aryl group such as phenyl group, tolyl group and the like, aralkyl group such as benzyl group and phenylethyl group, etc., and at least one of the hydrogen atoms of the hydrocarbon group is halogen, carboxyl group, hydroxyl group, alkoxy group And those substituted with.

The component (A) described in the general formula (II) is a cyclic polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s, preferably 0.001 to 10 Pa · s for ease of handling. Specific examples include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-methyl-3,5,7-trivinyl-1,3,5,7. -Tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dimethyl-1,3,5,7-tetramethylcyclotetrasiloxane and the like.

Examples of the branched and / or three-dimensional network polyorganosiloxane (A2) include, for example, the following general formulas (III) to (VI):

（式中、Ｒ^１１は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１１は異なっていても同一であってもよい。）から選択される単位からなり、全構成単位のうち少なくともアルケニル基を２個有している組成物が挙げられる。

(Wherein R ¹¹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹¹ may be different or the same). A composition having at least two alkenyl groups among the structural units is exemplified.

The branched and / or three-dimensional network polyorganosiloxane described in the general formulas (III) to (VI) has a three-dimensional network structure composed of tetrafunctional structural units (Q units) as a main structure, It has a structure in which the terminal is blocked with a monofunctional structural unit (M unit), and the viscosity at 25 ° C. is 0.001 to 100 Pa · s, preferably 0.001 to 10 Pa · s, for ease of handling. s branched and / or three-dimensional network polyorganosiloxane.

(A) A component can use said (A1) and (A2) individually or in mixture of 2 or more types.

((B) component)
Next, the component (B) will be described.

The component (B) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, it is a compound described in International Publication WO96 / 15194, and at least two SiH groups in one molecule. From the viewpoint of availability, a linear and / or cyclic and / or three-dimensional network polyorganosiloxane having at least two SiH groups in one molecule is preferable.

As the chain organopolysiloxane of component (B), the following general formula (VII)

（式中、それぞれのＲ^１２、Ｒ^１３は、水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１２、Ｒ^１３は異なっていても同一であってもよいが、一分子中少なくとも２個のＳｉＨ基を有し、ｎは１〜１０００の数である。）で表されるものが挙げられる。

(In the formula, each of R ¹² and R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each of R ¹² and R ¹³ may be different or the same, It has at least 2 SiH groups in one molecule, and n is a number from 1 to 1000).

In the general formula (VII), examples of the monovalent organic group having 1 to 30 carbon atoms represented by R ¹² and R ¹³ include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, Branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl An alkenyl group such as a group, an aryl group such as a phenyl group and a tolyl group, an aralkyl group such as a benzyl group and a phenylethyl group, and at least one of the hydrogen atoms of the hydrocarbon group is a halogen, a carboxyl group, The thing substituted by the hydroxyl group, the alkoxy group, and the siloxy group is also mentioned.

The component (B) described in the general formula (VII) is a chain polyorganosiloxane compound having a viscosity at 25 ° C. of 0.001 to 100 Pa · s, preferably 0.001 to 10 Pa · s, for ease of handling. Specific examples include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,3-bis (trimethylsiloxy) -1,3-dimethyldi Siloxane, 1,3-diphenyltetrakis (dimethylsiloxy) disiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane, 3 -Phenyl-1,1,3,5,5-pentamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, trifluoropropyltrisiloxane (Dimethylsiloxy) silane, methyl tris (dimethylsiloxy) silane, phenyl tris (dimethylsiloxy) silane, vinyltris (dimethylsiloxy) silane, tetrakis (dimethylsiloxy) silane.

Examples of the cyclic polyorganosiloxane of the component (B) include the following general formula (VIII)

（式中、Ｒ^１４は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１４は異なっていても同一であってもよいが、少なくとも２個はＳｉＨ基であり、ｎは３〜１０の数を表す。）で表されるものが挙げられる。

(Wherein R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁴ may be different or the same, but at least two are SiH groups; n represents a number of 3 to 10.).

Examples of the monovalent organic group having 1 to 30 carbon atoms represented by R ¹⁴ in the general formula (VIII) include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an isopropyl group, and an isobutyl group. Group, branched alkyl group such as tert-butyl group, cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, alkenyl such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group Group, aryl group such as phenyl group, tolyl group and the like, aralkyl group such as benzyl group and phenylethyl group, etc., and at least one of the hydrogen atoms of the hydrocarbon group is halogen, carboxyl group, hydroxyl group, alkoxy group And those substituted with.

The component (B) described in the general formula (VIII) is a cyclic polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s, preferably 0.001 to 10 Pa · s, for ease of handling. Specific examples include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and the like. .

Examples of the branched and / or three-dimensional network polyorganosiloxane (B) include, for example, the following general formulas (IX) to (XII):

（式中、Ｒ^１５は水素原子あるいは炭素数１〜３０の一価の有機基を表し、それぞれのＲ^１５は異なっていても同一であってもよい。）から選択される単位からなり、全構成単位のうち少なくともＳｉＨ基を２個有している組成物が挙げられる。

(Wherein R ¹⁵ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁵ may be different or the same). A composition having at least two SiH groups among the structural units is exemplified.

The branched and / or three-dimensional network polyorganosiloxanes described in the general formulas (IX) to (XII) have a three-dimensional network structure composed of tetrafunctional structural units (Q units) as a main structure, It has a structure in which the terminal is blocked with a monofunctional structural unit (M unit), and the viscosity at 25 ° C. is 0.001 to 100 Pa · s, preferably 0.001 to 10 Pa · s, for ease of handling. s branched and / or three-dimensional network polyorganosiloxane.

From the viewpoint of having good compatibility with the component (A), and from the viewpoint that the problem of outgas from the composition that can reduce the volatility of the component (B) is less likely to occur, the component (B) is a SiH group. At least two carbon-carbon double bond sites reactive with the organic skeleton part (A1) having at least two carbon-carbon double bond sites in one molecule and / or SiH group in one molecule. Two silicon skeleton parts (A2) and chain and / or cyclic and / or branched and / or three-dimensional network polyorganosiloxane (B) having at least two SiH groups in one molecule are hydrosilylated. It is preferable that it is a modified body (B1) which can be obtained by a chemical reaction.

  The component (A) used to obtain (B1) has the above general formula (XVII) from the viewpoint of high heat resistance and light resistance.

（式中Ｒ^５は炭素数１〜３０の一価の有機基を表し、それぞれのＲ^５は異なっていても同一であってもよい。）の骨格を有する化合物が好ましい。

A compound having a skeleton (wherein R ⁵ represents a monovalent organic group having 1 to 30 carbon atoms, and each R ⁵ may be different or the same) is preferable.

Specific examples of the general formula (XVII) include triallyl isocyanurate, trimethallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monophenyl isocyanurate, tris (2-acryloyloxyethyl) ) Isocyanurate and the like.

Alternatively, (A1) includes the phenylene compounds, cyclohexane derivatives, adamantane derivatives, and norbornene derivatives represented by the general formulas (XVI) to (XIX) described above.

Specific examples of the compounds represented by the general formulas (XVI) to (XIX) include divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, bisphenol A diallyl ether, 1, Examples include 2,4-trivinylcyclohexane, bisstyryladamantane, 2- (1-adamantyl) propane-1,3-diylbis (meth) acrylate, 5-ethynylidene-2-norbornene, 5-vinyl-2-norbornene and the like. The

As (A2) used to obtain (B1), chain and / or cyclic and / or branched and / or having at least two SiH groups in one molecule of the above-mentioned general formulas (I) to (VI) Alternatively, a three-dimensional network polyorganosiloxane is preferable.

Examples of the linear polyorganosiloxane represented by the above formula (I) include 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,3-divinyl-1,3- Diphenyl-1,3-dimethyldisiloxane, 1,3-divinyl-tetraethoxydisiloxane, divinyltetrakis (trimethylsiloxy) disiloxane, 1,3-divinyl-1,3-dimethyl-1,3-dichlorodisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane 1,3-diallyltetrakis (trimethylsiloxy) disiloxane, hexavinyldisiloxane, 1,3-diallyltetramethyldisiloxane, 1,5-divinylhexamethyltrisiloxane Siloxane, 1,5-divinyl-3-phenyl-pentamethyltrisiloxane 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, tris ( Examples include vinyldimethylsiloxy) methylsilane, tris (vinyldimethylsiloxy) phenylsilane, and tetrakis (vinyldimethylsiloxy) silane.

Examples of the cyclic polyorganosiloxane represented by the above formula (II) include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-methyl-3, Examples include 5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dimethyl-1,3,5,7-tetramethylcyclotetrasiloxane.

(Preliminary reaction)
Reaction for obtaining modified body (B1) containing organic skeleton part (A1) represented by general formula (XV) or (XVI) and containing at least two SiH groups in one molecule having organic skeleton explain.

Hydrosilylation reaction of organic skeleton part (A1) containing two or more carbon-carbon double bond sites in one molecule and polyorganosiloxane (B) having at least two SiH groups in one molecule The mixing ratio of both components is not particularly limited as long as two or more SiH groups remain in one molecule.

When considering the strength of the resulting cured product, the number of moles (X) of carbon-carbon double bonds having reactivity with SiH groups in (A1) and the number of moles of SiH groups in component (B) ( The ratio with Y) is preferably Y / X ≧ 2, more preferably Y / X ≧ 3.

In the case of hydrosilylation, an appropriate catalyst may be used. As the catalyst, for example, the component (C) described later can be used.

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is 10 ^{−10 with} respect to 1 mol of SiH groups of the component (B) in order to keep the reactivity sufficiently and keep the cost of the composition relatively low. mol, more preferably ^{10 -8} mole, preferable amount of the upper limit (B) ^{10 -1} moles per mole of the SiH group in component, more preferably ^{10 -3} mol.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

Various methods can be used as a catalyst mixing method at the time of reaction, and a method in which a mixture of (A1) and a hydrosilylation catalyst is mixed with component (B) is preferable. In some cases, it is difficult to control the reaction by a method in which a hydrosilylation catalyst is mixed with a mixture of the components (A1) and (B). In addition, in the method of mixing the component (α) with the mixture of the component (B) and the hydrosilylation catalyst, the component (B) in the presence of the hydrosilylation catalyst has reactivity with the water in which it is mixed, and therefore changes in quality. Sometimes.

Although various reaction temperatures can be set, the lower limit of the preferred temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferred temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficient reaction tends to be long, and if the reaction temperature is high, it may be industrially disadvantageous. The reaction may be carried out at a constant temperature, and the temperature may be changed in multiple steps or continuously as required.

Various reaction times and pressures during the reaction can be set as required. The reaction time is not particularly limited. From the economical aspect, it is preferably within 20 hours, more preferably within 10 hours. The pressure is not particularly limited, but is preferably from atmospheric pressure to 5 MPa, more preferably from atmospheric pressure to 2 MPa from the viewpoint that a special apparatus is required and the operation becomes complicated.

A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

The solvent and / or unreacted compound may be removed after the synthesis reaction. Examples of the removal method include vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 120 ° C, more preferably 100 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

In order to improve storage stability, storage at 10 ° C. or lower is preferable in an inert gas atmosphere such as nitrogen or argon, storage at 0 ° C. or lower is particularly preferable, and storage at −10 ° C. or lower is further preferable. .

Examples of such modified products include modified products of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane. Modified product of monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, modified product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, bisphenol A Modified product of diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, modified product of bis [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetramethylcyclotetrasiloxane Etc. are exemplified.

The chain and / or cyclic and / or branched and / or three-dimensional network polyorganosiloxane (B) components can be used alone or in admixture of two or more.

((C) component)
Next, the hydrosilylation catalyst as component (C) will be described.

The hydrosilylation catalyst of component (C) is not particularly limited as long as it has catalytic activity for the hydrosilylation reaction. For example, platinum alone; solid platinum supported on a carrier such as alumina, silica, carbon black; Platinum acid; complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin complex (for example, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); Platinum-vinylsiloxane complex (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _a , Pt [(MeViSiO) ₄ ] _b ); platinum-phosphine complex (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ); platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents Til group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and a and b represent an integer.); Dicarbonyldichloroplatinum; Karlstedt catalyst; platinum-hydrocarbon complex (for example, Platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,662; platinum alcoholate catalysts (eg, described in US Pat. No. 3,220,972 to Lamoreaux). And platinum alcoholate catalyst). In addition, platinum chloride-olefin complexes (eg, the platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946) are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. Etc.

Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The amount of component (C) added is not particularly limited, but the lower limit of the amount added is preferably 1 mol of SiH groups in component (B) in order to have sufficient curability and keep the cost of the curable composition relatively low. ^{10 -8} mol relative to, more preferably from ^{10 -7} moles, preferable amount of the upper limit is ^{10 -1} moles per mole of the SiH group in component (B), more preferably ^{10 -2} mol .

In addition, a cocatalyst can be used in combination with the catalyst. Examples of the cocatalyst include a sulfur-based compound such as simple sulfur, and an amine-based compound such as triethylamine.

The addition amount of the cocatalyst is not particularly limited, but a lower limit of 10 ⁻² mol and an upper limit of 10 ² mol are preferable, and a lower limit of 10 ⁻¹ mol and an upper limit of 10 mol are preferable with respect to 1 mol of the hydrosilylation catalyst. It is.

(Other additives)
(Storage stabilizer)
It is preferable to add a storage stabilizer for the purpose of improving the storage stability of the curable composition for optical materials of the present invention. Examples of the storage stabilizer include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Among these storage stabilizers, 1-ethynylcyclohexanol, 3-hydroxy-3-methyl-1-butyne, and dimethyl malate are preferable from the viewpoint of good storage stability and good raw material availability.

The addition amount of the storage stabilizer is preferably in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, with respect to 1 mol of the hydrosilylation catalyst used.

(Anti-aging agent)
An aging inhibitor may be added to the curable composition for optical materials of the present invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.

Various types of hindered phenol-based anti-aging agents such as Irganox 1010 available from Ciba Specialty Chemicals are used.

Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

These anti-aging agents may be used alone or in combination of two or more.

(Radical inhibitor)
You may add a radical inhibitor to the curable composition for optical materials of this invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.

These radical inhibitors may be used alone or in combination of two or more.

(UV absorber)
You may add a ultraviolet absorber to the curable composition for optical materials of this invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.

These ultraviolet absorbers may be used alone or in combination of two or more.

(Inorganic filler)
An inorganic filler may be added to the curable composition for optical materials of the present invention. Addition of an inorganic filler is effective in increasing the strength of the material and improving flame retardancy. The inorganic filler is preferably a fine particle, and examples thereof include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, barium sulfate, and a phosphor.

As a method for adding the filler, for example, hydrolyzable silane monomers or oligomers such as alkoxysilane, acyloxysilane, and halogenated silane, metal alkoxides such as titanium and aluminum, acyloxide, or halides, and the like are cured according to the present invention. Examples thereof include a method in which an inorganic filler is produced in the composition by adding to the functional composition and reacting in the composition or a partial reaction product of the composition.

The curable composition of the present invention includes other colorants, mold release agents, flame retardants, flame retardant aids, surfactants, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, thixo Property imparting agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, antifoaming agent, plasticizer, reactive diluent, antioxidant, thermal stabilizer, conductivity The purpose and effect of the present invention include an imparting agent, an antistatic agent, a radiation shielding agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent, and a physical property modifier. It can be added as long as it is not impaired.

Component (A) and Component (B) of the curable composition for optical materials of the present invention [[number of moles of carbon-carbon double bond having reactivity with SiH group of component (A) / SiH of component (B)] The number of moles of the group] is preferably a ratio with a lower limit of 0.05 and an upper limit of 10, more preferably a ratio of a lower limit of 0.1 and an upper limit of 5 with a lower limit of 0.5. The upper limit is particularly preferably 2. When the lower limit value is smaller than 0.05, the effect of crosslinking due to the reaction between the carbon-carbon double bond and the SiH group tends to be insufficient, and when the upper limit value is larger than 10, the cured product is unreacted ( A) The component may bleed.

The preparation method of a curable composition is not specifically limited, It can prepare with various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance. After mixing all the components, only a part of the functional groups in the composition may be reacted by utilizing reaction control conditions or differences in functional group reactivity. In addition to the modified polyorganosiloxane compound, when using additives such as thermoplastic resins for the purpose of improving physical properties, these additives and a platinum compound that is a curing catalyst are mixed and stored in advance and immediately before curing. The respective predetermined amounts may be mixed with each other.

(Cured product)
Although it does not specifically limit as a method of hardening the curable composition of this invention, It can also make it react only by mixing each component, and can also make it react by heating. From the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and reacting is preferable.

Although various reaction temperatures can be set, the lower limit of the preferable temperature is 30 ° C, more preferably 60 ° C, and still more preferably 90 ° C. The upper limit of the preferable temperature is 300 ° C, more preferably 250 ° C, and still more preferably 200 ° C. When the reaction temperature is low, the reaction time for sufficient reaction is prolonged. If the reaction temperature is high, coloring or bulging may occur. If the reaction temperature is low, the reaction time for sufficient reaction tends to be long, and if the reaction temperature is high, coloring or bulging may occur.

The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that a uniform cured product without distortion can be easily obtained.

The pressure during the reaction can be variously set as required, and the reaction can be carried out at normal pressure, high pressure or reduced pressure.

The cured product obtained by curing the composition of the present invention is preferably a 3 mm thick sample having a light transmittance of 70% or more at a wavelength of 400 nm. Furthermore, even if this cured product is heat-treated at 280 ° C. for 3 minutes, the change in light transmittance at a wavelength of 400 nm can be maintained at 10% or less, and therefore, it is considered that there is solder reflow resistance. Such high heat resistance can increase the degree of design freedom and application destinations of optical semiconductors, modules, and optical components.

(Use)
The curable composition of the present invention is used for optical materials. The optical material here is a material used for the purpose of allowing light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material, and specific examples thereof include the following.

For example, camera lenses such as (digital) cameras, mobile phones, and in-vehicle cameras, optical lenses such as projection lenses, f-θ lenses, and pickup lenses, optical films, optical sheets, dicing tape, insulating materials (printed boards, wire coatings) Etc.), high voltage insulation materials, interlayer insulation films, insulation coating materials, coating materials (including hard coats, sheets, films, release paper coats, optical disc coats, optical fiber coats, etc.), molding materials (sheets) , Film, FRP, etc.), potting material, optical semiconductor sealing material, resist material, liquid resist material, colored resist, dry film resist material, solder resist material, color filter material, stereolithography, solar cell material, It can be applied to display materials, recording materials, and photosensitive drums for copying machines.

EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples. In addition, each measuring method of the physical property measured in the following Examples and Comparative Examples is as follows.

(1) Measurement of residual volatile matter Gas chromatographic analysis was performed on the composition after devolatilization, and the residual volatile matter amount was calculated based on the area ratio to the calibration curve.

(2) Measurement of haze (cloud value) The obtained composition was put into a 10 mm-thick cell, and the haze value was measured with a haze meter (NDA300-A, manufactured by Nippon Denshoku).

(3) Transparency of cured product The light transmittance at 400 nm of the obtained cured product (3 mm thickness) was measured with a spectrophotometer (U-3300, Hitachi).

(4) SiH base value A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. (B) Reaction tracking in component synthesis was measured by adding a reaction solution diluted to about 1% with deuterated chloroform to an NMR tube and measuring the peak of unreacted SiH groups or unreacted carbon-carbon double bond groups. It calculated | required from the peak of the methylene group derived from, and the peak of the methylene group derived from the reaction carbon-carbon double bond group. As the functional group value of the component (B), the carbon-carbon double bond value (mmol / g) and SiH value (mmol / g) in terms of dibromoethane were determined.

(Devolatilization)
Example 1
(A1) Volatilization of triallyl isocyanate / platinum catalyst / antioxidant mixture (2L autoclave)
-Irganox1010: 20.04 g, 3% -PtVTS toluene solution: 8 g was added to TAIC: 1623.47 g and dissolved in a constant temperature shaker at 70 ° C for 1 hour.
・ The internal temperature was set to 40 ° C, and after reaching 40 ° C, the devolatilization operation was started.
-The stirring speed was set to about 480 rpm. The devolatilization operation was carried out by bubbling and devolatilization by supplying nitrogen at 0.467 L / min (17.5 L / Hr · kg) from the bottom of the kettle while devolatilizing with a vacuum pump.
・ Sampling was performed as needed, and residual volatiles were measured by GC, and the devolatilization experiment was completed in 2 hours.

Table 1 shows the results of measuring the residual volatile components in the component (A1) after devolatilization. Further, this devolatilized component (A1) and the modified product (B1) 1,3,5,7-tetramethylcyclotetrasiloxane triallyl isocyanurate modified product (one component) Table 1 also shows the appearance and haze. The modified product (B1) was produced by the method of Synthesis Example 1 shown below.

(Example 2)
The same operation as in Example 1 was performed except that the devolatilization temperature was changed to 60 ° C. and the nitrogen supply amount was changed to 0.234 L / min (8.8 L / Hr · kg).

  Table 1 shows the results of measuring the residual volatile content in the component (A1) after devolatilization, and the appearance and haze measurement results of the curable composition (one liquid) prepared by mixing in the same manner as in Example 1. It was.

(Example 3)
Except that the devolatilization temperature was 80 ° C, the raw material charge was halved, the stirring speed was 375 rpm, and 3% oxygen-97% nitrogen mixed gas was supplied at 0.467 L / min (35 L / Hr · kg). The same operation as in Example 1 was performed.

  Table 1 shows the results of measuring the residual volatile content in the component (A1) after devolatilization, and the appearance and haze measurement results of the curable composition (one liquid) prepared by mixing in the same manner as in Example 1. It was.

Example 4
The devolatilization temperature was 80 ° C., the raw material charge was ¼, the stirring rotation speed was 300 rpm, and the devolatilization operation was performed by pressurizing the gas phase part to 0.3 MPaG with nitrogen and stirring for 2 minutes, and then using a vacuum pump. The same operation as in Example 1 was performed except that devolatilization was repeated for a minute.

  Table 1 shows the results of measuring the residual volatile content in the component (A1) after devolatilization, and the appearance and haze measurement results of the curable composition (one liquid) prepared by mixing in the same manner as in Example 1. It was.

(Comparative Example 1)
The same operation as in Example 1 except that the devolatilization temperature was 120 ° C., the raw material charge was ¼, the stirring rotation speed was 100 rpm, and the devolatilization operation was only devolatilization by a vacuum pump without supplying nitrogen. went.

  Table 1 shows the results of measuring the residual volatile content in the component (A1) after devolatilization, and the appearance and haze measurement results of the curable composition (one liquid) prepared by mixing in the same manner as in Example 1. It was.

(Comparative Example 2)
The same operation as in Comparative Example 1 was performed except that the devolatilization temperature was 80 ° C.

Table 1 shows the results of measuring the residual volatile content in the component (A1) after devolatilization, and the appearance and haze measurement results of the curable composition (one liquid) prepared by mixing in the same manner as in Example 1. It was.

(Comparative Example 3)
The same operation as Comparative Example 1 was performed except that the devolatilization temperature was 40 ° C.

Table 1 shows the results of measuring the residual volatile content in the component (A1) after devolatilization, and the appearance and haze measurement results of the curable composition (one liquid) prepared by mixing in the same manner as in Example 1. It was.

  The curable compositions (one liquid) of Example 1 and Comparative Example 1 were poured into a glass cell sandwiching a 1 mm thick spacer and heated in an oven at 120 ° C. to be cured. Table 2 shows the measurement results of haze and light transmittance of 400 nm of the obtained cured product.

(Synthesis Example 1)
Into a 2 L autoclave, 650 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 600 g of toluene were added, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed solution of 90 g of triallyl isocyanurate, 110 g of toluene and 3.5 g of a xylene solution of platinum vinylsiloxane complex (containing 0.03 wt% as platinum) was added in 10 divided portions. After 6 hours of heating and stirring from the end of dropping, ¹ H-NMR confirmed that the allyl group reaction rate was 95% or more, and the reaction was terminated by cooling. The reaction was terminated by cooling.
Toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were devolatilized under reduced pressure at 60 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a colorless and transparent liquid. ^{According to 1} H-NMR, this product was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the allyl group of triallyl isocyanurate (referred to as (β1). Although it was a mixture, it was found that it contains the following compounds containing 9 SiH groups in one molecule as the main component). Further, when the content of SiH group was determined by ¹ H-NMR using 1,2-dibromoethane as an internal standard, it was found to contain 9.0 mmol / g.

Claims (51)

A devolatilization method comprising removing a volatile component contained in a compound having at least one reactive double bond in one molecule under reduced pressure. The devolatilization method according to claim 1, wherein a devolatilization device including a vacuum decompression device, a stirring device, a gas blowing tube, and a heating jacket is used. The devolatilization method according to claim 1 or 2, wherein gas is introduced under reduced pressure conditions. The devolatilization method according to any one of claims 1 to 3, wherein the gas is introduced by an intermittent pressurization method to the gas phase portion. The devolatilization method according to any one of claims 1 to 3, wherein the gas introduction method is performed by a bubbling method to the liquid phase part. The devolatilization method according to claim 1, wherein the gas used for devolatilization is air or oxygen-containing nitrogen. The devolatilization method according to claim 1, wherein the gas used for devolatilization is an inert gas. The devolatilization method according to claim 1, wherein the inert gas is selected from the group consisting of nitrogen, argon, helium and neon. The devolatilization method according to any one of claims 1 to 8, wherein the devolatilization method is performed at 500 Torr or less. The devolatilization method according to claim 1, wherein the devolatilization method is performed at a temperature of 0 to 100 ° C. The following component (A) is a compound obtained by the devolatilization method according to any one of claims 1 to 10, and one molecule of a carbon-carbon double bond site reactive with an SiH group A curable composition comprising, as essential components, a compound (A) having at least two in the compound, a compound (B) having at least two SiH groups in the molecule, and a hydrosilylation catalyst (C). The curable composition according to claim 11, wherein the component (A) is an aliphatic chain diene having 20 or less carbon atoms. The component (A) is 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene and 1, The curable composition according to claim 11 or 12, wherein the curable composition is selected from the group consisting of 9-decadiene. The curable composition according to claim 11, wherein the component (A) is an aliphatic cyclic diene having 20 or less carbon atoms. The curable composition according to claim 11 or 14, wherein the component (A) is 1,3-cyclohexadiene, 1,4-cyclohexadiene, or 2,5-norbornadiene. The curable composition according to claim 11, wherein the component (A) is an alkenyl group-substituted alicyclic compound having 20 or less carbon atoms. The component (A) is selected from the group consisting of 1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, 5-vinyl-2-norbornene and 4-vinylcyclohexene. The curable composition according to claim 11 or 16. The curable composition according to claim 11, wherein the component (A) is an alkenyl group-substituted aromatic compound having 20 or less carbon atoms. The component (A) is selected from the group consisting of divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, diallyl phthalate and triallyl trimellitate. The curable composition according to claim 11 or 18, characterized in that The curable composition according to claim 11, wherein the component (A) is an alkenyl group-substituted isocyanurate. 21. The curable composition according to claim 11 or 20, wherein the component (A) is triallyl isocyanurate, diallyl monoglycidyl isocyanurate or tris (2-acryloyloxyethyl) isocyanurate. The component (A) is a polyorganosiloxane having at least two carbon-carbon double bond sites reactive with SiH groups in one molecule, and is a linear, cyclic, branched, or three-dimensional network structure The curable composition according to claim 11, comprising: (A) component is the following general formula (I)

(In the formula, each R ⁸ and R ⁹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ⁸ and R ⁹ may be different or the same, The curing according to claim 11 or 22, which is a linear polyorganosiloxane having at least two alkenyl groups in one molecule and n is a number from 1 to 1000. Sex composition. The curing according to claim 11, 22 or 23, wherein the component (A) described in the general formula (I) is a linear polyorganosiloxane having a viscosity at 25 ° C of 0.001 to 100 Pa · s. Sex composition. 25. The component (A) described in the general formula (I) is a linear polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s, 25, 24, or 24 Curable composition. The component (A) is 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3- Divinyl-tetraethoxydisiloxane, divinyltetrakis (trimethylsiloxy) disiloxane, 1,3-divinyl-1,3-dimethyl-1,3-dichlorodisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane 1 , 3-diallyltetrakis (trimethylsiloxy) disiloxane, hexavinyldisiloxane, 1,3-diallyltetramethyldisiloxane, 1,5-divinyl-hexamethyltrisiloxane, 1,5-divinyl-3-phenyl-pentamethyl Trisiloxane, 1,5-divinyl-3,3-diphenyl-1,1,5 Tetramethyltrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, tris (vinyldimethylsiloxy) methylsilane, tris (vinyldimethylsiloxy) phenylsilane and tetrakis (vinyldimethyl) 26. The curable composition according to claim 11, 22, 23, 24 or 25, which is selected from the group consisting of (siloxy) silanes. (A) component is the following general formula (II)

(Wherein R ¹⁰ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁰ may be different or the same, but at least two are alkenyl groups; 21. The curable composition according to claim 11, wherein n is a cyclic polyorganosiloxane represented by the formula: The curability according to claim 11, 22 or 27, wherein the component (A) described in the general formula (II) is a cyclic polyorganosiloxane having a viscosity at 25 ° C of 0.001 to 100 Pa · s. Composition. 29. The component (A) described in the general formula (II) is a cyclic polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. Curable composition. (A) component is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-methyl-3,5,7-trivinyl-1,3,5,7 12. A material selected from the group consisting of tetramethylcyclotetrasiloxane and 1,5-divinyl-3,7-dimethyl-1,3,5,7-tetramethylcyclotetrasiloxane. , 22, 27, 28 or 29. (A) component is the following general formula (III)-(VI)

(Wherein R ¹¹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹¹ may be different or the same) and / or 23. The curable composition according to claim 11 or 22, which is a three-dimensional network polyorganosiloxane and is a compound having at least two alkenyl groups in one molecule. The component (A) described in the general formulas (III) to (VI) is a branched and / or three-dimensional network polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s. The curable composition according to claim 11, 22 or 31. The component (A) described in the general formulas (III) to (VI) is a branched and / or three-dimensional network polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. The curable composition according to claim 11, 22, 31 or 32. (B) component is the following general formula (VII)

(In the formula, each of R ¹² and R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each of R ¹² and R ¹³ may be different or the same, The curable composition according to claim 11, wherein the curable composition has a chain polyorganosiloxane having at least two SiH groups in one molecule and n is a number from 1 to 1000. . The curable composition according to claim 11 or 34, wherein the component (B) described in the general formula (VII) is a linear polyorganosiloxane having a viscosity at 25 ° C of 0.001 to 100 Pa · s. object. The curing according to claim 11, 34 or 35, wherein the component (B) described in the general formula (XIV) is a linear polyorganosiloxane having a viscosity at 25 ° C of 0.001 to 10 Pa · s. Sex composition. (B) component is 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,3-bis (trimethylsiloxy) -1,3-dimethyldisiloxane, 1,3-diphenyltetrakis (dimethylsiloxy) disiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane, 3-phenyl -1,1,3,5,5-pentamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, trifluoropropyltris (dimethylsiloxy) silane, methyltris (dimethyl (Siloxy) silane, phenyltris (dimethylsiloxy) silane, vinyltris (dimethylsiloxy) silane and tetrakis (dimethylsiloxy) silane. The curable composition of claim 11,34,35 or 36, characterized in that one selected from the group. (B) component is the following general formula (VIII)

(In the formula, R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁴ may be different or the same, but at least two SiH groups in one molecule. And n is a number from 3 to 10.) The curable composition according to claim 11, wherein the curable composition is a cyclic polyorganosiloxane. The curable composition according to claim 11 or 38, wherein the component (B) described in the general formula (VIII) is a cyclic polyorganosiloxane having a viscosity at 25 ° C of 0.001 to 100 Pa · s. . The curability according to claim 11, 38 or 39, wherein the component (B) described in the general formula (VIII) is a cyclic polyorganosiloxane having a viscosity at 25 ° C of 0.001 to 10 Pa · s. Composition. The component (B) is 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane or 1,3,5,7,9-pentamethylcyclopentasiloxane. 41. A curable composition according to claim 11, 38, 39 or 40. (B) component is the following general formula (IX)-(XII)

(Wherein R ¹⁵ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and each R ¹⁵ may be different or the same) and / or The curable composition according to claim 11, which is a three-dimensional network polyorganosiloxane and is a compound having at least two SiH groups in one molecule. The component (B) described in the general formulas (IX) to (XII) is a branched and / or three-dimensional network polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 100 Pa · s. 43. The curable composition according to claim 11 or 42. The component (B) described in the general formulas (IX) to (XII) is a branched and / or three-dimensional network polyorganosiloxane having a viscosity at 25 ° C. of 0.001 to 10 Pa · s. The curable composition according to claim 11, 42 or 43. The component (B) has an organic skeleton part (A) having at least two carbon-carbon double bond sites reactive with SiH groups in one molecule and at least two SiH groups in one molecule. A modified product (B1) obtainable by hydrosilylation reaction with a polyorganosiloxane (B) having a linear, cyclic, branched or three-dimensional network structure, wherein at least two per molecule It is a compound which has SiH group, The curable composition of Claim 11 characterized by the above-mentioned. The component (B) is a modified product obtained by hydrosilylation reaction of an isocyanuric acid derivative and a cyclic polyorganosiloxane, and is a compound having at least two SiH groups in one molecule. The curable composition according to claim 11 or 45. Component (B) is a modified product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, a modified product of diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane. A modified product of monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, a modified product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, and bisphenol A diallyl ether A modified group of 1,3,5,7-tetramethylcyclotetrasiloxane, and a group consisting of a modified form of bis [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetramethylcyclotetrasiloxane 47. In claim 11, 45 or 46, characterized in that The curable composition of the mounting. The curable composition according to any one of claims 11 to 47, wherein the haze of the liquid measured by putting the curable composition into a cell having an optical path length of 10 mm using a haze meter is 10% or less. . Hardened | cured material formed by hardening | curing the curable composition in any one of Claims 11-48. The optical member using the hardened | cured material of the curable composition in any one of Claims 11-49. The optical module using the optical member in any one of Claims 11-50.