JP4805229B2 - Electronic components sealed or coated with radiation curable silicone rubber composition - Google Patents

Description

  The present invention relates to a radiation curable silicone rubber composition capable of forming a cured product having excellent adhesiveness.

  Examples of organopolysiloxane compositions that can be cured by irradiation with radiation such as ultraviolet rays include, for example, a plurality of vinyl functional group-containing organopolysiloxanes such as acryloyloxy groups and methacryloyloxy groups, and photopolymerization initiators. A radiation-curable optical fiber coating agent (see Patent Document 1) is known. However, this composition has low adhesiveness to a substrate, and in particular, it could not be used as a coating agent, adhesive or potting agent related to electric / electronic parts.

  In addition, the applicant previously contained an alkoxysilane (and / or a partially hydrolyzed condensate thereof) together with an organopolysiloxane having a plurality of acryloyloxy groups and / or methacryloyloxy groups, and a photosensitizer. Has proposed a radiation curable silicone rubber composition (Patent Document 2) capable of forming a cured product having excellent properties. However, this composition does not exhibit sufficiently rapid adhesion, and is particularly difficult under severe conditions. In this case, there is a problem that the adhesion to the substrate is still insufficient.

Japanese Patent Publication No. 4-25231 JP-A-11-302348

  An object of the present invention is to provide a radiation curable composition that is rapidly cured by irradiation for a short time and exhibits good adhesion to various substrates.

The present invention solves the above problems.
(A) The following general formula (1):

〔式中、Ｒ¹ は独立に非置換または置換の炭素原子数１〜９の１価炭化水素基であり、
Ｘは独立に下記一般式(2)：

[Wherein, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 9 carbon atoms,
X is independently the following general formula (2):

｛式中、Ｒ² は炭素原子数２〜４の２価炭化水素基または酸素原子であり、Ｒ³ は独立に下記一般式：

{In the formula, R ² represents a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and R ³ independently represents the following general formula:

（式中、Ｒは水素原子またはメチル基である）
で表されるアクリロイル基および／またはメタクリロイル基を１〜３個有する炭素原子数４〜25の１価の有機基であり、Ｒ⁴ は独立に非置換または置換の炭素原子数１〜９の１価炭化水素基であり、Ｒ⁵ は独立に炭素原子数１〜18の１価炭化水素基であり、ｎは１〜３、ｍは０〜２、かつｎ＋ｍの和は１〜３の整数である。但し、ｎ＝１のとき、前記Ｒ³ は２〜３個のアクリロイル基および／またはメタクリロイル基を有する有機基である。｝で表される基であり、Ｌは８〜10,000の整数である〕
で表されるオルガノポリシロキサン、
(B) 放射線増感剤、並びに、
(C) 式：−ＳｉＲ⁶ ₃（Ｒ⁶ は独立に炭素原子数１〜８のアルキル基またはアルコキシ基である）で表されるトリオルガノシリル基を有するイソシアヌレート化合物および／またはその加水分解縮合物
を含有する放射線硬化性シリコーンゴム組成物を提供する。

(In the formula, R is a hydrogen atom or a methyl group)
A monovalent organic group having 4 to 25 carbon atoms and having 1 to 3 acryloyl groups and / or methacryloyl groups, and R ⁴ is independently an unsubstituted or substituted 1 having 1 to 9 carbon atoms. R ⁵ is independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, n is 1 to 3, m is 0 to 2, and the sum of n + m is an integer of 1 to 3. is there. However, when n = 1, the R ³ is an organic group having 2 to 3 acryloyl groups and / or methacryloyl groups. } And L is an integer of 8 to 10,000.
An organopolysiloxane represented by
(B) a radiosensitizer, and
(C) An isocyanurate compound having a triorganosilyl group represented by the formula: —SiR ⁶ ₃ (wherein R ⁶ is independently an alkyl group or alkoxy group having 1 to 8 carbon atoms) and / or its hydrolytic condensation. A radiation-curable silicone rubber composition containing the product is provided.

  The composition of the present invention is easily cured by irradiation for a short time with radiation, for example, ultraviolet rays, and quickly develops adhesiveness. Therefore, it is useful for adhesion, coating, potting and the like of various substrates. In addition, since the curing speed is high, for example, effects such as shortening of the process, improvement of productivity, energy saving, etc. can be obtained in the manufacture of electric / electronic parts. Furthermore, since the adhesiveness of the composition of the present invention is strongly expressed immediately after curing, the resulting adhesive part can be easily handled.

  Hereinafter, the present invention will be described in detail. In this specification, (meth) acryloyl, (meth) acryl, (meth) acrylate, and the like are acryloyl, methacryloyl, acryl and methacryl, and acrylate and methacrylate, respectively. It is used as a term encompassing etc. “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, and “iPr” represents an isopropyl group.

[(A) Organopolysiloxane]
The organopolysiloxane of component (A) is represented by the following general formula (1) and is used as the main component (base polymer) of the radiation curable silicone rubber composition of the present invention.

〔式中、Ｒ¹ は独立に非置換または置換の炭素原子数１〜９の１価炭化水素基であり、
Ｘは独立に下記一般式(2)：

[Wherein, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 9 carbon atoms,
X is independently the following general formula (2):

｛式中、Ｒ² は炭素原子数２〜４の２価炭化水素基または酸素原子、Ｒ³ は独立に下記一般式：

{In the formula, R ² represents a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and R ³ independently represents the following general formula:

（式中、Ｒは水素原子またはメチル基である）
で表されるアクリロイル基および／またはメタクリロイル基を１〜３個有する炭素原子数４〜25、好ましくは５〜20の１価の有機基、Ｒ⁴ は独立に非置換または置換の炭素原子数１〜９、好ましくは１〜６の１価炭化水素基、Ｒ⁵ は独立に炭素原子数１〜18、好ましくは１〜８の１価炭化水素基であり、ｎは１〜３、ｍは０〜２、かつｎ＋ｍの和は１〜３の整数である。但し、ｎ＝１のとき、前記Ｒ³ は２〜３個のアクリロイル基および／またはメタクリロイル基を有する有機基である。｝で表される基であり、Ｌは８〜10,000、好ましくは 48〜1,000の整数である〕

(In the formula, R is a hydrogen atom or a methyl group)
A monovalent organic group having 1 to 3 carbon atoms and preferably 5 to 20 carbon atoms having 1 to 3 acryloyl groups and / or methacryloyl groups, and R ⁴ is independently an unsubstituted or substituted carbon atom 1 to 9, preferably a monovalent hydrocarbon group of 1 to 6, R ⁵ is 1 to 18 carbon atoms independently, preferably 1-8 monovalent hydrocarbon radical, n is 1 to 3, m is 0 The sum of ˜2 and n + m is an integer of 1 to 3. However, when n = 1, the R ³ is an organic group having 2 to 3 acryloyl groups and / or methacryloyl groups. And L is an integer of 8 to 10,000, preferably 48 to 1,000.

Specific examples of R ¹ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl. Group, alkyl group such as nonyl group; cycloalkyl group such as cyclohexyl group, cycloheptyl group; alkenyl group such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group; phenyl group, tolyl group, etc. Aryl groups such as benzyl, phenylethyl, 3-phenylpropyl, and the like; and at least part of the hydrogen atoms bonded to carbon atoms of these groups are substituted with substituents such as halogen atoms and cyano groups And a chloromethyl group, a cyanoethyl group, a 3,3,3-trifluoropropyl group, and the like.

Among them, more than 50 mole% of the methyl groups are all R ^1, and more preferably 80 mol% or more, particularly well those accounts for at least 90 mol%, 25 mol% of the phenyl groups are all R ¹ or less, preferably 10 mol% The following (0 to 10 mol%) is desirable.

R ² in the general formula (2) is a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and is preferably a divalent hydrocarbon group from the viewpoint of chemical stability against hydrolysis or the like. Specific examples of the divalent hydrocarbon group include alkylene groups such as an ethylene group, a propylene group, a methylethylene group, and a tetramethylene group, with an ethylene group being preferred.

R ³ in the general formula (2) is 1 to 3, preferably 2 to 3, more preferably 3 (meth) acryloyl groups, that is, CH ₂ ═CHCO— and / or CH ₂ ═C (CH ₃ ) CO- is a monovalent organic group having, for example, a (meth) acryloyloxy group. Specific examples of the monovalent organic group containing this (meth) acryloyl group include CH ₂ = CHCOOCH ₂ CH _2- , [CH ₂ = C (CH ₃ ) COOCH ₂ ] ₃ C-CH _2- , (CH ₂ = CHCOOCH ₂ ) ₃ C-CH _2- , (CH ₂ = CHCOOCH ₂ ) ₂ C (C ₂ H ₅ ) CH _2- ,

等の、１〜３個の(メタ)アクリロイルオキシ基で置換された炭素原子数１〜10、好ましくは２〜６のアルキル基等が挙げられる。中でも好ましくは、[CH₂=C(CH₃)COOCH₂]₃C-CH₂-、(CH₂=CHCOOCH₂)₃C-CH₂-、(CH₂=CHCOOCH₂)₂C(C₂H₅)CH₂-および

And an alkyl group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, substituted with 1 to 3 (meth) acryloyloxy groups. Among them, [CH ₂ = C (CH ₃ ) COOCH ₂ ] ₃ C-CH _2- , (CH ₂ = CHCOOCH ₂ ) ₃ C-CH _2- , (CH ₂ = CHCOOCH ₂ ) ₂ C (C ₂ H ₅ ) CH ₂ -and

であり、更に好ましくは、[CH₂=C(CH₃)COOCH₂]₃C-CH₂-、(CH₂=CHCOOCH₂)₃C-CH₂-および

And more preferably [CH ₂ = C (CH ₃ ) COOCH ₂ ] ₃ C-CH _2- , (CH ₂ = CHCOOCH ₂ ) ₃ C-CH ₂ -and

である。

It is.

Specific examples of R ⁴ in the general formula (2) include the same as those exemplified as R ¹ in the general formula (1). However, as in the case of R ¹ , the methyl groups are all R ⁴ . It should occupy at least mol%, more preferably at least 80 mol%, especially at least 90 mol%, and the phenyl group is at most 25 mol%, preferably at most 10 mol% (0 to 10 mol%) of all R ¹ Things are desirable.

Specific examples of R ⁵ in the general formula (2) include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group and neopentyl group; cycloalkyl such as cyclohexyl group Groups: aryl groups such as phenyl groups; alkenyl groups such as allyl groups, propenyl groups, and butenyl groups, and the like, preferably non-aliphatic unsaturated groups such as alkenyl groups.

  Preferable specific examples of the organopolysiloxane represented by the general formula (1) include, for example, those represented by the following formula.

〔上記各式中、Ｒ'はメチル基、フェニル基または 3,3,3-トリフルオロプロピル基を表し、Ｌは前記のとおりである。〕

[In the above formulas, R ′ represents a methyl group, a phenyl group or a 3,3,3-trifluoropropyl group, and L is as defined above. ]

The organopolysiloxane of component (A) has —OR ³ groups as radiation polymerizable groups (that is, a plurality of, specifically 2 to 9, preferably 2 at each of both ends of the molecular chain). ˜6 (ie, 4-18, preferably 4-12 in a molecule) (meth) acryloyl group), this is ultraviolet, far ultraviolet, electron beam, X-ray The composition of the present invention can be easily polymerized by irradiation with radiation such as γ rays to cure the composition of the present invention. The organopolysiloxane of component (A) can be used alone or in combination of two or more.

  The (A) component organopolysiloxane can be prepared, for example, by a dehydrochlorination reaction between a corresponding chlorosiloxane and a (meth) acryloyl group-containing compound having an active hydroxyl group. Examples of the chlorosiloxanes include those represented by the following formula.

  Examples of the (meth) acryloyl group-containing compound having an active hydroxyl group include 2-hydroxylethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy-1- Examples include acryloyloxy-3-methacryloyloxypropane.

  The organopolysiloxane of the component (A) preferably has a plurality of (meth) acryloyl groups on one silicon atom described in the general formula (2). From this point of view, trimethylolpropane di (meta ) Acrylate and pentaerythritol tri (meth) acrylate are preferred, and pentaerythritol tri (meth) acrylate is particularly preferred.

[(B) Radiosensitizer]
The radiation sensitizer of the component (B) is not particularly limited, but is preferably a benzoyl compound (or phenyl ketone compound) such as benzophenone, particularly 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and other benzoyl compounds having a hydroxy group on the α-position carbon atom of the carbonyl group ( Or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyl monoorganophosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4, -trimethylpentylphosphine oxide, etc. Organophosphine oxide compounds; benzoin ether compounds such as isobutyl benzoin ether; Ketal compounds such as acetophenone diethyl ketal; thioxanthone compounds; acetophenone compounds, and the like. These can be used singly or in combination of two or more.

  The content of the component (B) in the composition of the present invention is not particularly limited as long as it is an amount effective for curing by irradiation with ultraviolet rays or the like of the composition of the present invention as a radiosensitizer. A) It is 0.1-10 weight part normally with respect to 100 weight part of components, Preferably it is 0.5-10 weight part, More preferably, it is 1.0-5.0 weight part.

[(C) Isocyanurate compound]
Formula of component (c) of the composition of the present invention: —SiR ⁶ ₃ (R ⁶ is independently an alkyl or alkoxy group having 1 to 8, preferably 1 to 6, more preferably 1 to 4 carbon atoms) An isocyanurate compound having 1 to 3, preferably 2 to 3 triorganosiloxy groups represented by the following formula and / or a hydrolysis condensate thereof (that is, an organopolysiloxane-modified isocyanurate compound) is vinyl Group, isocyanurate having an alkenyl group such as allyl group, and hydrogenation organosilane such as trialkylsilane or trialkoxysilane having a hydrogen atom (SiH) bonded to a silicon atom in the presence of a platinum catalyst. (See Japanese Patent Publication No. 45-233544, US Pat. No. 3,821,218, US Pat. No. 3,517,001) ).

R ⁶ is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, an octyl group, or 2-ethylhexyl; a cycloalkyl group such as a cyclohexyl group An alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a tert-butoxy group;

  Examples of the isocyanurate compound of component (C) include isocyanurates having 1 to 3 trialkoxysilyl-substituted alkyl groups such as γ-trimethoxypropyl group and γ-triethoxypropyl group in one molecule, and Those obtained by hydrolytic condensation of these trialkoxysilyl groups (that is, organopolysiloxane-modified isocyanurate) can be exemplified, and specifically, those represented by the following formula can be exemplified.

（上記各式中、Ｒは独立に水素、アルキル基、アラルキル基、低級アルケニル基、アリール基、または複素環式アリール基である。）
この(C)成分は、１種単独でも２種以上を組み合わせても使用することができる。

(In the above formulas, R is independently hydrogen, an alkyl group, an aralkyl group, a lower alkenyl group, an aryl group, or a heterocyclic aryl group.)
This component (C) can be used alone or in combination of two or more.

This component (C) functions as an adhesion aid, and the compounding of this component can improve the adhesion to various substrates such as metal substrates, plastic substrates, ceramic substrates, and glass substrates. It becomes possible.
The content of the component (C) in the composition of the present invention is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 100 parts by weight of the component (A). 5 parts by weight.

[(D) Titanium-containing organic compound]
In the composition of the present invention, in addition to the components (A) to (C), as an optional component to be blended as necessary, (D) at least selected from the group consisting of a titanate compound and a titanium chelate compound A kind of titanium-containing organic compound can be blended. The titanium-containing organic compound selected from the group consisting of the titanate compound of component (D) and the titanium chelate compound is cured by radiation irradiation in combination with the isocyanurate compound of component (C) that functions as an adhesion aid. In this case, it is a component that quickly develops adhesiveness to various substrates.

As the component (D), for example, the formula: (R ⁷ O) _p Ti (OSiR ⁸ R ⁹ R ¹⁰ ) _4-p (wherein R ⁷ has 1 to 8 carbon atoms, preferably 2 to 4 carbon atoms). R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl or alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and p is an integer of 0 to 4). The compound which is made is mentioned. Examples of R ⁷ and R ^{8 to} R ¹⁰ include the same alkyl groups and alkoxy groups as exemplified above for R ⁶ .

Specific examples of the compound represented by the above formula include, for example, tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetrahexyl titanate, tetra (2-ethylhexyl) titanate and the like. (C ₃ H ₇ O) ₃ TiOSi (CH ₃ ) (OC ₃ H ₇ ) ₂ , (C ₃ H ₇ O) ₃ TiOSi (CH ₃ ) ₂ (OC ₃ H ₇ ), [(CH ₃ ) ₃ SiO] ₃ TiOSi (CH ₃ ) ₂ (OC ₃ H ₇ ), [(CH ₃ ) ₃ SiO] ₄ Ti and other trialkylsiloxy groups, alkoxydialkylsiloxy groups, trialkoxysiloxy groups, alkyldialkoxysiloxy groups And a titanium compound having a triorganosiloxy group.

  Examples of the component (D) further include titanium chelate compounds having a ligand derived from acetylacetone, methyl acetoacetate or ethyl acetoacetate. The titanium chelate compound preferably has a silicon atom-containing group together with the ligand, and a silicon atom in the silicon atom-containing group is bonded to the titanium atom via an oxygen atom. Specific examples of the titanium chelate compound include the following.

（式中、ｎは２〜100の整数である）

(Where n is an integer from 2 to 100)

This component (D) can be used alone or in combination of two or more.
The content of the component (D) in the composition of the present invention is 20 parts by weight or less (that is, 0 to 20 parts by weight) with respect to 100 parts by weight of the component (A) as necessary. Usually, it is 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

[Other ingredients]
In addition to the components (A) to (D), it is optional to add other components to the composition of the present invention as long as the objects and effects of the present invention are not impaired. For example, for the purpose of appropriately adjusting the shrinkage ratio at the time of curing and the thermal expansion coefficient, mechanical strength, heat resistance, chemical resistance, flame resistance, fuel expansion coefficient, gas permeability, etc. of the resulting cured product You may mix | blend an additive.

For the purpose of further improving the adhesive strength of the resulting cured product, (E) alkoxysilane and / or a partially hydrolyzed condensate thereof can be blended. Examples of the alkoxysilane include tetraalkoxysilanes represented by the formula: Si (OR ¹¹ ) ₄ (wherein R ¹¹ is an unsubstituted or alkoxy-substituted alkyl group having 1 to 4 carbon atoms). Can do. Examples of R ¹¹ include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups and other alkyl groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, and the like. Examples include an alkoxy-substituted alkyl group, preferably a methyl group or an ethyl group. The partial hydrolysis-condensation product of alkoxysilane is a siloxane compound (number of silicon atoms) produced by hydrolysis-condensation reaction of the alkoxy group in which at least one, preferably two or more alkoxy groups remain in the molecule. 2 to 100, preferably about 2 to 30 siloxane oligomers).

  This component (E) can be used alone or in combination of two or more. Moreover, when mix | blending with the composition of this invention, the content is 10 parts weight or less (namely, 0-10 weight part) with respect to 100 weight part of (A) component, Usually, 0.5-10 weight part, Preferably it is about 0.5 to 5.0 parts by weight.

  In addition, for example, inorganic fillers such as fumed silica, silica airgel, quartz powder, glass fiber, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate; hydroquinone, methoxyhydroquinone, 2,6-di-tert- A radical polymerization inhibitor (pot life extending agent) such as butyl-p-cresol may be blended.

[Preparation and Curing of Composition]
It can be obtained by mixing the above components (A) to (D) of the present invention and, if necessary, other blending components. The obtained composition is rapidly cured by irradiating it with radiation to give a rubber-like elastic body that exhibits strong adhesiveness immediately after curing.

Examples of radiation to be irradiated include ultraviolet rays, far-infrared rays, electron beams, X-rays, γ rays and the like, but it is preferable to use ultraviolet rays from the viewpoint of ease of handling and easy handling. Examples of the light source that emits ultraviolet light include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a xenon lamp. UV (peak wavelength: 320~390nm) dose of, for example, a composition of the present invention for those that have been formed in the thickness 2mm, 200~2,400mJ / cm ^2, is preferably 400~1,600mJ / cm ² .

[Usage]
The cured product obtained from the composition of the present invention has excellent adhesion to substrates such as silicon, silicon oxide film, glass, aluminum, polyimide (for example, Kapton (trade name, manufactured by DuPont), polycarbonate, epoxy resin, etc. In addition, it exhibits excellent adhesion to metal substrates such as Ni, Cr, Ag, Au, etc., which have poor adhesion, so that it is an electrode sealant for electronic parts (for example, liquid crystal devices), and a hybrid IC. It is useful as a coating material for various electronic components such as an electronic component mounting circuit that cannot be heated and cured at a high temperature, and it is possible to improve productivity by shortening the curing process.

  Hereinafter, the present invention will be described with reference to synthesis examples and examples. In the following, “parts” represents parts by weight.

(Synthesis example)
In a 1,000 mL reactor equipped with a stirrer, reflux condenser, dropping funnel and dry air introducer, (A) the following average general formula:

で示されるオルガノポリシロキサン 571ｇ、2-ヒドロキシ-1-アクリロイルオキシ-3-メタクリロイルオキシプロパン（商品名：ＮＫエステル701−A、新中村化学工業(株)製）47ｇ、トルエン 200mL、トリエチルアミン 26ｇ、および重合禁止剤としてジブチルヒドロキシトルエン（2,6-ジ-tert-ブチル-p−クレゾール）2,000ppmとを仕込み、これらを攪拌しながら、70℃に昇温して７時間加熱した。その後、放冷し、濾過し、得られたろ液に中和剤としてプロピレンオキサイド４ｇを添加し室温にて１時間攪拌した。その後、100℃/30mmHgの条件でストリップを行って、次式で示される透明なオイル状のオルガノポリシロキサンを得た。

571 g, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane (trade name: NK ester 701-A, manufactured by Shin-Nakamura Chemical Co., Ltd.) 47 g, toluene 200 mL, triethylamine 26 g, and As a polymerization inhibitor, 2,000 ppm of dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol) was charged, and while stirring these, the temperature was raised to 70 ° C. and heated for 7 hours. Thereafter, the mixture was allowed to cool and filtered, and 4 g of propylene oxide was added as a neutralizing agent to the obtained filtrate, followed by stirring at room temperature for 1 hour. Thereafter, stripping was performed under the conditions of 100 ° C./30 mmHg to obtain a transparent oily organopolysiloxane represented by the following formula.

[Example 1]
(A) 100 parts of an oily organopolysiloxane obtained in Synthesis Example 1, (B1) 2 parts of 2-hydroxy-2-methyl-1-phenylpropane-1-one, (B2) 2,4,6-trimethyl 1 part of benzoyldiphenylphosphine oxide, (C1)

で示されるイソシアヌレート化合物１部、および(D)下記式：

1 part of an isocyanurate compound represented by: and (D) the following formula:

で示されるチタンキレート化合物 0.1部を混合して、放射線硬化性オルガノポリシロキサン組成物を得た。

A radiation-curable organopolysiloxane composition was obtained by mixing 0.1 part of a titanium chelate compound represented by the formula:

This composition is poured into a mold having a depth of 1 mm, a width of 120 mm, and a length of 170 mm, and irradiated with ultraviolet rays for 2 seconds (energy amount: 800 mJ) in a conveyor furnace equipped with two metal halide mercury lamps (illuminance: 80 W / cm ² ). A cured product was obtained.

<Various performance evaluation>
-Physical property About the obtained hardened | cured material, the physical property (hardness, elongation, and tensile strength) was measured based on JISK6301 (In addition, hardness was measured with the spring type A type testing machine). The results are shown in Table 1.
-Adhesiveness Moreover, after apply | coating the said composition on each board | substrate made from a silicon | silicone, a silica, glass, aluminum, a polyimide (brand name, Kapton), and chromium to 2 mm in thickness of 2 cm x 2 cm, the said It was cured by irradiation with ultraviolet rays under irradiation conditions (illuminance: 80 W / cm ² , energy amount: 800 mJ). After being allowed to stand at room temperature for 1 hour after curing, the adhesion of the obtained cured film to each substrate was evaluated as follows. The results are shown in Table 1.

I grabbed one end of the cured film with tweezers and tried to peel off the film. It was evaluated as follows by observing the peeling state or not.
In the case of complete adhesion and inability to peel (cohesive failure rate: 90% or more), the adhesiveness was evaluated as good and indicated by ◯.
When a part of the film peeled off (cohesive failure rate: 20% or more and less than 90%), the adhesiveness was evaluated as slightly poor and indicated by Δ.
When all peeled completely (cohesive failure rate: less than 20%), the adhesiveness was evaluated as poor and indicated by x.

-Storage stability In order to evaluate the storage stability of the obtained composition, the composition was allowed to stand at 5 ° C and 25 ° C, and the change in viscosity with time was measured. The results are shown in Table 2.

[Example 2]
Instead of the (C1) isocyanurate compound described in Example 1, (C2) the following formula:

で示されるイソシアヌレート化合物１重量部を用いること、および、更に(E)テトラメトキシシランの部分加水分解縮合物（メトキシシロキサンオリゴマー）１部を追加したこと以外は、実施例１と同様にして組成物を調製し、実施例１と同様の試験を行った。その結果を表１および表２に示す。

The composition was the same as in Example 1 except that 1 part by weight of the isocyanurate compound represented by the formula (1) and 1 part of (E) tetramethoxysilane partially hydrolyzed condensate (methoxysiloxane oligomer) were added. A product was prepared and tested in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Example 3]
Instead of the (C1) isocyanurate compound described in Example 1, (C3) the following formula:

で示されるイソシアヌレート化合物１重量部を用いること、および、更に(E)テトラメトキシシランの部分加水分解縮合物（メトキシシロキサンオリゴマー）１部を追加したこと以外は、実施例１と同様にして組成物を調製し、実施例１と同様の試験を行った。その結果を表１および表２に示す。

The composition was the same as in Example 1 except that 1 part by weight of the isocyanurate compound represented by the formula (1) and 1 part of (E) tetramethoxysilane partially hydrolyzed condensate (methoxysiloxane oligomer) were added. A product was prepared and tested in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Comparative Example 1]
A composition was prepared in the same manner as in Example 1 except that the (C1) isocyanurate compound described in Example 1 was not used, and this composition was tested in the same manner as in Example 1. The results are shown in Tables 1 and 2.

（注）粘度単位：Ｐａ・ｓ

(Note) Viscosity unit: Pa · s

Claims (13)

(A) The following general formula (1):

[Wherein, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 9 carbon atoms,
X is independently the following general formula (2):

{In the formula, R ² represents a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and R ³ independently represents the following general formula:

(In the formula, R is a hydrogen atom or a methyl group)
A monovalent organic group having 4 to 25 carbon atoms and having 1 to 3 acryloyl groups and / or methacryloyl groups, and R ⁴ is independently an unsubstituted or substituted 1 having 1 to 9 carbon atoms. R ⁵ is independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, n is 1 to 3, m is 0 to 2, and the sum of n + m is an integer of 1 to 3. is there. However, when n = 1, the R ³ is an organic group having 2 to 3 acryloyl groups and / or methacryloyl groups. } And L is an integer of 8 to 10,000.
An organopolysiloxane represented by
(B) radiosensitizer ,
(C) An isocyanurate compound having a triorganosilyl group represented by the formula: —SiR ⁶ ₃ (wherein R ⁶ is independently an alkyl group or alkoxy group having 1 to 8 carbon atoms) and / or its hydrolytic condensation. Thing , as well as
(D) A cured silicone rubber obtained by irradiating a radiation curable silicone rubber composition containing at least one titanium-containing organic compound selected from the group consisting of a titanate compound and a titanium chelate compound. Electronic parts that are sealed or coated. The electronic component according to claim 1, wherein R ^{3 in the} general formula (2) of the component (A) is an alkyl group having 2 to 3 acryloyloxy groups and / or methacryloyloxy groups. The titanium-containing organic compound as the component (D) has the formula: (R ⁷ O) _p Ti (OSiR ⁸ R ⁹ R ¹⁰ ) _4-p (wherein R ⁷ is an alkyl group having 1 to 8 carbon atoms). , R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms, and p is an integer of 0 to 4), and acetylacetone and acetoacetic acid A complex having a ligand derived from methyl or ethyl acetoacetate, and a complex having a silicon atom-containing group and having a silicon atom bonded to a titanium atom via an oxygen atom it is a compound selected from the group, the electronic component of claim 1, wherein. The radiation curable silicone rubber composition is used in an amount of 0.1 to 10 parts by weight of the component (B), 0.1 to 20 parts by weight of the component (C), and 100 parts by weight of the component (A). The electronic component according to any one of claims 1 to 3 , comprising 0.001 to 20 parts by weight of component (D). The electronic component according to claim 4 , wherein the radiation curable silicone rubber composition further comprises (E) 0 to 10 parts by weight of alkoxysilane and / or a partial hydrolysis condensate thereof. The radiation UV, far infrared, electron beam, selected from X-rays and γ-rays, any one electronic component according to claim 1-5. (A) The following general formula (1):

[Wherein, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 9 carbon atoms,
X is independently the following general formula (2):

{In the formula, R ² represents a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and R ³ independently represents the following general formula:

(In the formula, R is a hydrogen atom or a methyl group)
A monovalent organic group having 4 to 25 carbon atoms and having 1 to 3 acryloyl groups and / or methacryloyl groups, and R ⁴ is independently an unsubstituted or substituted 1 having 1 to 9 carbon atoms. R ⁵ is independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, n is 1 to 3, m is 0 to 2, and the sum of n + m is an integer of 1 to 3. is there. However, when n = 1, the R ³ is an organic group having 2 to 3 acryloyl groups and / or methacryloyl groups. } And L is an integer of 8 to 10,000.
An organopolysiloxane represented by
(B) radiosensitizer ,
(C) An isocyanurate compound having a triorganosilyl group represented by the formula: —SiR ⁶ ₃ (R ⁶ is independently an alkyl group or alkoxy group having 1 to 8 carbon atoms) and / or its hydrolytic condensation. Thing , as well as
(D) Radiation is applied to an electronic component coated or potted with a radiation curable silicone rubber composition containing at least one titanium-containing organic compound selected from the group consisting of a titanate compound and a titanium chelate compound. A method for sealing or coating an electronic component, comprising curing the composition. The method according to claim 7 , wherein R ^{3 in the} general formula (2) of the component (A) is an alkyl group having 2 to 3 acryloyloxy groups and / or methacryloyloxy groups. The titanium-containing organic compound as the component (D) has the formula: (R ⁷ O) _p Ti (OSiR ⁸ R ⁹ R ¹⁰ ) _4-p (wherein R ⁷ is an alkyl group having 1 to 8 carbon atoms). , R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms, and p is an integer of 0 to 4), and acetylacetone and acetoacetic acid A complex having a ligand derived from methyl or ethyl acetoacetate, and a complex having a silicon atom-containing group and having a silicon atom bonded to a titanium atom via an oxygen atom The method according to claim 7 , which is a compound selected from the group. The radiation curable silicone rubber composition is used in an amount of 0.1 to 10 parts by weight of the component (B), 0.1 to 20 parts by weight of the component (C), and 100 parts by weight of the component (A). The method according to any one of claims 7 to 9 , comprising 0.001 to 20 parts by weight of component (D). The method according to claim 10 , wherein the radiation curable silicone rubber composition further comprises (E) 0 to 10 parts by weight of an alkoxysilane and / or a partial hydrolysis condensate thereof. The method according to claim 7 , wherein the radiation is selected from ultraviolet rays, far infrared rays, electron beams, X-rays and γ rays. (A) The following general formula (1):

[Wherein, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 9 carbon atoms,
X is independently the following general formula (2):

{In the formula, R ² represents a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and R ³ independently represents the following general formula:

(In the formula, R is a hydrogen atom or a methyl group)
A monovalent organic group having 4 to 25 carbon atoms and having 1 to 3 acryloyl groups and / or methacryloyl groups, and R ⁴ is independently an unsubstituted or substituted 1 having 1 to 9 carbon atoms. R ⁵ is independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, n is 1 to 3, m is 0 to 2, and the sum of n + m is an integer of 1 to 3. is there. However, when n = 1, the R ³ is an organic group having 2 to 3 acryloyl groups and / or methacryloyl groups. } And L is an integer of 8 to 10,000.
An organopolysiloxane represented by
(B) radiosensitizer ,
(C) An isocyanurate compound having a triorganosilyl group represented by the formula: —SiR ⁶ ₃ (R ⁶ is independently an alkyl group or alkoxy group having 1 to 8 carbon atoms) and / or its hydrolytic condensation. Thing , as well as
(D) A cured silicone rubber coating obtained by irradiating a radiation curable silicone rubber composition containing at least one titanium-containing organic compound selected from the group consisting of a titanate compound and a titanium chelate compound .