JP5766657B2 - Silicone resin composition - Google Patents

Description

  The present invention relates to a silicone resin composition that can be cured sufficiently in a short period of time even when irradiated with low energy radiation, and provides a cured product having excellent moisture resistance. The present invention relates to a silicone resin composition suitable as a stopper.

  Organopolysiloxane compositions that cure by irradiation with radiation such as ultraviolet light are already known. For example, Patent Document 1 describes a radiation-curable optical fiber coating agent containing a vinyl functional group-containing organopolysiloxane and a photopolymerization initiator. However, when a part is coated with the coating agent and allowed to stand with a liquid, the coating agent may flow into the device and contaminate the device.

  As a composition that has improved such drawbacks, Patent Document 2 discloses a specific organopolysiloxane having a radiation-functional (meth) acryloyl group at both ends of a molecular chain, a photosensitizer, a tetraalkylsilane, or a partial hydrolyzate thereof. An organopolysiloxane composition containing a decomposition condensate is described. However, the composition has not been able to adequately answer the recent demand for high curing speed and the demand for low illumination during irradiation. In addition, the organopolysiloxane composition does not have sufficient moisture resistance, and is insufficient for use as a coating material for protecting liquid crystal electrodes, organic EL electrodes, and plasma display electrodes that are easily affected by humidity and the like. there were.

  In Patent Document 3, an organosiloxane resin having a (meth) acryl group and a phenyl ester derivative having an acrylic group are included in a molecule as a composition that can be cured quickly and sufficiently by simply irradiating a small amount of radiation for a short time. A radiation curable composition is described. Patent Document 4 describes a cycloalkyl group-containing silicone resin composition as an organopolysiloxane having low water vapor permeability.

Japanese Patent Publication No. 4-25231 JP-A-11-302348 JP 2012-97251 A JP 2012-7002 A

  However, the composition described in Patent Document 3 does not have sufficient curability for irradiation with low energy radiation, and the resulting cured product has insufficient moisture resistance. Moreover, since the silicone resin composition of patent document 4 hardens | cures by hydrosilylation, a comparatively high temperature (about 100-150 degreeC) is required for hardening. Therefore, it cannot be applied to electronic devices or resin casings that are vulnerable to heat.

  The present invention has been made in order to solve the above problems, and is a silicone resin that can be sufficiently cured even when irradiated with a small amount of radiation for a short time and that provides a cured product having excellent moisture resistance. An object is to provide a composition. Another object of the present invention is to provide a highly reliable device, in particular, an electric device and an electronic device, in which corrosion of a base material and electric / electronic parts is suppressed. In the present invention, “radiation” means all electromagnetic waves and particle beams in a broad sense, and includes ionizing radiation (electron beams, X-rays, γ rays, ultraviolet rays having a short wavelength, etc.) and non-ionizing radiations (near ultraviolet rays, Including far infrared rays).

  As a result of intensive studies to solve the above problems, the present inventors have found that a silicone resin composition containing an organopolysiloxane represented by the following general formula (1) is short even when irradiated with low energy radiation. It has been found that the cured product can be sufficiently cured in time and the obtained cured product has sufficient moisture resistance, and has led to the present invention.

（１）
（式（１）中、Ｒ^１は、互いに独立に、炭素数４〜８のシクロアルキル基であり、Ｒ^２は−ＯＸで示される基であり、Ｘは、互いに独立に、アクリル基又はメタクリル基を有する１価の有機基であり、Ｒ^３は、互いに独立に、シクロアルキル基でない、置換もしくは非置換の、炭素数１〜１０の一価炭化水素基であり、Ｑは、互いに独立に、酸素原子又は炭素数１〜１０のアルキレン基であり、ａ、ｂ、ｃは、互いに独立に、０〜３の整数であり、但しケイ素原子ごとにａ、ｂ、ｃは夫々ａ＋ｂ＋ｃ＝３を満たし、ｄは、互いに独立に、１または２の整数であり、ｅは、互いに独立に、０または１の整数であり、但しケイ素原子ごとにｄ、ｅは夫々ｄ＋ｅ＝２を満たし、ｎは０〜４０の整数であり、Ｒ^４は、互いに独立に、Ｒ ^１ 及びＲ^３の選択肢の中から選ばれる基であり、上記式（１）におけるＲ ^４ の少なくとも１がＲ ^１ の選択肢の中から選ばれる基であり、Ｒ^５は、互いに独立に、下記式（２）で表される基であり、

（２）
式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｑ、ａ、ｂ、ｃ、ｄ、及びｅは上記の通りであり、ｍは０〜１５の整数であり、
但し、該オルガノポリシロキサンは１分子中に少なくとも１のＲ ^２を有する）、及び
（Ｂ）光重合開始剤 （Ａ）成分を硬化させる有効量
を含有する、シリコーン樹脂組成物及び該シリコーン樹脂組成物を硬化して得られる硬化物を備える装置を提供する。 That is, the present invention
(A) Organopolysiloxane represented by the following general formula (1)

(1)
(In the formula (1), ^{R 1} are each independently a cycloalkyl group having 4 to 8 carbon atoms, ^{R 2} is a group represented by -OX, X, independently of one another, acryl or methacryl R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms that is not a cycloalkyl group and is a substituted or unsubstituted cycloalkyl group, and Q is independently of each other. , An oxygen atom or an alkylene group having 1 to 10 carbon atoms, a, b and c are each independently an integer of 0 to 3, provided that a, b and c are each a + b + c = 3 for each silicon atom. D is an integer of 1 or 2 independently of each other, e is an integer of 0 or 1 independently of each other, provided that d and e satisfy d + e = 2 for each silicon atom, and n is is an integer of 0 to 40, ^{R 4,} independently of one another, ^{R 1} 及 beauty ^{R 3} Wherein at least one of R ⁴ in the above formula (1) is a group selected from the options of R ¹ , and R ⁵ is independently selected from the following formula (2): A group represented by

(2)
In formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Q, a, b, c, d, and e are as described above, m is an integer of 0 to 15,
However, the organopolysiloxane has at least one R ² in one molecule), and (B) a photopolymerization initiator (A) a silicone resin composition and an silicone resin composition containing an effective amount for curing the component An apparatus including a cured product obtained by curing an object is provided.

  The silicone resin composition of the present invention can be sufficiently cured even when irradiated with low energy radiation for a short time, and the obtained cured product can have sufficient moisture resistance. Therefore, a cured film having an effect of suppressing corrosion of the base material and the electric / electronic parts can be formed, and an apparatus having excellent reliability, in particular, an electric apparatus and an electronic apparatus can be provided. In particular, since the composition of the present invention is easily cured by irradiation with a small amount of energy, it is a protective coating agent for liquid crystal electrodes, organic EL electrodes, flat panel display electrodes, plasma display electrodes and the like that are easily affected by radiation such as ultraviolet rays. It is useful as a protective coating agent or sealant for various electric and electronic parts.

  Hereinafter, the present invention will be described in detail. In addition, the term (meth) acryloyl, (meth) acryl, and (meth) acrylate described in this specification means acryloyl and / or methacryloyl, acrylic and / or methacryl, acrylate, and / or methacrylate in this order. . “Me” means a methyl group.

[(A) Organopolysiloxane]
(A) The organopolysiloxane is represented by the following general formula (1), and has at least 1, preferably 1 to 80, more preferably 2 to 60, and still more preferably 2 to 20 cyclohexane per molecule. Has an alkyl group. The (A) organopolysiloxane has at least 1, preferably 2 to 20, more preferably 2 to 10 monovalent organic groups having an acryl group or a methacryl group in one molecule.

In the above formula (1), R ¹ is independently a cycloalkyl group having 4 to 8 carbon atoms, preferably 5 to 6 carbon atoms, and particularly preferably a cyclohexyl group. R ³ independently of each other is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which is not a cycloalkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Alkyl groups such as isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; benzyl group, phenylethyl group , An aralkyl group such as a phenylpropyl group and a hydrogen atom bonded to a carbon atom of these groups partially or entirely substituted with a halogen atom, a cyano group, etc., such as a chloromethyl group, a cyanoethyl group, a trifluoropropyl group, etc. A halogen-substituted alkyl group, and a cyanoethyl group. Among them, R ³ is preferably a methyl group.

R ² is a group represented by —OX, and X is a monovalent organic group having an acrylic group or a methacryl group independently of each other. Examples of such X include a monovalent organic group having a (meth) acryloyloxy group, and a part of hydrogen atoms bonded to carbon atoms are substituted with 1 to 3 (meth) acryloyloxy groups. And an alkyl group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms.

As said X, the group shown below is mentioned, for example.

Of these, the groups shown below are preferred.

More preferred are the groups shown below.

  In the above formula (1), Q independently represents an oxygen atom or an alkylene group having 1 to 10 carbon atoms, preferably an oxygen atom or an alkylene group having 2 to 6 carbon atoms. Examples of the alkylene group include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group, heptylene group, octylene group, and nonylene group.

In the above formula (1), a, b and c are each independently an integer of 0 to 3, preferably b is an integer of 1 to 3, a and c are integers of 0 to 2, provided that For each silicon atom, a, b and c satisfy a + b + c = 3. In particular, it is preferable that a is 0, b is 1, and c is 2. d and e are each independently an integer of 0 to 2, preferably d is an integer of 1 or 2, e is an integer of 0 or 1, provided that d and e are each silicon atom. d + e = 2 is satisfied. n is an integer of 0 to 40, preferably an integer of 1 to 30, more preferably an integer of 2 to 10. Note that n may be an average value. The organopolysiloxane represented by the above formula (1) has at least one R ¹ and R ² in one molecule.

上記式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｑ、ａ、ｂ、ｃ、ｄ、及びｅは上記の通りである。中でも、式（２）においてａが０であり、ｂが１であり、ｃが２であるのが好ましい。また、式（２）においてｄが２であり、ｅが０であるのが好ましい。また、式（２）においてＲ^４がＲ^３の選択肢の中から選ばれる基であるのが好ましい。ｍは０〜１５の整数、好ましくは１〜１０の整数である。尚、ｍは平均値であってよい。特には、式（１）及び（２）においてａが０であり、ｂが１であり、ｃが２であるのが好ましい。また、式（２）においてａが０であり、ｂが１であり、ｃが２であり、かつ、式（１）においてａが０であり、ｂが０であり、ｃが３であるオルガノポリシロキサンも好適である。 In the formula (1), R ⁴ is a group independently selected from the options of R ¹ , R ² and R ³ . Preferably, R ⁴ is a group selected from the options of R ¹ and R ³ , and more preferably, at least one of R ⁴ is a group selected from the options of R ¹ , that is, a cycloalkyl group. R ⁵ is independently a group represented by the following formula (2).

In the above formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Q, a, b, c, d, and e are as described above. Among these, in formula (2), it is preferable that a is 0, b is 1, and c is 2. In the formula (2), d is 2 and e is preferably 0. In the formula (2), R ⁴ is preferably a group selected from the options of R ³ . m is an integer of 0-15, preferably an integer of 1-10. Note that m may be an average value. In particular, in formulas (1) and (2), it is preferable that a is 0, b is 1, and c is 2. In the formula (2), a is 0, b is 1, c is 2, and in formula (1), a is 0, b is 0, and c is 3. Polysiloxane is also suitable.

（Ｒ^３及びＸは上記の通りであり、ｎは平均値であってよい１〜１０の整数である。）

（Ｒ^３及びＸは上記の通りであり、ｎは平均値であってよい１〜１０の整数である。）

（Ｒ^３及びＸは上記の通りであり、ｎ^１、ｎ^２は、互いに独立に、平均値であってよい１〜１０の整数である。） The organopolysiloxane represented by the above formula (1) is preferably the following organopolysiloxane.

(R ³ and X are as described above, and n is an integer of 1 to 10, which may be an average value.)

(R ³ and X are as described above, and n is an integer of 1 to 10, which may be an average value.)

(R ³ and X are as described above, and n ¹ and n ² are each independently an integer of 1 to 10, which may be an average value.)

The organopolysiloxane represented by the above formula (1) is, for example, an organohydrogenpolysiloxane represented by the following general formula (3) R ¹ _p (R ³ ) _q (H) _r SiO _{(4-pq -R / 2)} (3)
(Wherein R ¹ and R ³ are as described above, p is a number satisfying 0 <p ≦ 1.4, preferably 0 <p ≦ 1.0, and q is 0.6 ≦ q ≦ 2. 5, preferably 0.8 ≦ q ≦ 2.0, r is a number 0.05 ≦ r ≦ 1.0, preferably 0.09 ≦ r ≦ 0.8, provided that p + q + r = 1 The position of the SiH group in the molecule is not particularly limited and may be at the end of the molecular chain or in the middle.
And a (meth) acrylate derivative represented by the following general formula (4): R ⁷ _s R ⁶ _t Si (OX) _4- st (4)
(Wherein R ⁶ is an alkenyl group having 2 to 8 carbon atoms, X is as described above, R ⁷ is a group selected from the options of R ¹ and R ³ above, and s is 0 to 0 2 is an integer of 2 and t is an integer of 1 to 3, provided that s + t is 1 to 3.)
Can be produced by hydrosilylation reaction in the presence of a platinum catalyst. The hydrosilylation reaction may be performed according to a conventionally known method.

The molecular structure of the organohydrogenpolysiloxane represented by the general formula (3) may be either a linear structure or a branched structure. For example, tris (dimethylhydrogensiloxy) cyclohexylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,3-dimethyl-1,3dicyclohexyldisiloxane, trimethylsiloxy group-blocked cyclohexylmethylpolysiloxane / methylhydrogenpolysiloxane at both ends Siloxane copolymer, trimethylsiloxy group-capped dimethylsiloxane / cyclohexyl hydrogensiloxane copolymer, trimethylsiloxy group-capped dimethylpolysiloxane / cyclohexylmethylpolysiloxane / methylhydrogenpolysiloxane copolymer, both end dimethylhydro Jensiloxy group-blocked cyclohexylmethyl polysiloxane, both ends dimethylhydrogensiloxy group-blocked dicyclohexyl polysiloxane Sun, both terminals with dimethylhydrogensiloxy group dimethylsiloxane-cyclohexyl methylpolysiloxane _{copolymer, (CH} 3) 2 _{HSiO 1/2} units and _{(CH 3)} and _{2 SiO 2/2} units _{(C 6} H 11) SiO _A copolymer comprising _3/2 units, a copolymer comprising (CH ₃ ) ₂ HSiO _1/2 units and (C ₆ H ₁₁ ) SiO _3/2 units, (CH ₃ ) (C ₆ H ₁₁ ) A copolymer comprising HSiO _1/2 units and SiO _4/2 units, a copolymer comprising (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units and (C ₆ H ₁₁ ) HSiO _3/2 units. A polymer etc. are mentioned.

（式中、ｎは１〜１０の整数）

（式中、ｎ^１、ｎ^２は、互いに独立に、１〜１０の整数）

（式中、ｎ^１、ｎ^２は、互いに独立に、１〜１０の整数）

（式中、ｎ^１、ｎ^２、ｎ^３は、互いに独立に、１〜１０の整数）

Among these, the organohydrogenpolysiloxane shown below is preferable.

(Where n is an integer from 1 to 10)

(Wherein n ¹ and n ² are each independently an integer of 1 to 10)

(Wherein n ¹ and n ² are each independently an integer of 1 to 10)

(Wherein n ¹ , n ² and n ³ are each independently an integer of 1 to 10)

（式中、Ｒ^６、Ｒ^７、及びＸは上記の通り。） Examples of the (meth) acrylate derivative represented by the above formula (4) include the following.

(Wherein R ⁶ , R ⁷ , and X are as described above.)

The (meth) acrylate derivative may be produced by a conventionally known method. For example, it can be produced by dehydrochlorination of a chlorosilane having an alkenyl group and a (meth) acrylate compound having a hydroxyl group represented by X—OH (X is as described above).

（式中、Ｒ^６、及びＲ^７は上記の通り。） The following are mentioned as a chlorosilane which has an alkenyl group.

(Wherein R ⁶ and R ⁷ are as described above.)

As the (meth) acrylate derivative represented by the above formula (4), the following are particularly preferable.

  (A) Since the organopolysiloxane has an organic group having a (meth) acryl group, it is easily polymerized by irradiation with radiation such as ultraviolet rays, far infrared rays, electron beams, X rays, or γ rays. It can be cured. (A) Organopolysiloxane may be used individually by 1 type, or may be used in combination of 2 or more type.

[(B) Photopolymerization initiator]
(B) The photoinitiator should just advance the photopolymerization reaction of the organopolysiloxane which has a (meth) acryl group, A conventionally well-known thing can be used. For example, a benzoyl compound (or phenyl ketone compound) such as benzophenone can be suitably used. Among them, carbonyls such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, etc. A benzoyl compound (or phenyl ketone compound) having a hydroxy group on the α-position carbon atom of the group is preferred. Other photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyl monoorganophosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4, -trimethylpentylphos Organophosphine oxide compounds such as fin oxide; benzoin ether compounds such as isobutyl benzoin ether; ketal compounds such as acetophenone diethyl ketal; thioxanthone compounds; and acetophenone compounds can be used. Examples of commercially available products include IRUGACURE (registered trademark) series (BASF) and KAYACURE (registered trademark) series (Nippon Kayaku Co., Ltd.). The said (B) photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the component (B) may be an amount effective for curing the component (A). The amount effective to cure the component (A) is an amount effective to cure the component (A) by polymerization reaction upon irradiation. In particular, 0.1-100 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.1-10 mass parts, More preferably, it is 0.5-10 mass parts, Most preferably, 1 0.0 to 5.0 parts by mass.

[Other ingredients]
In addition to the above components (A) and (B), the silicone resin composition of the present invention can be appropriately mixed with other components as long as the objects and effects of the present invention are not impaired. For example, various additions for adjusting the shrinkage ratio during curing and the thermal expansion coefficient, mechanical strength, heat resistance, chemical resistance, flame resistance, thermal expansion coefficient, gas permeability, etc. of the resulting cured product An agent may be blended.

  Examples of the other components include 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- A radical polymerization inhibitor (pot life extending agent) such as tert-butyl-p-cresol can be blended.

Preparation Method of Silicone Resin Composition The silicone resin composition of the present invention comprises the above component (A), component (B), and other components as necessary, stirring and mixing, etc. while subjecting to heat treatment as necessary. Can be obtained. Although the apparatus used for operations, such as stirring, is not specifically limited, A raikai machine provided with stirring and a heating apparatus, 3 rolls, a ball mill, a planetary mixer etc. can be used. Moreover, you may combine these apparatuses suitably. The silicone resin composition of the present invention can be quickly cured by irradiation with radiation, and the obtained curing agent has excellent moisture resistance.

As the radiation applied to the silicone resin composition of the present invention, ultraviolet rays, far infrared rays, electron beams, X rays, γ rays and the like can be used. Among these, it is preferable to use ultraviolet rays from the viewpoints of ease of use and ease of handling of the apparatus. Examples of the ultraviolet light source include a UVLED lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a xenon lamp. The ultraviolet ray is preferably an ultraviolet ray having a peak wavelength of 200 to 450 nm, particularly 320 to 390 nm. The irradiation amount of the ultraviolet ray is preferably 50 to 2 with respect to, for example, a sheet obtained by molding the composition of the present invention to a thickness of 1 mm. , 400 mJ / cm ² , more preferably 50-800 mJ / cm ² . The silicone resin composition of the present invention can be sufficiently cured in a short time even when irradiated with ultraviolet rays having an energy smaller than 100 mJ / cm ² .

The silicone resin composition of the present invention has a water vapor transmission rate at a thickness in the range of 1 to 10 mm of 20 g / mm ² day or less, preferably 15 g / m ² · day or less, particularly preferably 10 g / m ² · day. A cured product is provided having: The water vapor transmission rate is a value measured according to JIS K 7129. The smaller the water vapor transmission rate, the better. If the water vapor transmission rate exceeds the above upper limit value, water vapor permeates under moisture absorption deterioration conditions, and thus, for example, the metal interface is corroded when cured on metal. Further, since the cured product swells, cracks of the resin itself and peeling at the resin interface occur. If the water vapor transmission rate of the cured product is within the above range, a coating excellent in anticorrosive effect such as a substrate can be formed.

  The cured product of the silicone resin composition of the present invention can be suitably used for sealing devices, particularly electronic devices and electrical devices. As described above, since the cured product of the silicone resin composition of the present invention has excellent moisture resistance, the cured film has an effect of suppressing corrosion of the base material and electric / electronic parts by sealing with the cured product. And an apparatus with excellent reliability can be provided. In particular, since the silicone resin composition of the present invention can be sufficiently cured in a short time even when irradiated with low energy radiation, a liquid crystal electrode, an organic EL electrode, a flat panel display electrode, and It is useful as a protective coating agent for plasma display electrodes and the like, and as a protective coating agent or sealant for various electric and electronic parts.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is further demonstrated, this invention is not limited to the following Example. In the following, “%” means mass%.

[Synthesis Example 1]
Synthesis of organohydrogenpolysiloxane 1 To a 2 L separable flask was added 470.9 g (2.5 mol) of cyclohexylmethyldimethoxysilane and 14.5 g of acetonitrile, and the mixture was stirred and cooled to an internal temperature of 10 ° C. or lower. . Next, 28.9 g of concentrated sulfuric acid was added dropwise to the separable flask, then 99 g of water was added dropwise. Finally, 251.9 g (1.9 mol) of (HSiMe ₂ ) ₂ O was added and stirred overnight. Waste acid separation was carried out, followed by washing with water and distillation under reduced pressure to obtain organohydrogenpolysiloxane 1 having the following structure. The amount of hydrogen gas generated from the organohydrogenpolysiloxane was 96.46 ml / g (0.4306 mol / 100 g).

[Synthesis Example 2]
Synthesis of organohydrogenpolysiloxane 2 To a 2 L separable flask, 449.6 g (2.2 mol) of cyclohexyltrimethoxysilane and 443.3 g (3.3 mol) of (HSiMe ₂ ) ₂ O were added, stirred, and iced. The inside temperature was 10 ° C. or lower by cooling. Next, 35.7 g of concentrated sulfuric acid was added dropwise to the separable flask, then 110.5 g of water was added dropwise and stirred overnight. Waste acid separation was carried out, washed with water, and distilled off under reduced pressure to obtain organohydrogenpolysiloxane 2 having the following structure. The amount of hydrogen gas generated from the organohydrogenpolysiloxane was 181.51 ml / g (0.810 mol / 100 g).

[Synthesis Example 3]
Synthesis of (meth) acrylate derivative 1 In a 1 L separable flask, 149.2 g (0.5 mol) of pentaerythritol triacrylate (trade name: V # 300, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 49.7 g of toluene, and 75.9 g (0.75 mol) of triethylamine was added, stirred, and ice-cooled to an internal temperature of 10 ° C. or lower. Next, 90.5 g (0.75 mol) of vinyldimethylchlorosilane was added dropwise to the separable flask, and the mixture was stirred for 2 hours after the completion of the addition. After the stirring, the produced triethylamine hydrochloride was filtered. The filtrate was washed with water and then distilled off under reduced pressure to obtain a (meth) acrylate derivative 1 having the following structure.

[Synthesis Example 4]
Synthesis of (meth) acrylate derivative 2 In a 1 L separable flask, 114.1 g of 2-hydroxy-1-acryloxy-3-methacryloxypropane (trade name: NK ester 701A, manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 mol), 38 g of toluene, and 75.9 g (0.75 mol) of triethylamine were added, stirred, and ice-cooled to an internal temperature of 10 ° C. or lower. Next, 90.5 g (0.75 mol) of vinyldimethylchlorosilane was added dropwise to the separable flask, and the mixture was stirred for 2 hours after the completion of the addition. After the stirring, the produced triethylamine hydrochloride was filtered. The filtrate was washed with water and then distilled off under reduced pressure to synthesize a (meth) acrylate derivative 2 having the following structure.

[Synthesis Example 5]
Synthesis of organopolysiloxane 1 256.4 g (1.0 mol) of (meth) acrylate derivative 1 obtained in Synthesis Example 3, 128.2 g of toluene, and 0.5% toluene solution of chloroplatinic acid in a 3 L separable flask 0.44 g was added, and 897.7 g (2.2 mol) of organohydrogenpolysiloxane 1 obtained in Synthesis Example 1 was added dropwise. After completion of the addition, the mixture was stirred at 80 ° C. for 3 hours. After completion of the stirring, distillation under reduced pressure was performed to obtain organopolysiloxane 1 having the following structure.

[Synthesis Example 6]
Synthesis of organopolysiloxane 2 368.6 g (1.0 mol) of (meth) acrylate derivative 2 obtained in Synthesis Example 4, 184.3 g of toluene, and 0.5% toluene solution of chloroplatinic acid in a 3 L separable flask 0.57.7 g was added, 897.7 g (2.2 mol) of organohydrogenpolysiloxane 1 obtained in Synthesis Example 1 was added dropwise, and after completion of the addition, the mixture was stirred at 80 ° C. for 3 hours. After completion of the stirring, distillation under reduced pressure was performed to obtain organopolysiloxane 2 having the following structure.

[Synthesis Example 7]
Synthesis of organopolysiloxane 3 In a 3 L separable flask, 368.6 g (1.0 mol) of (meth) acrylate derivative 2 obtained in Synthesis Example 4, 184.3 g of toluene, and 0.5% toluene solution of chloroplatinate 0.53.4 g was added, and 1183.4 g (2.2 mol) of organohydrogenpolysiloxane 2 obtained in Synthesis Example 2 was added dropwise. After completion of the addition, the mixture was stirred at 80 ° C. for 3 hours. After completion of the stirring, distillation under reduced pressure was performed to obtain organopolysiloxane 3 having the following structure.

[Examples 1 to 5]
The organopolysiloxanes 1 to 3 obtained in Synthesis Examples 5 to 7 and (B) photopolymerization initiator shown in Table 1 below were mixed in the composition shown in Table 1 to prepare a silicone resin composition.

^１）ＩＲＵＧＡＣＵＲＥ（登録商標）９０７：２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン、ＢＡＳＦ社製
^２）ＫＡＹＡＣＵＲＥ（登録商標）ＢＭＳ：４−ベンゾイル−４’−メチルフェニルサルファイド、日本化薬株式会社製

¹⁾ IRUGACURE (registered trademark) 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by BASF
²⁾ KAYACURE (registered trademark) BMS: 4-benzoyl-4′-methylphenyl sulfide, manufactured by Nippon Kayaku Co., Ltd.

[Comparative Examples 1 and 2]
In Comparative Example 1, a composition was prepared in the same manner as in Example 1 except that organopolysiloxane 1 was changed to urethane acrylate (UX-4101, manufactured by Nippon Kayaku Co., Ltd.). In Comparative Example 2, the composition was changed in the same manner as in Example 1 except that the organopolysiloxane 1 was changed to the organopolysiloxane 4 represented by the following formula (7) and described in JP-A-11-302348. Prepared.

The evaluation method of each physical property is shown below.
-Hardness The hardness of each cured product was measured using a spring type A tester in accordance with JIS K6301.
Water vapor transmission rate The water vapor transmission rate of each cured product having a thickness of 1 mm was measured in accordance with JIS K 7129.
-Surface tackiness The presence or absence of tackiness on the surface of each cured product was visually observed.

Each composition of Examples 1 to 5 and Comparative Examples 1 and 2 was poured into a mold having a depth of 1 mm, a width of 120 mm, and a length of 170 mm, and in a conveyor furnace provided with two metal halide mercury lamps (illuminance: 40 W / cm ² ). Then, ultraviolet rays having a wavelength of 200 nm to 450 nm were irradiated for 2 seconds (energy amount: 200 mJ / cm ² ) to obtain a cured product. The ultraviolet irradiation amount was adjusted to 200 mJ / cm ² with an illuminometer by adjusting the speed and height of the conveyor. The hardness, water vapor transmission rate, and surface tackiness of the cured product were measured according to the above methods. The results are shown in Table 2.

Curing with low energy irradiation Each composition of Examples 1 to 5 and Comparative Examples 1 and 2 was poured into a mold having a depth of 1 mm, a width of 120 mm, and a length of 170 mm, in a conveyor furnace equipped with two metal halide mercury lamps (illuminance : 40W / cm ²⁾ at 2 seconds, irradiated with ultraviolet rays having a wavelength 200 to 450 nm (energy: 50 mJ / ^cm 2), to obtain a cured product. The ultraviolet irradiation amount was adjusted to 50 mJ / cm ² with an illuminometer by adjusting the speed and height of the conveyor. The hardness, water vapor transmission rate, and surface tackiness of the cured product were measured according to the above methods. The results are shown in Table 3.

  As shown in Table 2, the silicone resin composition of the present invention provides a cured product excellent in water vapor permeability. In addition, as shown in Table 3, the silicone resin composition of the present invention can be cured sufficiently in a short time even when the irradiation energy of radiation is small, and is a cured product excellent in water vapor permeability. Can be provided.

  The silicone resin composition of the present invention can be suitably used as a sealant or coating agent for devices, particularly electrical devices and electronic devices. In particular, even when irradiated with low-energy radiation, it can be cured sufficiently in a short time, so liquid crystal electrodes, organic EL electrodes, flat panel display electrodes, plasma display electrodes, etc. that are easily affected by radiation such as ultraviolet rays It is extremely useful as a protective coating agent and as a protective coating agent for various electric and electronic parts.

Claims (8)

(A) Organopolysiloxane represented by the following general formula (1)

(1)
(In the formula (1), ^{R 1} are each independently a cycloalkyl group having 4 to 8 carbon atoms, ^{R 2} is a group represented by -OX, X, independently of one another, acryl or methacryl R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms that is not a cycloalkyl group and is a substituted or unsubstituted cycloalkyl group, and Q is independently of each other. , An oxygen atom or an alkylene group having 1 to 10 carbon atoms, a, b and c are each independently an integer of 0 to 3, provided that a, b and c are each a + b + c = 3 for each silicon atom. D is an integer of 1 or 2 independently of each other, e is an integer of 0 or 1 independently of each other, provided that d and e satisfy d + e = 2 for each silicon atom, and n is is an integer of 0 to 40, ^{R 4} independently of one another, ^{R 1} 及 beauty ^{R 3} Wherein at least one of R ⁴ in the above formula (1) is a group selected from the options of R ¹ , and R ⁵ is independently selected from the following formula (2): A group represented by

(2)
In formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Q, a, b, c, d, and e are as described above, m is an integer of 0 to 15,
However, the organopolysiloxane has at least one R ² in one molecule), and (B) a photopolymerization initiator (A) a silicone resin composition containing an effective amount for curing the component. In the above formula (2), d is 2, e is 0, a group R ⁴ is selected from the options of R ^3, claim 1 Symbol placement of silicone resin composition. In the above formula (1), b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 0 to 2, provided that a, b, and c are a + b + c for each silicon atom. The silicone resin composition of Claim 1 or 2 satisfy | filling = 3. The silicone resin composition according to claim 3 , wherein a is 0, b is 1 and c is 2 in the above formulas (1) and (2). In the formula (1), a is 0, b is 0, c is 3, and in the formula (2), a is 0, b is 1, and c is 2. The silicone resin composition according to claim 1 or 2. The amount of (B) component is 0.1-100 mass parts with respect to 100 mass parts of (A) component, The silicone resin composition of any one of Claims 1-5 . The silicone resin according to any one of claims 1 to 6 , which gives a cured product having a water vapor transmission rate of 20 g / mm ² day or less measured in accordance with JIS K 7129 with a thickness in the range of 1 to 10 mm. Composition. Device comprising a cured product obtained by curing the silicone resin composition of any one of claims 1-7.