JP2012121950A - Curable silicone composition and silicone resin cured product - Google Patents

Abstract

[PROBLEMS] To provide a curable silicone composition that gives a cured product having both the film-forming property and toughness of poly (meth) acrylic acid ester and the thermal stability of silicone, and a silicone resin obtained by curing the composition. Provide a cured product.
(A) A polymer of (meth) acrylic acid ester containing at least one hydrogen atom (Si-H group) bonded to a silicon atom in one molecule, or a Si-H group in one molecule. A copolymer of at least one (meth) acrylic acid ester and at least one selected from (meth) acrylic acid esters and siloxane-containing (meth) acrylic acid esters; (B) a silicon atom in one molecule; A curable silicone composition comprising an organopolysiloxane having at least two bonded alkenyl groups and (C) a hydrosilylation reaction catalyst.
[Selection figure] None

Description

  The present invention relates to a curable silicone composition and a cured silicone resin, and in particular, a curable silicone composition that provides a cured product having both properties of a poly (meth) acrylic acid ester and silicone, and curing the composition. It relates to a cured silicone resin obtained by the above.

  Silicone is widely used in all industrial fields because it has excellent heat resistance, optical transparency, gas permeability, and excellent moldability and workability. However, silicone has a low mechanical strength and is a very difficult material to handle as a film or thin film. In order to improve this, Japanese Patent Publication No. 4-001652 (Patent Document 1) discloses a copolymer of polycarbonate and siloxane, and Japanese Patent Application Laid-Open No. 5-285216 (Patent Document 2) includes an aromatic polyamide-siloxane system. Block copolymers have been proposed. However, these polymers have the problem that, in addition to being extremely complicated to synthesize, they are hydrolyzable and lack long-term stability.

  On the other hand, poly (meth) acrylic acid ester is a thermoplastic polymer material having excellent mechanical strength. Its glass transition temperature is generally as low as 100 ° C. or lower, and is excellent in heat moldability, so that it is used as a raw material for coating agents, films, housings and the like. However, poly (meth) acrylic acid ester has a problem that it cannot withstand long-term use, such as poor thermal stability, and therefore becomes brittle over time, and these improvements are strongly desired.

  In order to solve the above problems, efforts are being made to develop materials having both properties of silicone and poly (meth) acrylate. For example, JP-A-1-009268 (Patent Document 3) and JP-A-2007-298974 (Patent Document 4) disclose silicone-poly (meth) acrylic acid using hydrolysis / condensation reaction of alkoxysilyl group. Japanese Unexamined Patent Application Publication No. 2010-10000742 (Patent Document 5) proposes a crosslinked structure of a silicone-poly (meth) acrylate ester utilizing urethane bond formation between an isocyanate group and a hydroxyl group. . However, the cross-linking reaction used here may have different efficiencies between the material surface and the inside, and therefore there is a problem that it is difficult to adjust the material composition and curing conditions related to the physical properties. Moreover, since the alkoxysilyl group and the isocyanate group are highly hydrolyzable, another problem that the storage stability of the raw material is lacking occurs.

Japanese Patent Publication No. 4-001652 Japanese Patent Laid-Open No. 5-285216 JP-A-1-009268 JP 2007-298974 A JP 2010-1000074 A

  The present invention has been made to solve the above-mentioned problems, and is a curable silicone composition that provides a cured product having both the film-forming property and toughness of poly (meth) acrylic acid ester and the thermal stability of silicone. Another object of the present invention is to provide a cured silicone resin obtained by curing the composition.

As a result of intensive studies to achieve the above object, the present inventors have (A) a hydrogen atom bonded to a silicon atom in one molecule represented by the following general formula (1) (hereinafter referred to as Si—H). (Meth) acrylic acid ester polymer containing at least one group) or (meth) acrylic acid containing at least one Si-H group in one molecule represented by the following general formula (1) A copolymer of an ester and at least one selected from a (meth) acrylic acid ester and a siloxane-containing (meth) acrylic acid ester represented by the following general formula (2), (B) a silicon atom in one molecule A curable silicone composition containing an organopolysiloxane having at least two bonded alkenyl groups and (C) a hydrosilylation reaction catalyst is a film-forming property and toughness of poly (meth) acrylate ester It was found that applying heat stability and a combining silicone resin cured product of the silicone.
Furthermore, the curable silicone composition has been found to be excellent in curability and storage stability because hydrosilylation is a cross-linking reaction, and has led to the present invention.

（式中、Ｒは水素原子又はメチル基、Ｒ¹は互いに同一又は異種の１価の有機基、Ｒ²は２価の有機基を示す。ａは１〜１０の整数、ｂは０又は１〜１００の整数であり、ｃは０、１又は２である。ａが付された単位とｂが付された単位は互いにランダムに配列している。）

（式中、Ｒ、Ｒ¹、Ｒ²、ｃは式（１）と同じである。ｄは１〜１００の整数である。）
（Ｂ）１分子中にケイ素原子に結合したアルケニル基を少なくとも２個有するオルガノポリシロキサン、
（Ｃ）ヒドロシリル化反応触媒
を含有する硬化性シリコーン組成物。
〔請求項２〕
上記式（１）中のＲ及びＲ¹がメチル基、Ｒ²がプロピレン基、ａが１、ｂが０、ｃが２である、請求項１に記載の硬化性シリコーン組成物。
〔請求項３〕
上記式（１）中のＲ及びＲ¹がメチル基、Ｒ²がプロピレン基、ａが１、ｂが０、ｃが０である、請求項１に記載の硬化性シリコーン組成物。
〔請求項４〕
上記式（２）中のＲ及びＲ¹がメチル基、Ｒ²がプロピレン基、ｃが０、ｄが１である請求項１〜３のいずれか１項に記載の硬化性シリコーン組成物。
〔請求項５〕
請求項１〜４のいずれか１項に記載の硬化性シリコーン組成物を成形、硬化させることにより得られるシリコーン樹脂硬化物。
〔請求項６〕
請求項１〜４のいずれか１項に記載の硬化性シリコーン組成物の薄膜を硬化させることにより得られるシリコーン樹脂硬化物。
〔請求項７〕
請求項１〜４のいずれか１項に記載の硬化性シリコーン組成物の溶媒溶液を硬化させることにより得られるゲル状のシリコーン樹脂硬化物。 Accordingly, the present invention provides the following curable silicone composition and cured silicone resin.
[Claim 1]
(A) A polymer of (meth) acrylic acid ester containing at least one hydrogen atom (Si—H group) bonded to a silicon atom in one molecule represented by the following general formula (1), or the following general formula (Meth) acrylic acid ester containing at least one Si-H group in one molecule represented by (1), (meth) acrylic acid ester, and siloxane containing (meta) represented by the following general formula (2) ) A copolymer with at least one selected from acrylic esters,

(Wherein R represents a hydrogen atom or a methyl group, R ¹ represents the same or different monovalent organic group, R ² represents a divalent organic group, a represents an integer of 1 to 10, and b represents 0 or 1) And c is 0, 1 or 2. The unit with a and the unit with b are randomly arranged.

(In the formula, R, R ¹ , R ² and c are the same as those in formula (1). D is an integer of 1 to 100.)
(B) an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule;
(C) A curable silicone composition containing a hydrosilylation reaction catalyst.
[Claim 2]
The curable silicone composition according to claim 1, wherein R and R ¹ in the formula (1) are methyl groups, R ² is a propylene group, a is 1, b is 0, and c is 2.
[Claim 3]
The curable silicone composition according to claim 1, wherein R and R ¹ in the formula (1) are methyl groups, R ² is a propylene group, a is 1, b is 0, and c is 0.
[Claim 4]
The curable silicone composition according to any one of claims 1 to 3, wherein R and R ¹ in the formula (2) are methyl groups, R ² is a propylene group, c is 0, and d is 1.
[Claim 5]
The silicone resin hardened | cured material obtained by shape | molding and hardening the curable silicone composition of any one of Claims 1-4.
[Claim 6]
The silicone resin hardened | cured material obtained by hardening the thin film of the curable silicone composition of any one of Claims 1-4.
[Claim 7]
The gel-like silicone resin hardened | cured material obtained by hardening the solvent solution of the curable silicone composition of any one of Claims 1-4.

  The curable silicone composition of the present invention is excellent in storage stability and curability because hydrosilylation is a cross-linking reaction. Moreover, the cured silicone resin obtained by thermosetting the composition is excellent in film forming property and toughness, particularly thin film strength, and also has thermal stability.

2 is a ¹ H-NMR chart of a polymer (A-1) obtained in Synthesis Example 1. FIG. 2 is a ¹ H-NMR chart of a polymer (A-2) obtained in Synthesis Example 2.

The present invention will be described in detail below.
[(A) component]
The component (A) is represented by a polymer of (meth) acrylic acid ester containing at least one Si-H group in one molecule represented by the following general formula (1), or represented by the following general formula (1). (Meth) acrylic acid ester (hereinafter referred to as “Si—H group-containing (meth) acrylic acid ester”) containing at least one Si—H group in one molecule, (meth) acrylic acid ester and the following general It is a copolymer with at least one selected from siloxane-containing (meth) acrylic acid esters represented by the formula (2), and is a characteristic component of the composition of the present invention. This component gives film forming property and toughness to the cured silicone resin of the present invention. In addition, as the properties of the component, the cured product can be given adhesion to a substrate (metal, plastic, ceramics, etc.), gas barrier properties, and hydrophilicity.
In the present invention, “(meth) acrylic acid ester” refers to acrylic acid ester and / or methacrylic acid ester.

（式中、Ｒは水素原子又はメチル基、Ｒ¹は互いに同一又は異種の１価の有機基、Ｒ²は２価の有機基を示す。ａは１〜１０の整数、ｂは０又は１〜１００の整数であり、ｃは０、１又は２である。ａが付された単位とｂが付された単位は互いにランダムに配列している。）

(Wherein R represents a hydrogen atom or a methyl group, R ¹ represents the same or different monovalent organic group, R ² represents a divalent organic group, a represents an integer of 1 to 10, and b represents 0 or 1) And c is 0, 1 or 2. The unit with a and the unit with b are randomly arranged.

（式中、Ｒ、Ｒ¹、Ｒ²、ｃは式（１）と同じである。ｄは１〜１００の整数である。）

(In the formula, R, R ¹ , R ² and c are the same as those in formula (1). D is an integer of 1 to 100.)

In the above formulas (1) and (2), R ¹ is the same or different monovalent organic group, and specifically includes 1 to 10 carbon atoms such as methyl group, ethyl group and propyl group, preferably Is exemplified by monovalent hydrocarbon groups such as an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms such as a phenyl group, and a methyl group and a phenyl group are preferable. R ² is a divalent organic group, specifically, a divalent hydrocarbon group such as an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, or a butylene group. An alkylene group having 1 to 3 atoms is preferred.

  The unit to which a is attached is an essential component in the present invention, but if it is present in a large amount in one molecule, it may gel during polymerization. Therefore, a is a positive integer of 1 to 10, preferably a positive integer of 1 to 6, more preferably a positive integer of 1 to 3. b is 0 or a positive integer of 1 to 100, preferably 0 or a positive integer of 1 to 10, more preferably 0 or a positive integer of 1 to 6. A + b is a positive integer of 1 to 100, preferably a positive integer of 1 to 10, more preferably a positive integer of 1 to 6, and the unit with a and the unit with b are mutually Randomly arranged. c is 0, 1 or 2. d is a positive integer of 1 to 100, preferably a positive integer of 1 to 50, more preferably a positive integer of 1 to 10.

  Examples of the Si—H group-containing (meth) acrylic acid ester represented by the formula (1) include the following compounds, but the present invention is not limited to these specific examples. Here, Me represents a methyl group and Ph represents a phenyl group (hereinafter the same).

  The Si—H group-containing (meth) acrylic acid ester represented by the formula (1) may be used alone or in combination of two or more.

  The acrylic acid ester and methacrylic acid ester that can be copolymerized with the Si—H group-containing (meth) acrylic acid ester represented by the formula (1) do not contain an Si—H group, and preferably have a silicon atom. Is not included. These can be used singly or in combination of two or more. The (meth) acrylic acid ester is preferably an alkyl ester having 1 to 18 carbon atoms of (meth) acrylic acid. Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, and acrylic. Examples include isobutyl acid, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, n-decyl acrylate, and isodecyl acrylate. Examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, and n-methacrylate. Examples include octyl, isononyl methacrylate, n-decyl methacrylate, and isodecyl methacrylate. Among them, acrylic acid alkyl esters and methacrylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl group, particularly 1 to 8 carbon atoms in the alkyl group are preferable.

  The siloxane-containing (meth) acrylic acid ester represented by the formula (2) that can be copolymerized with the Si-H group-containing (meth) acrylic acid ester represented by the formula (1) includes Si-H groups. Although it does not have, the following compounds can be illustrated, but this invention is not limited to these specific examples.

  The siloxane-containing (meth) acrylic acid ester represented by the formula (2) can be used alone or in combination of two or more.

  The (co) polymer containing the (A) component Si—H group-containing (meth) acrylic acid ester is a azo compound such as 2,2′-azobisisobutyronitrile (AIBN) It can be obtained by using an organic peroxide such as t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator.

  As the solvent used in the polymerization, all conventionally known solvents can be used, for example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and aliphatic carbonization such as hexane, heptane, octane, decane and isododecane. Hydrogen solvents, halogenated hydrocarbon solvents such as methylene chloride, perchloroethylene, trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethanol, isopropanol, butanol, etc. Examples include alcohol solvents, ligroin, cyclohexanone, diethyl ether, tetrahydrofuran, volatile rubber oil, silicone solvents, and the like. Of these, aromatic hydrocarbon solvents and ester solvents are preferred. In consideration of safety to the human body, it is preferable to use a silicone solvent.

  The structural unit derived from the Si—H group-containing (meth) acrylic acid ester represented by the above formula (1) is 0.5 to 100 mol%, preferably 1 to 60 mol%, more preferably in the polymer. Is 1-30 mol%. (A) Although a component can also be made into the polymer of only the Si-H group containing (meth) acrylic acid ester represented by the said Formula (1), this Si-H group containing (meth) acrylic acid ester and , (Meth) acrylic acid ester or a copolymer with a siloxane-containing (meth) acrylic acid ester represented by the above formula (2). In this case, Si—H represented by the formula (1) If the number of structural units derived from the group-containing (meth) acrylic acid ester is too small, sufficient strength may not be obtained when a cured product is obtained. If the amount is too large, adhesiveness may be improved, but it may be brittle. Therefore, it is preferable to adjust appropriately according to the purpose of use.

  A (meth) acrylic acid ester and a siloxane-containing (meth) acrylic acid ester represented by the formula (2) that can be copolymerized with the Si—H group-containing (meth) acrylic acid ester represented by the formula (1) The structural unit derived from is 0 to 99.5 mol% in the copolymer, preferably 40 to 99 mol%, more preferably 70 to 99 mol%. The structural unit derived from acrylic acid ester and methacrylic acid ester contributes to the strength development when cured and the improvement of gas barrier properties. In the siloxane-containing (meth) acrylic acid ester represented by formula (2), The derived structural unit contributes to improvement in solubility and compatibility with the component (B) of the composition. Therefore, it is preferable to adjust appropriately according to the purpose of use. Specifically, the proportion of structural units derived from (meth) acrylic acid ester is 20 to 90 mol%, particularly 30 to 70 mol% in the copolymer. The proportion of the structural units derived from the siloxane-containing (meth) acrylic acid ester is preferably 30 to 90 mol%, particularly 40 to 80 mol% in the copolymer.

  The molecular weight of the (co) polymer containing the (A) component-containing (meth) acrylic acid ester is the number in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The average molecular weight (Mn) is preferably in the range of 1,000 to 1,000,000, more preferably 5,000 to 500,000. When the molecular weight is smaller than 1,000, the cured product may be inferior in strength, and when the molecular weight is larger than 1,000,000, the handling property and solubility may be inferior.

[Component (B)]
Component (B) is an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule, and is added to the component (A) by a hydrosilylation reaction to cure a silicone resin having a three-dimensional network structure. Give things.

  The molecular structure of (B) component is not specifically limited, For example, a linear structure, a branched structure, a cyclic structure, and the composite structure containing these are mentioned. Among these, the component (B) is preferably a substantially linear organopolysiloxane. Specifically, the molecular chain mainly consists of repeating diorganosiloxane units, and both ends of the molecular chain are A linear organopolysiloxane blocked with a triorganosiloxy group is preferred. The component (B) may be a polymer composed of a single siloxane unit or a copolymer composed of two or more siloxane units.

  Further, the position of the alkenyl group bonded to the silicon atom in the component (B) is not particularly limited, and it may be bonded to only one of the silicon atom at the molecular chain end portion and the silicon atom at the non-terminal portion of the molecular chain. It may be combined with both of them. It is sufficient that at least two alkenyl groups bonded to silicon atoms are contained in one molecule, and preferably 2 to 4 alkenyl groups are contained in one molecule.

(B) a viscosity at 23 ° C. as measured by Ostwald meter component is usually 1~100,000mm ² / s, preferably 10~5,000mm ² / s. If the viscosity is too low, the strength of the resulting cured product may be inferior. If the viscosity is too high, the workability of the composition will be inferior, and the compatibility with the component (A) will be poor. The strength of the cured product may be inferior.

As the component (B), for example, it can be represented by the following average composition formula (3).
R ³ _e R ⁴ _f SiO _{(4-ef) / 2} (3)
(In the formula, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, R ⁴ independently represents an alkenyl group, and e is usually 0.7-2. .2, preferably 1.8 to 2.1, more preferably 1.95 to 2.0, and f is usually 0.0001 to 0.2, preferably 0.0005 to 0.1, More preferably, it is a number of 0.01 to 0.05, provided that e + f is usually 0.8 to 2.3, preferably 1.9 to 2.2, more preferably 1.98 to 2.05. Number.)

As said R < ³ >, the unsubstituted or substituted monovalent hydrocarbon group which does not contain a C1-C10 aliphatic unsaturated bond is mentioned, for example. Specific examples include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, t-butyl groups, hexyl groups, octyl groups, decyl groups and other alkyl groups; phenyl groups, tolyl groups, xylyl groups, Aryl groups such as naphthyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as benzyl group, 2-phenylethyl group and 3-phenylpropyl group; hydrogen bonded to carbon atoms in these hydrocarbon groups Halogen atoms such as chlorine atom and bromine atom, a part or all of atoms; groups substituted by cyano group, such as chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, cyanoethyl group Etc.

Among these, a methyl group, a phenyl group, or a combination of both is preferable. The component (B) in which R ³ is a methyl group, a phenyl group, or a combination of both is easy to synthesize and has good chemical stability. In addition, as the component (B), R ³ is a combination of a methyl group, a phenyl group, or a combination of both, and a 3,3,3-trifluoropropyl group, indicating that the solvent resistance of the composition is high. This is preferable.

Examples of R ⁴ include alkenyl groups having 2 to 8 carbon atoms. Specific examples include vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, isobutenyl group, hexenyl group and the like. Among these, a vinyl group is preferable from the viewpoint of easy synthesis and chemical stability.

Component (B) can be used alone or in combination of two or more.
(B) The compounding quantity of a component is 5-900 mass parts with respect to 100 mass parts of (A) component, Preferably it is 10-700 mass parts. If the amount is too small, the thermal stability may be inferior, and if it is too large, the mechanical strength may be inferior.

[Component (C)]
Component (C) is a hydrosilylation reaction catalyst. Any conventionally known hydrosilylation reaction catalyst can be used. For example, carbon powder supporting platinum metal, platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of platinum and vinylsiloxane such as divinyltetramethyldisiloxane, Examples thereof include platinum group catalysts such as complexes of chloroplatinic acid and olefins, platinum-based catalysts such as platinum bisacetylacetonate, palladium-based catalysts, and rhodium-based catalysts.

  The compounding amount of the component (C) may be an effective amount as a hydrosilylation reaction catalyst, and is not particularly limited as long as a desired curing rate can be obtained. As the blending amount, for example, the amount of the platinum group metal in the component (C) with respect to the total amount of the composition of the present invention (particularly the total amount of the components (A) and (B)) is usually based on mass. 0.1 to 1,000 ppm, preferably 0.1 to 500 ppm, and more preferably 0.5 to 200 ppm.

[Other ingredients]
In addition to the above-mentioned components (A) to (C), it is optional to add other components to the composition of the present invention as long as the object and effect of the present invention are not impaired. Examples of other components include those described below. Moreover, each component shown below can be used even if single 1 type also combines 2 or more types.

<Addition reaction control agent>
In order to ensure the pot life of the composition of the present invention, an addition reaction control agent can be blended. Specific examples of the addition reaction control agent include 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, and the like.
When the addition reaction control agent is blended with the composition of the present invention, the blending amount is not particularly limited as long as it is an effective amount as the addition reaction control agent, but a total of 100 masses of the components (A) and (B). Usually, it is in the range of 0.01 to 5 parts by mass with respect to parts.

<Adhesion aid>
In order to further improve the adhesion of the cured silicone resin of the present invention to a substrate (metal, plastic, ceramics, etc.), an adhesion aid can be blended as necessary. Examples of general adhesion assistants include silane coupling agents. Specific examples include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane, epoxy group-containing silane coupling agents such as glycidoxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, and acryloyl. (Meth) acrylic group-containing silane coupling agents such as oxypropyltrimethoxysilane, isocyanate group-containing silane coupling agents such as isocyanatepropyltrimethoxysilane, amino group-containing silane coupling agents such as aminopropyltriethoxysilane, etc. A vinyl group-containing silane coupling agent, an epoxy group-containing silane coupling agent, and a (meth) acryl group-containing silane coupling agent are preferred.
In the case where an adhesion aid is blended in the composition of the present invention, the blending amount is not particularly limited as long as it is an effective amount as an adhesion aid, but the total amount of the components (A) and (B) is 100 parts by mass. On the other hand, it is usually 0.05 to 5 parts by mass, preferably 0.1 to 2 parts by mass.

<Filler>
For the purpose of further improving the properties of the composition and the cured product of the present invention, a filler can be blended. Examples of the filler include reinforcing agents such as fine powder silica, inorganic pigments such as cobalt blue, colorants such as organic dyes, diatomaceous earth, potassium oxide, zinc oxide, iron oxide, titanium oxide, aluminum oxide, copper oxide, and carbonic acid. Examples include calcium, zinc carbonate, manganese carbonate, bengara, carbon black, pulverized quartz powder, aluminum hydroxide, aluminum, copper, silver, gold, nickel, and other heat resistance / flame retardant / thermal conductivity improvers.
When blending a filler in the composition of the present invention, the blending amount is not particularly limited as long as it is an effective amount as a filler, but with respect to a total of 100 parts by mass of the components (A) and (B). Usually, it exceeds 0 mass part and is 2,000 mass parts or less, preferably 0.1 to 1,500 mass parts.

<Antioxidant>
In the cured product of the composition of the present invention, the carbon-carbon double bond in the component (B) may remain unreacted. If this carbon-carbon double bond is contained, it may be oxidized by oxygen in the atmosphere and the cured product may be colored. Then, coloring can be prevented beforehand by mix | blending antioxidant with the composition of this invention as needed.
As this antioxidant, any conventionally known ones can be used. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2, Examples include 5-di-t-butylhydroquinone, 4,4′-butylidene (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and the like.
When the antioxidant is blended in the composition of the present invention, the blending amount is not particularly limited as long as it is an effective amount as an antioxidant, but the total amount of the components (A) and (B) is 100 parts by mass. On the other hand, it is 0.001-1 mass part normally, Preferably it is 0.01-0.1 mass part.

<Light stabilizer>
In order to impart resistance to photodegradation of the cured product of the composition of the present invention, a light stabilizer can be added to the composition. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidation degradation is suitable, and specific examples thereof include bis (2,2,6,6-tetramethyl-4- Piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like.
When the light stabilizer is blended in the composition of the present invention, the blending amount is not particularly limited as long as it is an effective amount as the light stabilizer, but the total amount of the components (A) and (B) is 100 parts by mass. On the other hand, it is 0.001-1 mass part normally, Preferably it is 0.01-0.1 mass part.

<Solvent>
In the composition of the present invention, a solvent can be used as a diluent. This solvent is the same as the solvent that can be used for the preparation of the component (A).
When a solvent is used as the diluent of the composition of the present invention, the blending amount is not particularly limited, but is usually 1 to 2,000 parts by mass with respect to 100 parts by mass in total of the components (A) and (B) Preferably it is 5-1,000 mass parts.

[Preparation]
The preparation method of the curable silicone composition of this invention is not limited, It can prepare by mixing (A)-(C) component and arbitrary components simultaneously as needed. Further, the base compound may be prepared by mixing the component (A) and the component (B), and the component (C) and an optional component may be added to the base compound. When preparing the composition of the present invention, a known kneading apparatus such as a two-roll mill, a three-roll mill, a kneader mixer, or a planetary mixer can be used.

[Hardened silicone resin]
The curable silicone composition of the present invention is excellent in curability because hydrosilylation is a cross-linking reaction. The curing conditions for the composition are not particularly limited, but it is usually preferable to set the conditions at 80 to 180 ° C. for 10 to 300 minutes.

  A cured silicone resin can be obtained by molding and curing the curable silicone composition of the present invention. The composition can be applied to conventionally used molding methods such as a dispensing method, a potting method, an injection molding method, and a transfer molding method. Moreover, since the cured silicone resin of the present invention is excellent in thin film strength, it can be handled as a film or a film. When it is set as such a form, this composition can be made into the solution diluted with the said solvent, and a solution casting method (cast method) can be used. Furthermore, the silicone composition of the present invention can be made into a gel-like cured product obtained by dissolving in a solvent and curing in a solution.

  Here, when making a silicone resin hardened | cured material into a film | membrane and a film, as the thickness, it is preferable to set it as 0.05-500 micrometers, especially 0.1-300 micrometers.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a viscosity shows the value in 23 degreeC measured with the Ostwald viscometer, Me shows a methyl group, Ph shows a phenyl group.

(A) Preparation of Component [Synthesis Example 1] Preparation of Polymer (A-1) In a 500 mL four-necked flask equipped with a stirrer, a condenser, and a thermometer, Si-H represented by the following formula (4) Group-containing methacrylic acid ester (hereinafter, monomer A) 104 g, 2,2′-azobisisobutyronitrile (AIBN) 0.15 g, and ethyl acetate 150 g were added, and the mixture was heated and stirred using an oil bath. The reaction was carried out for 6 hours under reflux of ethyl acetate. After completion of the reaction, the solution was poured into a large amount of methanol, the polymer was precipitated, washed by filtration, and dried under reduced pressure at 60 ° C. for 12 hours to obtain 99 g (yield 95%) of polymer (A-1). When the molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, the number average molecular weight (Mn) was 103,000, and the polydispersity (PDI) was 2.1. The glass transition temperature (Tg) of the polymer (A-1) measured by differential scanning calorimetry (DSC) was −3 ° C. In FIG. 1, the result of the < ¹ > H-NMR measurement of a polymer (A-1) is shown.

The obtained polymer (A-1) was dissolved in toluene so as to be 20% by mass, and the solution was sealed and allowed to stand in a dryer at 50 ° C. for 1 week, but no gelation was observed.

[Synthesis Example 2] Preparation of polymer (A-2) In a 500 mL four-necked flask equipped with a stirrer, a condenser, and a thermometer, a Si-H group-containing methacrylate represented by the above formula (4) ( Monomer A) 3.1 g, methyl methacrylate (hereinafter referred to as monomer B) 16.0 g, siloxane-containing methacrylic acid ester (hereinafter referred to as monomer C) 96.5 g represented by the following formula (5), 2,2′-azobis Isobutyronitrile (AIBN) 0.15 g and ethyl acetate 150 g were added, and the mixture was heated and stirred using an oil bath. The reaction was carried out for 6 hours under reflux of ethyl acetate. After completion of the reaction, the solution was poured into a large amount of methanol, and the polymer was precipitated, washed by filtration, and dried under reduced pressure at 60 ° C. for 12 hours to obtain 112 g (yield 97%) of polymer (A-2). When the molecular weight was measured by GPC using THF as a solvent, the number average molecular weight (Mn) was 97,000, and the polydispersity (PDI) was 1.8. The glass transition temperature (Tg) of the polymer (A-2) measured by DSC was 21 ° C. As a result of ¹ H-NMR measurement, the ratio of the structures derived from monomers A, B, and C in the polymer (A-2) was A / B / C = 3/40/57 (mol / mol / mol). It was. FIG. 2 shows the result of ¹ H-NMR measurement of the polymer (A-2).

The obtained polymer (A-2) was dissolved in toluene so as to be 20% by mass, and the solution was left sealed in a dryer at 50 ° C. for 1 week, but no gelation was observed.

[Synthesis Example 3] Preparation of polymer (A-3) In place of the Si-H group-containing methacrylic acid ester (monomer A) represented by the formula (4), an Si-H group represented by the following formula (6) 113 g (yield 97%) of the polymer (A-3) was obtained in the same manner as in Synthesis Example 2 except that 4.6 g of the methacrylic acid ester (hereinafter, monomer D) was used. When the molecular weight was measured by GPC using THF as a solvent, the number-average molecular weight (Mn) was 69,000 and the polydispersity (PDI) was 1.6. The glass transition temperature (Tg) of the polymer (A-3) measured by DSC was 8 ° C. As a result of ¹ H-NMR measurement, the ratio of the structures derived from the monomers D, B, and C in the polymer (A-3) was D / B / C = 3/40/57 (mol / mol / mol). It was.

The obtained polymer (A-3) was dissolved in toluene so as to be 20% by mass, and the solution was left sealed in a dryer at 50 ° C. for 1 week, but no gelation was observed.

[Synthesis Example 4] Preparation of polymer (A-4) 111 g in the same manner as in Synthesis Example 2 except that 16.0 g of ethyl acrylate (hereinafter, monomer E) was used instead of methyl methacrylate (monomer B). Polymer (A-4) (yield 96%) was obtained. When the molecular weight was measured by GPC using THF as a solvent, the number average molecular weight (Mn) was 82,000 and the polydispersity (PDI) was 2.0. The glass transition temperature (Tg) of the polymer (A-4) measured by DSC was −9 ° C. As a result of ¹ H-NMR measurement, the ratio of the structures derived from the monomers A, E, and C in the polymer (A-4) was A / E / C = 3/40/57 (mol / mol / mol). It was.
The obtained polymer (A-4) was dissolved in toluene so as to be 20% by mass, and the solution was sealed and left in a dryer at 50 ° C. for 1 week, but no gelation was observed.

[Synthesis Example 5] Preparation of polymer (A-5) In a 500 mL four-necked flask equipped with a stirrer, a condenser, and a thermometer, a Si-H group-containing methacrylate represented by the above formula (4) ( Monomer A) 3.1 g, 2-ethylhexyl acrylate (hereinafter referred to as monomer F) 36.8 g, siloxane-containing methacrylic acid ester (monomer C) represented by the above formula (5) (monomer C) 79.5 g, 2,2′-azo Bisisobutyronitrile (AIBN) 0.15 g and ethyl acetate 150 g were added, and the mixture was heated and stirred using an oil bath. The reaction was carried out for 6 hours under reflux of ethyl acetate. After completion of the reaction, the solution was poured into a large amount of methanol, the polymer was precipitated, washed by filtration, and dried under reduced pressure at 60 ° C. for 12 hours to obtain 114 g (yield 95%) of polymer (A-5). When the molecular weight was measured by GPC using THF as a solvent, the number average molecular weight (Mn) was 62,000, and the polydispersity (PDI) was 2.2. The glass transition temperature (Tg) of the polymer (A-5) measured by DSC was −47 ° C. As a result of ¹ H-NMR measurement, the ratio of the structures derived from the monomers A, F and C in the polymer (A-5) was A / F / C = 3/50/47 (mol / mol / mol). It was.
The obtained polymer (A-5) was dissolved in toluene so as to be 20% by mass, and the solution was left sealed in a dryer at 50 ° C. for 1 week, but no gelation was observed.

Table 1 shows the results of Synthesis Examples 1-5.

[Examples 1 to 5]
(A-1) Polymer obtained in Synthesis Example 1 (A-2) Copolymer obtained in Synthesis Example 2 (A-3) Copolymer obtained in Synthesis Example 3 (A-4) Synthesis Copolymer obtained in Example 4 (A-5) Copolymer obtained in Synthesis Example 5 (B-1) Dimethylpolysiloxane blocked with dimethylvinylsiloxy group blocked at both ends of the molecular chain
(Viscosity 100mm ² / s)
(C) Platinum-divinyltetramethyldisiloxane complex toluene solution (D) Optional component: 1-ethynyl-1-cyclohexanol (addition reaction control agent)
(E-1) Optional component: Toluene (diluent)
Were blended in the blending amounts shown in Table 2, and compositions of Examples 1 to 5 were obtained. That is, first, any one of the components (A-1) to (A-5), the component (B-1), the component (D) and the component (E-1) is shown in Table 2 in a 500 mL planetary mixer. Prepared in a blended amount, mixed for 1 hour at room temperature, then added component (C) in the blended amount shown in Table 2 and mixed for 1 hour at room temperature so as to be uniform to obtain a paste-like composition. .
(E-1) component was further added and diluted so that composition content might be 30 mass% to the obtained composition, and the uniform composition solution was obtained. The appearance of this composition solution was visually confirmed and is shown in Table 2.
Each obtained composition solution was poured into a mold, air-dried, and then cured in an oven at 150 ° C. for 2 hours to obtain a cured product (F1 to F5) having a thickness of 200 μm. The characteristics of the obtained cured product were evaluated by the methods shown below. These results are shown in Table 4.

<Fracture strength and fracture elongation>
The breaking strength and breaking elongation were measured by punching the obtained cured product into a No. 2 dumbbell shape, fixing it to a probe of a testing machine, and pulling it at a speed of 50 mm / min.
<Oxygen transmission rate>
The oxygen transmission rate was measured by an isobaric method using a 10 cm diameter circular sample of the obtained cured product.
<Thermal stability>
The heat stability was evaluated by measuring the change in thickness before and after leaving the obtained cured product in a dryer at 150 ° C. for 24 hours.

（Ｇ−２）下記式で示されるオルガノハイドロジェンポリシロキサン

（Ｂ−１）分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン
（粘度１００ｍｍ²／ｓ）
（Ｃ）白金−ジビニルテトラメチルジシロキサン錯体トルエン溶液
（Ｄ）任意成分：１−エチニル−１−シクロヘキサノール（付加反応制御剤）
を、表３に示す配合量で配合し、比較例１、２の組成物を得た。即ち、まず、５００ｍＬのプラネタリーミキサーに（Ｇ−１）成分又は（Ｇ−２）成分、（Ｂ−１）成分及び（Ｄ）成分を表３に示す配合量で仕込み、室温にて１時間混合し、次に（Ｃ）成分を表３に示す配合量で加えて均一になるように室温にて１時間混合してオイル状の組成物を得た。この組成物の外観を目視にて確認し、表３に併記した。
得られたそれぞれの組成物を型に流し込み、１５０℃のオーブンで２時間硬化させて、厚み２００μｍの硬化物（Ｈ１、Ｈ２）を作製した。しかしながら、Ｈ１は強度が弱く、厚み２００μｍでの取扱いが困難であった。そこで、厚み１ｍｍのシート状硬化物とした。また、Ｈ２は脆く、厚み１ｍｍのシート状硬化物としても取り扱うことが困難であった。Ｈ１の特性を上記と同様に評価し、結果を表４に示した。 [Comparative Examples 1 and 2]
(G-1) Organohydrogenpolysiloxane represented by the following formula

(G-2) Organohydrogenpolysiloxane represented by the following formula

(B-1) Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain
(Viscosity 100mm ² / s)
(C) Platinum-divinyltetramethyldisiloxane complex toluene solution (D) Optional component: 1-ethynyl-1-cyclohexanol (addition reaction control agent)
Were blended in the blending amounts shown in Table 3 to obtain compositions of Comparative Examples 1 and 2. That is, first, the (G-1) component or the (G-2) component, the (B-1) component, and the (D) component are charged in a 500 mL planetary mixer at the blending amounts shown in Table 3, and one hour at room temperature. Next, the component (C) was added at the blending amount shown in Table 3 and mixed for 1 hour at room temperature so as to be uniform to obtain an oily composition. The external appearance of this composition was confirmed by visual observation and listed in Table 3.
Each of the obtained compositions was poured into a mold and cured in an oven at 150 ° C. for 2 hours to produce cured products (H1, H2) having a thickness of 200 μm. However, H1 has a low strength and is difficult to handle at a thickness of 200 μm. Therefore, a sheet-like cured product having a thickness of 1 mm was used. Moreover, H2 was fragile and it was difficult to handle it as a sheet-like cured product having a thickness of 1 mm. The characteristics of H1 were evaluated in the same manner as described above, and the results are shown in Table 4.

ａ）１ｍｍシートでの測定結果。
ｂ）１５０℃乾燥機に２４時間放置。放置前後の厚み変化を評価。

a) Measurement results with a 1 mm sheet.
b) Leave in a 150 ° C. dryer for 24 hours. Evaluate thickness change before and after being left.

[Example 6]
(A-2) 50 g of the copolymer obtained in Synthesis Example 2
(B-2) Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain
(Viscosity 5,000 mm ² / s) 78 g
(C) Platinum-divinyltetramethyldisiloxane complex toluene solution 0.16 g
(E-2) Optional component: Decamethylcyclopentasiloxane (diluent) 100 g
Was added to a 1 L four-necked flask equipped with a stirrer, a condenser, and a thermometer, and heated and stirred at 90 ° C. for 3 hours using an oil bath. After completion of the reaction, 1,052 g of (E-2) component was further added to the obtained rubber-like composition, and a gel-like composition (J1) having a composition component of 10% by mass was prepared with a ceramic three roll. did. The appearance of this composition was confirmed by visual observation and listed in Table 5.
Water was added to the obtained gel composition (J1) in each amount shown in Table 5 and mixed at room temperature with a 500 mL planetary mixer for 1 hour to disperse and mix water. The dispersion state was confirmed visually, and the results are also shown in Table 5.

（Ｂ−２）分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン
（粘度５，０００ｍｍ²／ｓ） ２１９ｇ
（Ｃ）白金−ジビニルテトラメチルジシロキサン錯体トルエン溶液 ０．１６ｇ
（Ｅ−２）任意成分：デカメチルシクロペンタシロキサン（希釈剤） ２００ｇ
を、攪拌装置、冷却管、温度計を備えた１Ｌの４つ口フラスコに加え、オイルバスを用いて９０℃で３時間加熱攪拌した。反応終了後、得られたゴム状組成物に（Ｅ−２）成分を更に２，２２１ｇ追加し、セラミック３本ロールにて組成物成分が１０質量％となるゲル状組成物（Ｋ１）を調製した。この組成物の外観を目視にて確認し、表５に併記した。
得られたゲル状組成物（Ｋ１）に、水を表５に示す各量で添加し、５００ｍＬのプラネタリーミキサーで１時間室温混合することで、水の分散配合を行った。分散状態を目視にて確認し、この結果を表５に併記した。 [Comparative Example 3]
(G-1) 50 g of organohydrogenpolysiloxane represented by the following formula

(B-2) Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain
(Viscosity 5,000 mm ² / s) 219 g
(C) Platinum-divinyltetramethyldisiloxane complex toluene solution 0.16 g
(E-2) Optional component: Decamethylcyclopentasiloxane (diluent) 200 g
Was added to a 1 L four-necked flask equipped with a stirrer, a condenser, and a thermometer, and heated and stirred at 90 ° C. for 3 hours using an oil bath. After completion of the reaction, 2,221 g of (E-2) component is further added to the obtained rubber-like composition, and a gel-like composition (K1) in which the composition component is 10% by mass is prepared with a ceramic three roll. did. The appearance of this composition was confirmed by visual observation and listed in Table 5.
Water was added to the obtained gel composition (K1) in each amount shown in Table 5 and mixed at room temperature with a 500 mL planetary mixer for 1 hour to disperse and mix water. The dispersion state was confirmed visually, and the results are also shown in Table 5.

ａ）分散配合の状態
○：分散
△：一部分離
×：分離

a) State of dispersion blending ○: Dispersion △: Partial separation ×: Separation

[Evaluation]
The above results show that the curable silicone composition of the present invention is excellent in curability and storage stability, and after thermosetting, it has excellent film forming properties and toughness, particularly thin film strength, and also has thermal stability. Yes. Moreover, it has also shown that the gas barrier property and hydrophilic property of this hardened | cured material can be adjusted with the structure of (A) component which is the characteristics of this invention. Therefore, the curable silicone composition of the present invention and the cured silicone resin obtained by curing the composition can be suitably used as raw materials for films, films, lenses, cosmetics, adhesives and the like. Application to potting materials, sealing materials, gel materials, etc. can also be expected.

Claims (7)

(A) A polymer of (meth) acrylic acid ester containing at least one hydrogen atom (Si—H group) bonded to a silicon atom in one molecule represented by the following general formula (1), or the following general formula (Meth) acrylic acid ester containing at least one Si-H group in one molecule represented by (1), (meth) acrylic acid ester, and siloxane containing (meta) represented by the following general formula (2) ) A copolymer with at least one selected from acrylic esters,

(Wherein R represents a hydrogen atom or a methyl group, R ¹ represents the same or different monovalent organic group, R ² represents a divalent organic group, a represents an integer of 1 to 10, and b represents 0 or 1) And c is 0, 1 or 2. The unit with a and the unit with b are randomly arranged.

(In the formula, R, R ¹ , R ² and c are the same as those in formula (1). D is an integer of 1 to 100.)
(B) an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule;
(C) A curable silicone composition containing a hydrosilylation reaction catalyst. The curable silicone composition according to claim 1, wherein R and R ¹ in the formula (1) are methyl groups, R ² is a propylene group, a is 1, b is 0, and c is 2. The curable silicone composition according to claim 1, wherein R and R ¹ in the formula (1) are methyl groups, R ² is a propylene group, a is 1, b is 0, and c is 0. The curable silicone composition according to any one of claims 1 to 3, wherein R and R ¹ in the formula (2) are methyl groups, R ² is a propylene group, c is 0, and d is 1.   The silicone resin hardened | cured material obtained by shape | molding and hardening the curable silicone composition of any one of Claims 1-4.   The silicone resin hardened | cured material obtained by hardening the thin film of the curable silicone composition of any one of Claims 1-4.   The gel-like silicone resin hardened | cured material obtained by hardening the solvent solution of the curable silicone composition of any one of Claims 1-4.

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