JP5342795B2 - 籠 Structure-containing curable silicone copolymer, method for producing the same, curable resin composition using 籠 structure-containing curable silicone copolymer, and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymer incorporating a cage structure into the main chain, and to provide a curable resin composition comprising the copolymer. <P>SOLUTION: The cage structure-containing curable silicone copolymer has a structural unit represented by general formula (1): Y-[Z-(O<SB>1/2</SB>-R<SP>2</SP><SB>2</SB>SiO<SB>1/2</SB>)<SB>a</SB>-(R<SP>1</SP>SiO<SB>3/2</SB>)<SB>n</SB>-(O<SB>1/2</SB>)<SB>b</SB>]<SB>m</SB>-Z-Y äwherein R<SP>1</SP>and R<SP>2</SP>represent each a vinyl group, an alkyl group, a phenyl group, an acryloyl group or a methacryloyl group, an allyl or a group having an oxirane ring; Z represents a divalent group represented by general formula (2); and Y is any of following (3) to (5): (3) [(R<SP>4</SP>O)R<SP>2</SP><SB>2</SB>SiO<SB>1/2</SB>]<SB>a</SB>-[R<SP>1</SP>SiO<SB>3/2</SB>]<SB>n</SB>-[O<SB>1/2</SB>]-, (4) [R<SP>4</SP>O<SB>1/2</SB>]<SB>b</SB>-[R<SP>1</SP>SiO<SB>3/2</SB>]<SB>n</SB>-[O<SB>1/2</SB>-R<SP>2</SP><SB>2</SB>SiO<SB>1/2</SB>]-, (5) (R<SP>4</SP>O<SB>1/2</SB>)-, and (6) (R<SP>2</SP><SB>3</SB>SiO<SB>1/2</SB>)- (wherein, R<SP>4</SP>is a hydrogen atom, a methyl group or an ethyl group)}. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a cocoon structure-containing curable silicone copolymer, a method for producing the same, a curable resin composition using the cocoon structure-containing curable silicone copolymer, and a cured product thereof, and more specifically, an alkoxyl group or silanol group-containing cocoon. The present invention relates to a cocoon structure-containing curable silicone copolymer using a silsesquioxane compound, a method for producing the same, and a curable resin composition containing the copolymer.

  There have been many studies on polymers using silsesquioxane having a cocoon structure or derivatives thereof. This polymer is expected to have superiority in heat resistance, weather resistance, optical properties, dimensional stability, and the like. For example, Non-Patent Document 1 discloses a silsesquioxane having an incompletely condensed structure (not a complete octahedral structure, but having a structure in which at least one site is cleaved and the space is not closed) with a siloxane bond. A method for producing a linked copolymer is disclosed. This production method is a method in which an amine or the like is introduced into an incomplete cage silsesquioxane via an organometallic compound and then crosslinked with an aromatic imide compound or phenyl ether. Non-Patent Document 2 discloses a method for producing a copolymer in which a silanol group possessed by an incomplete cage silsesquioxane is reacted with aminosilane or the like.

  In particular, in electronic materials and optical materials, in addition to heat resistance, durability, and moldability, further improvements in transparency, weather resistance, and the like are required depending on the part used. However, in the conventional silsesquioxane copolymer, the structure is unclear and lacks stability, or when the cage silsesquioxane is graft polymerized to the main chain, it becomes a crosslinking point and gels. It is difficult to obtain a structure that completely has the above characteristics. Therefore, there is a demand for a copolymer with excellent moldability, which has a cage silsesquioxane having excellent heat resistance, weather resistance, optical properties, etc. as the main chain, and the position of the bond is clearly limited. However, there are few examples of copolymers in which a cage silsesquioxane is incorporated in the main chain.

Patent Documents 1 and 2 below have Si-ONa as a reactive group by hydrolyzing a silane compound having a trifunctional hydrolyzable group in an organic solvent in the presence of a monovalent alkali metal hydroxide. After synthesis of incomplete cage-type silsesquioxane, by reacting this incomplete cage-type silsesquioxane with a chlorosilane having a functional group according to the purpose, by copolymerization with various compounds A method for obtaining a copolymer has been reported. However, as far as the present inventor knows, no other examples have been reported, and the above method is limited in the side chain of the cage silsesquioxane skeleton and does not have curability. We are anxious about inferiority. That is, it is difficult to produce a material having excellent characteristics arbitrarily and with good reproducibility.
JP 2006-265243 A WO2003 / 024870 Brochure Chem. Mater. 2003, 15, 264-268 Macromolecules. 1993, 26, 2141-2142

  If the molecular weight can be controlled arbitrarily as described above and material design according to the purpose becomes possible, the degree of freedom of molding electronic materials and optical materials should be further increased. There are few examples of the synthesis of incorporated copolymers and the specific properties of such copolymers have not been fully elucidated. Therefore, an object of the present invention is to provide a copolymer produced from a cage silsesquioxane compound containing an alkoxyl group or a silanol group and having a cage structure in the main chain, and a curable resin composition containing the copolymer. It is to provide.

  As a result of intensive studies in order to solve the above problems, the present inventors have condensated a cage silsesquioxane compound containing an alkoxyl group or a silanol group under specific reaction conditions, so that It has been found that a copolymer incorporating a structure can be obtained. And since the curable resin composition containing this copolymer can give the cured | curing material excellent in transparency and heat resistance, it came to complete this invention.

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ³は互いに同じか異なるものであってもよく、また、ｐは0〜30の数を示す。）で表される２価の基であり、Ｙは下記一般式（3）〜（6）から選ばれるいずれかの１価の基である。
[(Ｒ⁴Ｏ)Ｒ² ₂ＳｉＯ_1/2]_a −[Ｒ¹ＳｉＯ_3/2]_n−[Ｏ_1/2]− （3）
[Ｒ⁴Ｏ_1/2]_b −[Ｒ¹ＳｉＯ_3/2]_n−[Ｏ_1/2−Ｒ² ₂ＳｉＯ_1/2]− （4）
(Ｒ⁴Ｏ_1/2) − （5）
(Ｒ² ₃ＳｉＯ_1/2) − （6）
（但し、Ｒ¹及びＲ²はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基、又はオキシラン環を有する基であって、Ｒ¹又はＲ²において、各置換基は互いに同じか異なるものであってもよく、Ｒ⁴は水素原子、メチル基又はエチル基から選ばれたいずれかである。また、a及びbは0〜3の数であり、nは8〜14の数を示す。）］で表される構成単位を有することを特徴とする籠構造含有硬化性シリコーン共重合体である。 That is, the present invention provides the following general formula (1)
^{_{Y- [Z- (O 1/2 -R 2}} 2 SiO 1/2) a - (R 1 SiO 3/2) n - (O 1/2) b] m -Z-Y (1)
[However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and in R ¹ or R ² , each substituent is Although they may be the same or different from each other, at least one of R ¹ contained in one molecule is any of a group having a vinyl group, a (meth) acryloyl group , an allyl group or an oxirane ring. is there. Moreover, a and b are numbers 0-3, satisfy | fill the relationship of 1 <= a + b <= 4, n shows the number of 8-14, m shows the number of 1-2000. Furthermore, Z is the following general formula (2)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. And p is a divalent group represented by 0 to 30), and Y is any monovalent group selected from the following general formulas (3) to (6). is there.
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [O _1/2 ]-(3)
[R ⁴ O _1/2 ] _b- [R ¹ SiO _3/2 ] _n- [O _1/2 -R ² ₂ SiO _1/2 ]-(4)
(R ⁴ O _1/2 ) − (5)
(R ² ₃ SiO _1/2 ) − (6)
(However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group, or an oxirane ring, and each substituent in R ¹ or R ² May be the same or different from each other, R ⁴ is any one selected from a hydrogen atom, a methyl group, or an ethyl group, a and b are a number from 0 to 3, and n is from 8 to 14) A skeleton structure-containing curable silicone copolymer having a structural unit represented by the following formula :

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ³は互いに同じか異なるものであってもよく、また、Ｘは水酸基、水素原子、塩素原子又はアルコキシル基であって、Ｘは互いに同じか異なるものであってもよく、更にｐは0〜30の数を示す。）で表される化合物とを縮合反応させ、又は縮合反応させて得られた反応物に対して更に下記一般式（9）
Ｒ² ₃Ｓｉ−Ｘ （9）
（但し、Ｒ²は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ²は互いに同じか異なるものであってもよい。また、Ｘは水酸基、水素原子、塩素原子又はアルコキシル基である）で表される化合物を縮合させることにより、下記一般式（1）
Ｙ−[Ｚ−(Ｏ_1/2−Ｒ² ₂ＳｉＯ_1/2) _a−(Ｒ¹ＳｉＯ_3/2)_n−（Ｏ_1/2）_b] _m−Ｚ−Ｙ (1)
［但し、Ｒ¹及びＲ²はビニル基、アルキル基、フェニル基、（メタ）アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ¹又はＲ²において、各置換基は互いに同じか異なるものであってもよいが、1分子中に含まれるＲ¹のうち少なくとも１つはビニル基、（メタ）アクリロイル基を有する基、アリル基又はオキシラン環を有する基のいずれかである。また、a及びbは0〜3の数であって１≦ a + b ≦4の関係を満たし、nは８〜１４の数を示し、ｍは1〜2000の数を示す。更に、Ｚは下記一般式（2）

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ³は互いに同じか異なるものであってもよく、また、ｐは0〜30の数を示す。）で表される２価の基であり、Ｙは下記一般式（3）〜（6）から選ばれるいずれかの１価の基である。
[(Ｒ⁴Ｏ)Ｒ² ₂ＳｉＯ_1/2]_a −[Ｒ¹ＳｉＯ_3/2]_n−[Ｏ_1/2]− （3）
[Ｒ⁴Ｏ_1/2]_b −[Ｒ¹ＳｉＯ_3/2]_n−[Ｏ_1/2−Ｒ² ₂ＳｉＯ_1/2]− （4）
(Ｒ⁴Ｏ_1/2) − （5）
(Ｒ² ₃ＳｉＯ_1/2) − （6）
（但し、Ｒ¹及びＲ²はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基、又はオキシラン環を有する基であって、Ｒ¹又はＲ²において、各置換基は互いに同じか異なるものであってもよく、Ｒ⁴は水素原子、メチル基又はエチル基から選ばれ、a及びbは0〜3の数であり、nは8〜14の数を示す。）]で表される構成単位を有する籠構造含有硬化性シリコーン共重合体を得ることを特徴とする籠構造含有硬化性シリコーン共重合体の製造方法である。 Further, the present invention provides the following general formula (7)
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [O _1/2 R ⁴ ] (7)
(However, R ¹ and R ² are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and R ⁴ is a hydrogen atom, a methyl group or an ethyl group. In R ¹ , R ² or R ⁴ , each substituent may be the same or different from each other, but at least one of R ¹ contained in one molecule is a vinyl group, (meth) A group having an acryloyl group , an allyl group, or a group having an oxirane ring, and a and b are numbers from 0 to 3, satisfying the relationship of 1 ≦ a + b ≦ 4, and n is 8 An alkoxyl group or silanol group-containing cage-type siloxane compound represented by the following general formula (8):

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. X is a hydroxyl group, a hydrogen atom, a chlorine atom or an alkoxyl group, X may be the same or different from each other, and p represents a number of 0 to 30). Condensation reaction with a compound, or a reaction product obtained by condensation reaction is further represented by the following general formula (9)
R ² ₃ Si-X (9)
(However, R ² is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ² is the same or different from each other. In addition, X is a hydroxyl group, a hydrogen atom, a chlorine atom, or an alkoxyl group, and the compound represented by the following general formula (1)
^{_{Y- [Z- (O 1/2 -R 2}} 2 SiO 1/2) a - (R 1 SiO 3/2) n - (O 1/2) b] m -Z-Y (1)
[ However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and in R ¹ or R ² , each substituent is Although they may be the same or different from each other, at least one of R ¹ contained in one molecule is any of a group having a vinyl group, a (meth) acryloyl group , an allyl group or an oxirane ring. is there. Further, a and b are numbers from 0 to 3, satisfying the relationship of 1 ≦ a + b ≦ 4, n represents a number from 8 to 14, and m represents a number from 1 to 2000. Furthermore, Z is the following general formula (2)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. And p is a divalent group represented by 0 to 30), and Y is any monovalent group selected from the following general formulas (3) to (6). is there.
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [O _1/2 ]-(3)
[R ⁴ O _1/2 ] _b- [R ¹ SiO _3/2 ] _n- [O _1/2 -R ² ₂ SiO _1/2 ]-(4)
(R ⁴ O _1/2 ) − (5)
(R ² ₃ SiO _1/2 ) − (6)
(However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group, or an oxirane ring, and each substituent in R ¹ or R ² May be the same or different from each other, R ⁴ is selected from a hydrogen atom, a methyl group or an ethyl group, a and b are a number from 0 to 3, and n is a number from 8 to 14.) ] A cocoon structure-containing curable silicone copolymer having a structural unit represented by the following formula:

In the present invention, among the alkoxyl group or silanol group-containing cage-type siloxane compound represented by the general formula (7), the alkoxyl group-containing cage-type siloxane compound can be represented by the following formula (7-1).
[(R ⁵ O) R ² ₂ SiO _1/2 ] _a − [R ¹ SiO _3/2 ] _n − [O _1/2 R ⁵ ] _b (7-1)
(Here, R ¹ and R ² are selected from vinyl group, alkyl group, phenyl group, group having (meth) acryloyl group , allyl group or group having oxirane ring, and R ⁵ is selected from methyl group or ethyl group. In R ¹ , R ² or R ⁵ , each substituent may be the same or different, but at least one of R ¹ contained in one molecule is a vinyl group or a (meth) acryloyl group. And a group having an allyl group or an oxirane ring, a and b are each a number of 0 to 3, satisfying a relation of 1 ≦ a + b ≦ 4, and n is 8 to 14 Is an integer.)

Examples of structural formulas of the alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) are shown in the following formulas (10) to (18), respectively. Structural formula (10) is n = 8, a = 1, b = 1, (11) is n = 8, a = 2, b = 0, (12) is n = 8, a = 0, When b = 2, (13) is n = 9, a = 1, b = 2, (14) is n = 10, a = 1, b = 1, (15) is n = 11, If a = 1, b = 2, (16) is n = 12, a = 1, b = 1, (17) is n = 13, a = 1, b = 2, (18) is This is the case where n = 14, a = 1, and b = 1. In addition, the alkoxyl group-containing siloxane compound has combinations with different numbers of n, a, and b, and is not limited to those shown here. In the structural formulas (10) to (18), R ¹ , R ² and R ⁵ are the same as those in the general formula (7-1).

About the manufacturing method of the alkoxyl group containing cage-type siloxane compound (7-1) used for this invention, the following general formula (19) manufactured by the well-known method, for example
[R ¹ SiO _3/2 ] _n (19)
And a siloxane compound represented by the following general formula (20)
R ² ₂ Si (OR ⁵ ) ₂ (20)
Can be obtained using a basic catalyst in a nonpolar solvent (R ¹ , R ² and R ⁵ are the same as those in formula (7-1)).

Examples of cage-type siloxane compounds represented by the general formula (19) used in the present invention are structural formulas corresponding to n = 8, 10, 12, and 14, respectively. ), (23) and (24). In the following structural formulas (21) to (24), R ¹ and R ² are the same as those in the general formula (7-1).

  The value of n in the cage-type siloxane compound represented by the general formula (19) is an integer of 8 to 14, preferably n = 8, 10 or 12, and more preferably 8. In the present invention, a mixture in which the cage siloxane compound represented by the general formula (19) is an integer in the range of n = 8 to 14 may be used, but it is preferable to use a compound having a single n.

  Further, preferred compounds of dialkoxysilane represented by the general formula (20) used in the present invention are dimethyldimethoxysilane, diethyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, ethylallyldimethoxysilane, styrylmethyl. Dimethoxysilane, divinyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-acryloxypropyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, phenylmethyldiethoxysilane, vinyl Methyldiethoxysilane, ethylallyldiethoxysilane, styrylmethyldiethoxysilane, divinyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 3-methacryloxypropyldiethoxysilane, 3-acryloxypropyldiethoxysilane, and the like.

  In addition, regarding the nonpolar solvent and the basic catalyst used when adding the cage type siloxane compound represented by the general formula (19) and the dialkoxysilane represented by the general formula (20), first, as the nonpolar solvent, Any solvent that is insoluble or hardly soluble in water may be used, but a hydrocarbon solvent is preferable. Among hydrocarbon solvents, nonpolar solvents having a relatively low boiling point such as toluene, benzene, xylene and the like are preferable, and toluene is preferably used. Basic catalysts include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And ammonium hydroxide salts such as benzyltriethylammonium hydroxide. Among these, a catalyst soluble in a nonpolar solvent such as tetraalkylammonium is preferable. Of these, tetramethylammonium hydroxide is more preferably used because of its high catalytic activity.

  Regarding the reaction in which the cage type siloxane compound represented by the general formula (19) and the dialkoxysilane represented by the general formula (20) are added using a basic catalyst in a nonpolar solvent, the following presumption is assumed. Can do. First, the siloxane bond constituting the cage siloxane is cleaved by a basic catalyst. Next, the cleaved siloxane bond ends are cleaved between the reaction of the alkoxyl group of dialkoxysilane and the addition of the alkoxyl group by the alcohol exchange reaction (addition reaction), and within and between the molecules of the cage siloxane. A reaction (recombination reaction) in which the siloxane bond ends are bonded to each other occurs competitively. Therefore, it is necessary to preferentially perform the former (addition reaction). In addition, since the reaction in the present invention is basically an equilibrium reaction, the number average molecular weight Mn, yield, and production rate of the target alkoxyl group-containing cage-type siloxane compound are the reaction temperature, reaction time, and both raw materials. Since it is naturally determined by the ratio of addition amount, the amount of base catalyst, etc., it is preferably carried out under the conditions described below.

That is, for the reaction conditions of the reaction in which the cage siloxane compound represented by the general formula (19) and the dialkoxysilane represented by the general formula (20) are added using a basic catalyst in a nonpolar solvent, the general formula ( In order that the alkoxyl group of 20) reacts with moisture in the reaction system to suppress conversion to silanol groups and hydrolysis condensation, the reaction is preferably performed in an inert atmosphere such as nitrogen gas. The reaction temperature is not higher than the boiling point of the dialkoxysilane represented by the general formula (20), preferably in the range of 70 to 200 ° C, more preferably 80 to 130 ° C. If the reaction temperature is too low, a sufficient driving force for the addition reaction cannot be obtained and the reaction does not proceed. If the reaction temperature is too high, it may cause a self-polymerization reaction when it contains a reactive functional group with an unsaturated bond such as a group having a vinyl group or a (meth) acryloyl group. It is necessary to add a polymerization inhibitor or the like.

The amount of the nonpolar solvent to be used is not particularly limited, but it is preferable to use 1 to 5 times the weight with respect to the weight of the cage siloxane compound in consideration of the stirring efficiency and the pot efficiency. About the addition amount of dialkoxysilane, it is preferable to add in 0.5-2.0 mol with respect to 1 mol of cage type siloxane compounds. By adjusting the amount of dialkoxysilane added, it is possible to adjust the amount of alkoxyl groups in the alkoxyl group-containing cage-type siloxane compound. For example, an alkoxyl group-containing cage-type siloxane compound obtained when 1 mol of dialkoxysilane is added and reacted with 1 mol of cage-type siloxane compound has the following general formula (7-1)
[(R ⁵ O) R ² ₂ SiO _1/2 ] _a − [R ¹ SiO _3/2 ] _n − [O _1/2 R ⁵ ] _b (7-1)
(Here, R ¹ , R ² , R ⁵ , and n are the same as described above.)
In this case, a + b = 2, and a mixture of alkoxyl group-containing cage-type siloxane compounds containing 2 alkoxyl groups in the cage structure unit is obtained. Moreover, when the cage type | mold siloxane compound to be used is a mixture, the content of the alkoxyl group per cage | basket structure unit can be adjusted by adjusting the addition amount of dialkoxysilane with respect to the average value of n. On the other hand, when the amount of dialkoxysilane added is more than the range of 0.5 to 2.0 moles per mole of saddle type siloxane compound, more siloxane bonds forming the saddle structure are cleaved and alkoxyl groups are added. Because it happens, the cocoon structure is decomposed.

  The basic catalyst is used in an amount of 0.01 to 0.15 mol, preferably 0.06 to 0.1 mol, based on 1 mol of the cage siloxane compound. Good. Moreover, when the cage-type siloxane compound to be used is a mixture, it is preferable to add a basic catalyst so that it may become 0.01-0.15 mol with respect to the average value of n, Preferably it is 0.06-0.1 mol. .

  The alkoxyl group-containing cage-type siloxane compound (7-1) used in the present invention depends on the type and purity of the cage-type siloxane compound used, the addition amount, type and purity of the dialkoxysilane compound, and the reaction conditions and the state of the polycondensate. In general, a and b in the general formula (7-1) are numbers from 0 to 3, satisfy 1 ≦ a + b ≦ 4, and n is a plurality of types represented by an integer of 8 to 14 It is preferable to use it as a mixture of alkoxyl group-containing cage-type siloxane compounds.

In the present invention, among the alkoxyl group or silanol group-containing cage-type siloxane compound represented by the general formula (7), the silanol group-containing cage-type siloxane compound can be represented by the following formula (7-2). The silanol group-containing cage-type siloxane compound can be obtained by hydrolyzing the alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) in the presence of an acid or base catalyst.
[(HO) R ² ₂ SiO _1/2 ] _a − [R ¹ SiO _3/2 ] _n − [O _1/2 H] _b (7-2)
(However, R ¹ and R ² are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring. In R ¹ or R ² , each substituent is Although they may be the same or different from each other, at least one of R ¹ contained in one molecule is any of a group having a vinyl group, a (meth) acryloyl group , an allyl group or an oxirane ring. A and b are numbers from 0 to 3, satisfying 1 ≦ a + b ≦ 4, and n is an integer of 8 to 14.)

Examples of structural formulas of silanol group-containing cage-type siloxane compounds are basically those in which R ⁵ in the structural formula examples (10) to (18) of the alkoxyl group-containing cage-type siloxane compounds described above is replaced with hydrogen atoms. Correspond. That is, structural formula (10) is n = 8, a = 1, b = 1, (11) is n = 8, a = 2, b = 0, (12) is n = 8, a = 0, b = 2 , (13) n = 9, a = 1, b = 2, (14) n = 10, a = 1, b = 1, (15) n = 11, a = 1, b = 2, ( 16) is n = 12, a = 1, b = 1, (17) is n = 13, a = 1, b = 2, and (18) is n = 14, a = 1, b = 1. is there. Note that silanol group-containing siloxane compounds are not limited to these because they have different combinations of n, a, and b numbers. In Structural Formulas (10) to (18), R ¹ and R ² are the same as those in General Formula (7-1).

  Examples of the acid catalyst used when hydrolyzing the alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) in the presence of an acid or base catalyst to obtain a silanol group-containing cage-type siloxane compound include hydrochloric acid Sulfuric acid, acetic acid, formic acid, trifluoromethanesulfonic acid and the like. Bases include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium. Illustrative are ammonium hydroxide salts such as hydroxide.

  Water necessary for hydrolysis may be water contained in an acid or base catalyst, or may be added separately. The amount of water is preferably 1 to 3 moles, more preferably 1 to 1.5 moles per mole of alkoxyl groups of the alkoxyl group-containing cage-type siloxane compound to be used. If the amount of water is too small, conversion of the alkoxyl group to the silanol group is not performed completely, and if it is too much, there is a possibility that the siloxane bond is broken.

  About the usage-amount of an acid or a base catalyst, 0.1-1.5 mol is preferable with respect to 1 mol of alkoxyl groups of the alkoxyl group containing cage-type siloxane compound to be used. If the amount of the catalyst used is too large, the siloxane bond is broken and the soot structure is decomposed.

  About hydrolysis reaction conditions, 0-40 degreeC is preferable and, as for reaction temperature, 10-30 degreeC is more preferable. When the reaction temperature is lower than 0 ° C., the reaction rate becomes slow, and the alkoxyl group remains unreacted, resulting in a long reaction time. On the other hand, when the temperature is higher than 40 ° C., in addition to hydrolysis, a condensation reaction of silanol groups proceeds, and as a result, an increase in the molecular weight of the hydrolysis product is promoted. The reaction time is preferably 2 hours or more. If the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently and the alkoxyl group remains in an unreacted state.

At the time of hydrolysis, one or both of a nonpolar solvent and a polar solvent may be used in combination, preferably both are used, or only a polar solvent is used. As the polar solvent, alcohols such as methanol, ethanol and 2-propanol, or other polar solvents can be used, and preferably a lower alcohol having 1 to 6 carbon atoms which is soluble in water. It is more preferable to use 2-propanol. If only a nonpolar solvent is used, the reaction system will not be uniform and hydrolysis will not proceed sufficiently. In addition, about the nonpolar solvent, what was mentioned in the example in the manufacturing method of an alkoxyl group containing cage type | mold siloxane compound can be used.

  After completion of the hydrolysis reaction, a polar solvent such as toluene is added, and depending on the catalyst used, the reaction solution is neutralized with a weak base or a weakly acidic solution, and water or a water-containing reaction solvent is separated. Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate.

The following general formula (7)
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [OR ⁴ ] (7)
Wherein R ¹ and R ² are selected from vinyl group, alkyl group, phenyl group, group having (meth) acryloyl group , allyl group or group having oxirane ring, and R ⁴ is hydrogen atom, methyl group or ethyl group In R ¹ , R ² or R ⁴ , each substituent may be the same or different from each other, but at least one of R ¹ contained in one molecule is a vinyl group, (meth) A group having an acryloyl group , an allyl group, or a group having an oxirane ring, and a and b are each a number of 0 to 3, satisfying a relation of 1 ≦ a + b ≦ 4, and n is 8 An alkoxyl group or silanol group-containing cage-type siloxane compound represented by the following formula:

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ³は互いに同じか異なるものであってもよく、また、Ｘは水酸基、水素原子、塩素原子又はアルコキシル基であって、Ｘは互いに同じか異なるものであってもよく、更にｐは0〜30の数を示す。）で表される化合物とを縮合反応させることにより、下記一般式（１-１）
Ｙ¹−[Ｚ−(Ｏ_1/2−Ｒ² ₂ＳｉＯ_1/2) _a−(Ｒ¹ＳｉＯ_3/2)_n−（Ｏ_1/2）_b] _m−Ｚ−Ｙ¹ (１-１)
｛但し、Ｒ¹及びＲ²はビニル基、アルキル基、フェニル基、（メタ）アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ¹又はＲ²において、各置換基は互いに同じか異なるものであってもよいが、Ｒ¹に関しては1分子中の少なくとも１つはビニル基、（メタ）アクリロイル基を有する基、アリル基又はオキシラン環を有する基のいずれかである。また、a及びbは０〜３の数であって１≦ a + b ≦4の関係を満たし、nは８〜１４の数を示し、ｍは1〜2000の数を示す。更に、Ｚは下記一般式(2)

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ³は互いに同じか異なるものであってもよく、また、ｐは0〜30の数を示す。）で表される２価の基であり、Ｙ¹は、下記一般式（３）
[(Ｒ⁴Ｏ)Ｒ² ₂ＳｉＯ_1/2]_a −[Ｒ¹ＳｉＯ_3/2]_n−[Ｏ_1/2]− (３)
又は下記一般式(４)
[Ｒ⁴Ｏ_1/2]_b −[Ｒ¹ＳｉＯ_3/2]_n−[Ｏ_1/2−Ｒ² ₂ＳｉＯ_1/2]− (４)
又は下記一般式(５)
(Ｒ⁴Ｏ_1/2) − (５)
（但し、Ｒ¹及びＲ²はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基、又はオキシラン環を有する基であって、Ｒ¹又はＲ²において、各置換基は互いに同じか異なるものであってもよく、Ｒ⁴は水素原子、メチル基又はエチル基から選ばれいずれかであり、a及びbは０〜３の数であり、nは8〜14の数で表される１価の基である。）]で表される構成単位を特徴とする籠構造含有硬化性シリコーン共重合体を得ることができる。 Next, the alkoxyl group or silanol group-containing cage-type siloxane compound represented by the general formula (7) and the following general formula (8)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. X is a hydroxyl group, a hydrogen atom, a chlorine atom or an alkoxyl group, X may be the same or different from each other, and p represents a number of 0 to 30). By a condensation reaction with a compound, the following general formula (1-1)
_{^{Y 1 - [Z- (O 1/2}} -R 2 2 SiO 1/2) a - (R 1 SiO 3/2) n - (O 1/2) b] m -Z-Y 1 (1-1 )
{However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and in R ¹ or R ² , each substituent is Although they may be the same or different from each other, with respect to R ¹ , at least one in one molecule is either a vinyl group, a group having a (meth) acryloyl group , an allyl group, or a group having an oxirane ring. Moreover, a and b are numbers 0-3, satisfy | fill the relationship of 1 <= a + b <= 4, n shows the number of 8-14, m shows the number of 1-2000. Furthermore, Z is the following general formula (2)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. may, also, p is a divalent group represented by indicating.) the number of 0 to 30, Y ¹ is represented by the following general formula (3)
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [O _1/2 ]-(3)
Or the following general formula (4)
[R ⁴ O _1/2 ] _b- [R ¹ SiO _3/2 ] _n- [O _1/2 -R ² ₂ SiO _1/2 ]-(4)
Or the following general formula (5)
(R ⁴ O _1/2 ) − (5)
(However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group, or an oxirane ring, and each substituent in R ¹ or R ² May be the same or different from each other, R ⁴ is any one selected from a hydrogen atom, a methyl group or an ethyl group, a and b are a number from 0 to 3, and n is a number from 8 to 14 The cocoon structure-containing curable silicone copolymer characterized by the structural unit represented by the following formula can be obtained.

  籠 structure-containing curing represented by general formula (1-1) obtained by condensation reaction between alkoxyl group or silanol group-containing cocoon type siloxane compound represented by general formula (7) and compound represented by general formula (8) The method for producing a conductive silicone copolymer includes the use of an alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) and a silanol group-containing cage-type siloxane compound represented by the formula (7-2) In the case of using a silanol group-containing cage-type siloxane compound represented by the general formula (7-2), the production method differs depending on whether or not the substituent X of the compound represented by the general formula (8) is used. The manufacturing method varies depending on the type.

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、互いに同じか異なるものであってもよく、ｐは0〜30の数を示す。）とを反応させる場合、一般式(７−１)で表されるアルコキシル基含有籠型シロキサン化合物１モルに対して０．５〜１０モル、好ましくは０．５〜３．０モルの範囲となるように上記一般式(８−１)で表されるシランジオール、またはα、ω−ジシラノールシロキサンを触媒存在下、非極性溶媒とエーテル系溶媒のうち1つもしくは両方をあわせた溶媒中で脱アルコール縮合させることで、一般式(１−１)で表される構成単位を有する籠構造含有硬化性シリコーン共重合体を得ることができる。 First, when an alkoxyl group-containing siloxane compound represented by the general formula (7-1) is subjected to a condensation reaction with a compound of the general formula (8) in which X is a hydroxyl group, that is, an alkoxyl group-containing compound represented by the general formula (7-1) Siloxane compound and compound of the following general formula (8-1)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, which may be the same or different from each other, p represents a number of 0 to 30), and 0.5 to 10 mol, preferably 0 with respect to 1 mol of the alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1). In the presence of a catalyst, the non-polar solvent and the ether solvent of the silane diol represented by the general formula (8-1) or α, ω-disianol siloxane so as to be in the range of 5 to 3.0 mol By carrying out dealcohol condensation in a solvent in which one or both are combined, a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (1-1) can be obtained.

  Specific dealcoholization condensation of the alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) and the silane diol or α, ω-disianol siloxane represented by the general formula (8-1) For example, the alkoxy group-containing cage-type siloxane compound represented by the general formula (7-1), the compound of the general formula (8-1), and the catalyst are used as one of a nonpolar solvent and an ether solvent. Or when it melt | dissolves in the solvent which combined both, the density | concentration is good to set it as 0.1-2.0M (mol / l) with respect to an alkoxyl group containing cage-type siloxane compound. The reaction temperature is preferably 0 to 130 ° C, more preferably 50 to 110 ° C. When the reaction temperature is lower than 0 ° C., the reaction rate becomes slow, resulting in a long reaction time. On the other hand, when the temperature is higher than 130 ° C., the cleavage reaction of the cage structure occurs, and as a result of a complicated condensation reaction, a gel-like solid is formed. The reaction time is preferably 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed.

  After completion of the reaction, the reaction solution is neutralized or acidic, and then water or a water-containing reaction solvent is separated. Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate. When an ether solvent is used, means such as evaporation under reduced pressure can be employed. After removing the ether solvent, a nonpolar solvent is added to dissolve the polycondensate, and washing and drying are performed in the same manner as described above.

  Specific examples of the silane diol in which p is 0 in the general formula (8-1) are as follows: dimethyl silane diol, ethyl methyl silane diol, phenyl methyl silane diol, diethyl silane diol, ethyl allyl silane diol, styryl methyl silane Examples include diol, divinyl silane diol, vinyl methyl silane diol, 3-glycidoxy propyl methyl silane diol, 3-acryloxy propyl methyl silane diol, 3-methacryloxy propyl methyl silane diol, diphenyl silane diol and the like.

  Specific examples of α, ω-disilanol siloxane in which p is represented by 1 to 30 for the general formula (8-1) include silanol-terminated polydimethylsiloxane, silanol-terminated polydiphenylsiloxane, and silanol-terminated diphenylsiloxane-methyl. Examples include siloxanes and copolymers.

  About organic solvent used for dealcoholization condensation of alkoxyl group-containing cage-type siloxane compound represented by general formula (7-1) and silane diol represented by general formula (8-1) or α, ω-disianol siloxane Can be arbitrarily selected as long as it is inert with respect to the alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) and silane diol, or α, ω-disianol siloxane. Of these, specific examples of nonpolar solvents include hydrocarbon solvents such as hexane, toluene, xylene, and benzene. Specific examples of the ether solvent include diethyl ether and tetrahydrofuran. Among these, it is preferable to use toluene as a solvent. Further, a mixed system of an ether solvent and a nonpolar solvent may be used. The preferred use ratio of the organic solvent is in the range of 0.01 to 10M (mol / l), preferably 0.1 to 1M (mol / l) per mole of the structural unit represented by the general formula (2). ).

  Moreover, the catalyst used for the dealcoholization condensation of the alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) and the silane diol represented by the general formula (8-1) or α, ω-disianol siloxane For, potassium hydroxide, sodium hydroxide and alkali metal hydroxides such as cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyl hydroxide Ammonium hydroxide salts such as triethylammonium, tetraethoxytitanium, tetrabutoxytitanium, tin oxide, dibutyltin oxide, zinc acetate dihydrate, lead acetate trihydrate, lead oxide, aluminum acetate, manganese acetate tetrahydrate , Cobalt acetate tetrahydrate, cadmium acetate, dibu Organometallic catalysts such as rutin laurate, dibutyltin maleate, dioctyltin marker peptide, and stannous octoate lead octenoate, triethylenediamine, tetramethylguanidine, 2- (dimethylaminomethyl) phenol, N, N, N ', N Examples include '-tetramethylhexane-1,6-diamine, 1,8-diazabicyclo [5.4.0] undecene-7, p-toluenesulfonic acid, and trifluoroacetic acid. Among these, it is preferable to use tetramethylammonium hydroxide from the viewpoint of high catalytic activity.

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、互いに同じか異なるものであってもよく、Ｒ⁵はメチル基、エチル基、プロピル基であって、互いに同じか異なるものであってもよい。ｐは0〜30の数を示す。）とを反応させる場合、一般式(７−２)で表されるシラノール基含有籠型シロキサン化合物1モルに対して0.5〜10モル、好ましくは0.5〜3.0モルの範囲で上記一般式(８−２)で表されるジアルコキシシラン、またはα、ω−ジアルコキシシロキサンを触媒存在下、非極性溶媒とエーテル系溶媒のうち1つもしくは両方をあわせた溶媒中で脱アルコール縮合させることで、一般式(１−１)で表される構成単位を有する籠構造含有硬化性シリコーン共重合体を得ることができる。 Next, when a silanol group-containing siloxane compound represented by the general formula (7-2) and a compound of the general formula (8) in which X is an alkoxyl group are subjected to a condensation reaction, that is, a silanol represented by the general formula (7-2) Group-containing siloxane compound and compound of general formula (8-2) below

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, which may be the same or different from each other, R ⁵ is a methyl group, an ethyl group, or a propyl group, and may be the same or different from each other, and p is a number of 0 to 30). The dialkoxysilane represented by the above general formula (8-2) in the range of 0.5 to 10 mol, preferably 0.5 to 3.0 mol, or α, ω with respect to 1 mol of the silanol group-containing cage-type siloxane compound represented by -Having a structural unit represented by the general formula (1-1) by dealcoholization condensation of dialkoxysiloxane in the presence of a catalyst in one or both of a nonpolar solvent and an ether solvent.籠 Structure-containing curable silicone It is possible to obtain the union.

  Specific dealcoholization of silanol group-containing cage-type siloxane compound represented by general formula (7-2) and dialkoxysilane or α, ω-dialkoxysiloxane represented by general formula (8-2) Regarding the reaction conditions for the condensation, for example, a silanol group-containing cage-type siloxane compound represented by the general formula (7-2) and a dialkoxysilane represented by the above general formula (8-2), or α, ω-dialkoxy When the siloxane and catalyst are dissolved in one or both of a non-polar solvent and an ether solvent, the amount of the solvent so that the concentration of silanol group-containing cage-type siloxane compound is 0.1 to 2.0 M (mol / l) Is preferably adjusted. The reaction temperature is preferably 0 to 130 ° C, more preferably 50 to 110 ° C. When the reaction temperature is lower than 0 ° C., the reaction rate becomes slow, resulting in a long reaction time. On the other hand, when the temperature is higher than 130 ° C., the cleavage reaction of the cage structure occurs, and as a result of a complicated condensation reaction, a gel-like solid is formed. The reaction time is preferably 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed.

  After completion of the reaction, the reaction solution is neutralized or acidic, and then water or a water-containing reaction solvent is separated. Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate. When an ether solvent is used, means such as evaporation under reduced pressure can be employed. After removing the ether solvent, a nonpolar solvent is added to dissolve the polycondensate, and washing and drying are performed in the same manner as described above.

  Specific examples of dialkoxysilanes in which p is 0 in formula (8-2) include dimethyldimethoxysilane, diethyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, ethylallyldimethoxysilane, and styrylmethyl. Dimethoxysilane, divinyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-acryloxypropyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, phenylmethyldiethoxysilane, vinyl Methyldiethoxysilane, ethylallyldiethoxysilane, styrylmethyldiethoxysilane, divinyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacrylic Propyl diethoxy silane, 3-acryloxy propyl diethoxy silane, and the like.

  Further, with respect to the general formula (8-2), specific examples of α, ω-dialkoxysiloxane in which p is represented by 1 to 30 include 1,3-dimethoxytetramethyldisiloxane and 1,3-diethoxytetra. Examples include methyldisiloxane, 1,5-dimethoxyhexamethyltrisiloxane, 1,7-dimethoxyoctamethyltetrasiloxane, 1,5-diethoxyhexamethyltrisiloxane, 1,7-diethoxyoctamethyltetrasiloxane, and the like.

  An organic solvent used for dealcoholization condensation of the silanol group-containing cage-type siloxane compound represented by the general formula (7-2) and the dialkoxysilane or α, ω-dialkoxysiloxane in the general formula (8-2); For the catalyst, the alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) and the silane diol represented by the general formula (8-1) or α, ω-disianol siloxane are used. The same organic solvent and catalyst as used for the dealcoholization condensation are used.

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、互いに同じか異なるものであってもよい。ｐは0〜30の数を示す。）とを反応させる場合、一般式(７−２)で表されるシラノール基含有籠型シロキサン化合物1モルに対して0.5〜10モル、好ましくは0.5〜3.0モルの範囲で上記一般式(８−３)で表されるジハイドロジェンシラン、またはα,ω−ジハイドロジェンシロキサンを触媒存在下、非極性溶媒とエーテル系溶媒のうち1つもしくは両方をあわせた溶媒中で脱水素縮合させることで、一般式(１-１)で表される構成単位を有する籠構造含有硬化性シリコーン共重合体を得ることができる。 Next, when the silanol group-containing siloxane compound represented by the general formula (7-2) is subjected to a condensation reaction with the compound of the general formula (8) in which X is a hydrogen atom, that is, the silanol represented by the general formula (7-2) Group-containing siloxane compound and compound of general formula (8-3) below

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and may be the same or different from each other. p represents a number of 0 to 30). 0.5 to 10 moles, preferably 0.5 to 3.0 moles per mole of silanol group-containing cage-type siloxane compound represented by the general formula (7-2). In the molar range, one or both of a nonpolar solvent and an ether solvent are combined in the presence of a catalyst of dihydrogensilane represented by the above general formula (8-3) or α, ω-dihydrogensiloxane. By dehydrogenating and condensing in a solvent, a cage structure-containing curable silicone copolymer having a structural unit represented by the general formula (1-1) can be obtained.

  Specific reaction of silanol group-containing cage-type siloxane compound represented by general formula (7-2) with dihydrogensilane or α, ω-dihydrogensiloxane represented by general formula (8-3) Regarding the conditions, for example, a silanol group-containing cage-type siloxane compound represented by the general formula (7-2) and dihydrogensilane, or α, ω-dihydrogensiloxane and a catalyst are selected from a nonpolar solvent and an ether solvent. It is preferable to adjust the amount of the solvent so that the concentration of the silanol group-containing cage-type siloxane compound is 0.1 to 2.0 M (mol / l) when dissolved in one or both solvents. The reaction temperature is preferably 0 to 100 ° C, more preferably 20 to 80 ° C. When the reaction temperature is lower than 0 ° C., the reaction rate becomes slow, resulting in a long reaction time. On the other hand, when the temperature is higher than 100 ° C., the reaction rate is too high, so that a complicated condensation reaction proceeds and a gel-like solid is formed. The reaction time is preferably 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed.

  After completion of the reaction, the reaction solution is neutralized or acidic, and then water or a water-containing reaction solvent is separated. At this time, those whose terminal groups are not silanol groups are converted into silanol groups by hydrolysis. Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate. When an ether solvent is used, means such as evaporation under reduced pressure can be employed. After removing the ether solvent, a nonpolar solvent is added to dissolve the polycondensate, and washing and drying are performed in the same manner as described above.

  With respect to the general formula (8-3), specific examples of dihydrogensilane in which p is 0 are diethylsilane, diphenylsilane and the like.

  Further, with respect to the general formula (8-3), specific examples of α, ω-dihydrogensiloxane represented by p of 1 to 30 include 1,1,3,3-tetramethyldisiloxane, 1, 1,3,3-tetracyclopentyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5 , 5,7,7-octamethyltetrasiloxane, hydrogen-terminated polydimethylsiloxane, hydrogen-terminated polymethylphenylsiloxane, hydrogen-terminated methylsiloxane-dimethylsiloxane copolymer, hydrogen-terminated methylsiloxane-methylphenylsiloxane copolymer, hydrogen-terminated Examples include phenyl (dimethylhydrosiloxy) siloxane.

  The organic solvent used when X of the compound represented by the general formula (8) is hydrogen can be arbitrarily selected as long as it is inactive with respect to dihydrogensilane or α, ω-dihydrogensiloxane, Of these, specific examples of nonpolar solvents include hydrocarbon solvents such as hexane, toluene, xylene, and benzene. Specific examples of the ether solvent include diethyl ether and tetrahydrofuran. Among these, it is preferable to use toluene as a solvent. Further, a mixed system of a polar solvent and an ether solvent may be used. The preferred use ratio of the organic solvent is in the range of 0.01 to 10 M (mol / l), preferably 0.1 to 1 M (mol / l) with respect to 1 mol of the structural unit represented by the general formula (2). ).

  Moreover, about the catalyst used when X of the compound represented by General formula (8) is hydrogen, tetraethoxytitanium, tetrabutoxytitanium, hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N-ethyl Examples include hydroxylamine compounds such as hydroxylamine and N, N-diethylhydroxylamine. Among these, it is preferable to use N, N-diethylhydroxylamine.

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、互いに同じか異なるものであってもよい。ｐは0〜30の数を示す。）とを反応させる場合、一般式(７−２)で表されるシラノール基含有籠型シロキサン化合物1モルに対して0.5〜10モル、好ましくは0.5〜3.0モルの範囲で上記一般式(８−４)で表されるジクロロシラン、またはα,ω−ジクロロシロキサンを触媒存在下、非極性溶媒とエーテル系溶媒のうち1つもしくは両方をあわせた溶媒中で脱塩酸縮合させることで、一般式(１-１)で表される構成単位を有する籠構造含有硬化性シリコーン共重合体を得ることができる。 Next, when the silanol group-containing siloxane compound represented by the general formula (7-2) is subjected to a condensation reaction with the compound of the general formula (8) in which X is a chlorine atom, that is, the silanol represented by the general formula (7-2) Group-containing siloxane compound and compound of the following general formula (8-4)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and may be the same or different from each other. p represents a number of 0 to 30). 0.5 to 10 moles, preferably 0.5 to 3.0 moles per mole of silanol group-containing cage-type siloxane compound represented by the general formula (7-2). In the range of mole, dichlorosilane represented by the above general formula (8-4) or α, ω-dichlorosiloxane in the presence of a catalyst in a solvent combining one or both of a nonpolar solvent and an ether solvent. By dehydrochlorination condensation, a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (1-1) can be obtained.

  Specific dehydrochlorination condensation reaction of silanol group-containing cage-type siloxane compound represented by general formula (7-2) with dichlorosilane or α, ω-dichlorosiloxane represented by general formula (8-4) As for the conditions, for example, dichlorosilane or α, ω-dichlorosiloxane is dissolved in one or both of a nonpolar solvent and an ether solvent, and dichlorosilane or α, ω-dichlorosiloxane is dissolved. Silanol group-containing cage-type siloxane compound was mixed with one or both of a nonpolar solvent and an ether solvent in a mixed solution in which 2 equivalents or more of triethylamine was added, or a mixed solution dissolved in an amine solvent as a solvent and base. A solution dissolved in a solvent is preferably dropped at room temperature under an inert gas atmosphere such as nitrogen, and then stirred at room temperature for 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed. After completion of the reaction, toluene and water are added, and the cocoon structure-containing curable silicone copolymer having the structural unit represented by the general formula (1-1) is dissolved in toluene, and excess chlorosilanes, by-product hydrochloric acid and The hydrochloride is dissolved in the aqueous layer and removed. Further, the organic layer is dried using a desiccant such as magnesium sulfate, and the used base and solvent are removed by concentration under reduced pressure.

  Specific examples of dichlorosilane in which p is 0 with respect to general formula (8-4) are allyldichlorosilane, allylhexyldichlorosilane, allylmethyldichlorosilane, allylphenyldichlorosilane, methyldichlorosilane, dimethyldichlorosilane. , Ethyldichlorosilane, methylvinyldichlorosilane, ethylmethyldichlorosilane, ethoxymethyldichlorosilane, divinyldichlorosilane, diethyldichlorosilane, methylpropyldichlorosilane, diethoxydichlorosilane, butylmethyldichlorosilane, phenyldichlorosilane, diallyldichlorosilane , Methylpentyldichlorosilane, methylphenyldichlorosilane, cyclohexylmethyldichlorosilane, hexylmethyldichlorosilane, phenylvinyldichlorosila 6-methyldichlorosilyl-2-norbornene, 2-methyldichlorosilylnorbornene, 3-methacryloxypropyldichloromethylsilane, heptylmethyldichlorosilane, dibutyldichlorosilane, methyl-β-phenethyldichlorosilane, methyloctyldichlorosilane, t -Butylphenyldichlorosilane, decylmethyldichlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dodecylmethyldichlorosilane, methyloctadecyldichlorosilane and the like.

  Further, with respect to the general formula (8-4), specific examples of α, ω-dichlorosiloxane in which p is represented by 1 to 30 include 1,1,3,3-tetramethyl-1,3-dichlorosiloxane. 1,1,3,3-tetracyclopentyl-1,3-dichlorosiloxane, 1,1,3,3-tetraisopropyl-1,3-dichlorosiloxane, 1,1,3,3,5,5- Examples include hexamethyl-1,5-dichlorotrisiloxane, 1,1,3,3,5,5,7,7-octamethyl-1,7-dichlorotetrasiloxane.

  The organic solvent used when X of the compound represented by the general formula (8) is chlorine can be arbitrarily selected as long as it is inert to dichlorosilane or α, ω-dichlorosiloxane. Specific examples of the nonpolar solvent include hydrocarbon solvents such as hexane, toluene, xylene, and benzene. Specific examples of the ether solvent include diethyl ether and tetrahydrofuran. Among these, ether solvents are preferable from the viewpoint of contribution to structure control due to the solvation effect, and tetrahydrofuran is more preferable among them. Moreover, you may use an amine solvent as a solvent and a base individually or as a mixed solution. Specific examples of the amine solvent include pyridine, triethylamine, aniline, N, N-diisopropylamine. When an amine solvent is not used, a base such as triethylamine is added. The preferred use ratio of the solvent should be in the range of 0.01 to 10 M (mol / l) with respect to 1 mol of the silanol group-containing cage-type siloxane compound structural unit represented by the general formula (7-2), preferably 0.01 to 1 M (mol / l).

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ³は互いに同じか異なるものであってもよく、また、ｐは0〜30の数を示す。）で表される２価の基であり、Ｙ¹は、下記一般式(3) 〜（6）から選ばれるいずれかの１価の基である。
[(Ｒ⁴Ｏ)Ｒ² ₂ＳｉＯ_1/2]_a −[Ｒ¹ＳｉＯ_3/2]_n−[Ｏ_1/2]− (3)
[Ｒ⁴Ｏ_1/2]_b −[Ｒ¹ＳｉＯ_3/2]_n−[Ｏ_1/2−Ｒ² ₂ＳｉＯ_1/2]− (4)
(Ｒ⁴Ｏ_1/2) − (5)
（但し、Ｒ¹、Ｒ²はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基、又はオキシラン環を有する基であって、Ｒ¹又はＲ²において、各置換基は互いに同じか異なるものであっても良く、Ｒ⁴は水素原子、メチル基、エチル基から選ばれたいずれかである。また、a及びbは0〜3の数であり、nは8〜14の数を示す。）｝で表される構成単位を特徴とする籠構造含有硬化性シリコーン共重合体を得ることができる。 The soot structure-containing curable silicone copolymer obtained as described above can be represented by the following general formula (1-1).
_{^{Y 1 - [Z- (O 1/2}} -R 2 2 SiO 1/2) a - (R 1 SiO 3/2) n - (O 1/2) b] m -Z-Y 1 (1-1 )
[However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and in R ¹ or R ² , each substituent is Although they may be the same or different from each other, at least one of R ¹ contained in one molecule is any of a group having a vinyl group, a (meth) acryloyl group , an allyl group or an oxirane ring. is there. A and b are numbers from 0 to 3 and satisfy the relationship of 1 ≦ a + b ≦ 4. Further, n represents a number from 8 to 14, m represents a number from 1 to 2000, and Z represents the following general formula (2)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. may, also, p is a divalent group represented by indicating.) the number of 0 to 30, Y ¹ is any monovalent selected from the following formulas (3) to (6) It is a group.
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [O _1/2 ]-(3)
[R ⁴ O _1/2 ] _b- [R ¹ SiO _3/2 ] _n- [O _1/2 -R ² ₂ SiO _1/2 ]-(4)
(R ⁴ O _1/2 ) − (5)
(However, R ¹ and R ² are vinyl groups, alkyl groups, phenyl groups, groups having (meth) acryloyl groups , allyl groups, or groups having an oxirane ring, and each of R ^{1 and} R ² is a substituent. May be the same or different from each other, R ⁴ is any one selected from a hydrogen atom, a methyl group, and an ethyl group, a and b are numbers from 0 to 3, and n is from 8 to The number of 14 can be obtained.] The cocoon structure containing curable silicone copolymer characterized by the structural unit represented by this can be obtained.

（但し、Ｒ³は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基又はオキシラン環を有する基であって、Ｒ³は互いに同じか異なるものであってもよく、また、ｐは0〜30の数を示す。）で表される２価の基であり、Ｙ²は、下記一般式(6)で表される１価の基である。
(Ｒ² ₃ＳｉＯ_1/2) − (6)
（但し、Ｒ²はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基を有する基、アリル基、又はオキシラン環を有する基であって、Ｒ²は互いに同じか異なるものであっても良い１価の基である。）｝で表される構成単位を有する籠構造含有硬化性シリコーン共重合体とすることもできる。 Further, among the cocoon structure-containing curable silicone copolymers represented by the general formula (1-1), the cocoon structure-containing curable silicone copolymer in which R ⁴ in the terminal Y ¹ is a hydrogen atom, that is, a silanol terminal cocoon structure Containing curable silicone copolymer and the following general formula (9)
R ² ₃ Si-X (9)
(However, R ² is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ² is the same or different from each other. And X is a hydrogen atom, a chlorine atom or an alkoxyl group).
_{^{Y 2 - [Z- (O 1/2}} -R 2 2 SiO 1/2) a - (R 1 SiO 3/2) n - (O 1/2) b] m -Z-Y 2 (1-2 )
[However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and in R ¹ or R ² , each substituent is Although they may be the same or different from each other, at least one of R ¹ contained in one molecule is any of a group having a vinyl group, a (meth) acryloyl group , an allyl group or an oxirane ring. is there. A and b are numbers from 0 to 3 and satisfy the relationship of 1 ≦ a + b ≦ 4. Further, n represents a number from 8 to 14, m represents a number from 1 to 2000, and Z represents the following general formula (2)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. And p is a divalent group represented by the formula (6), and Y ² is a monovalent group represented by the following general formula (6).
(R ² ₃ SiO _1/2 ) − (6)
(However, R ² is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group, or an oxirane ring, and R ² may be the same or different from each other. It is also a monovalent group.)} A cocoon structure-containing curable silicone copolymer having a structural unit represented by

Here, among the cocoon structure-containing curable silicone copolymer represented by the general formula (1-1), R ⁴ in the terminal Y ¹ is a methyl group or an ethyl group, that is, an alkoxyl terminal cocoon structure-containing curable silicone. It is also possible to obtain a curable silicone copolymer containing a silanol terminal cage structure by hydrolyzing it in the presence of an acid or base catalyst and converting the terminal to silanol. In addition, about the method of a hydrolysis, what was mentioned in the example in the manufacturing method of a silanol group containing cage-type siloxane compound can be used.

Of the cocoon structure-containing curable silicone copolymer represented by the general formula (1-1), a cocoon structure-containing curable silicone copolymer in which R ^{4 at the} terminal Y ¹ is a hydrogen atom, that is, a silanol-terminated cocoon structure-containing cure. In the method for producing a cocoon structure-containing curable silicone copolymer obtained by a condensation reaction of a functional silicone copolymer and a compound represented by the following general formula (9), as described below, the following general formula (9 The production method differs depending on the type of the substituent X of the compound represented by ().

First, when X of the compound represented by the general formula (9) is an alkoxyl group, that is, the following general formula (9-1)
R ² ₃ Si-OR ⁵ (9-1)
(However, R ² is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ² is the same or different from each other. In the case of R ⁵ being a methyl group, an ethyl group or a propyl group, which may be the same or different from each other, the curable structure-containing curability represented by the general formula (1-1) Of the silicone copolymers, a に お け る structure-containing curable silicone copolymer in which R ^{4 at the} terminal Y ¹ is a hydrogen atom, that is, a range of 2 to 100 mol per 1 mol of a silanol-terminated 籠 structure-containing curable silicone copolymer. In the presence of a catalyst in the presence of a catalyst in one or both of a nonpolar solvent and an ether solvent, and the alcohol silane is subjected to dealcohol condensation. -2) It is possible to obtain a curable cage-type silicone copolymer with a constituent unit that. Here, about the preferable usage-amount of alkoxysilane, it is 2-30 mol with respect to 1 mol of cage structure containing curable silicone copolymers which have a structural unit represented by General formula (1-1). Good. In addition, about the method of dealcohol condensation, in the manufacturing method of the cage structure containing curable silicone copolymer which has a structural unit represented by general formula (1-1), silanol group containing which can be represented by general formula (7-2) Examples of the dealcoholization condensation of a siloxane compound and a dialkoxysilane represented by the general formula (8-2) or α, ω-dialkoxysiloxane can be used.

  The alkoxyl group-containing cage-type siloxane compound represented by the general formula (7-1) and the silane diol represented by the general formula (8-1) or the α, ω-disianol siloxane are subjected to dealcoholization condensation to obtain the general formula (1 -1) to obtain a cocoon-structure-containing curable silicone copolymer having a structural unit represented by formula (7-2), and a silanol group-containing cocoon-type siloxane compound represented by the general formula (7-2) and the general formula (8-2) In the case of obtaining a cocoon structure-containing curable silicone copolymer having a constitutional unit represented by the general formula (1-1) by dealcoholization condensation with a dialkoxysilane represented by (II) or an α, ω-dialkoxysiloxane. As long as the general formula (1-1) is not taken out, the alkoxysilane represented by the general formula (9-1) is added to the reaction system and allowed to react, whereby the structure represented by the general formula (1-2) A curable structure containing cocoon structure It can be obtained cone copolymer.

  Specific examples of the alkoxysilane represented by the general formula (9-1) include trimethylmethoxysilane, vinyldimethylmethoxysilane, dimethylmethoxysilane, phenyldimethylmethoxysilane, phenylmethoxysilane, triethylmethoxysilane, and trivinylmethoxysilane. , Methyldivinylmethoxysilane, allyldimethylmethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-acryloxypropyldimethylmethoxysilane, styryldimethylmethoxysilane, trimethylethoxysilane, vinyldimethylethoxysilane, dimethylethoxysilane, phenyldimethyl Ethoxysilane, phenylethoxysilane, triethylethoxysilane, trivinylethoxysilane, methyldivinylethoxysilane, allyldimethyl Toxisilane, 3-methacryloxypropyldimethylethoxysilane, 3-acryloxypropyldimethylethoxysilane, styryldimethylethoxysilane, trimethylpropoxysilane, vinyldimethylpropoxysilane, dimethylpropoxysilane, phenyldimethylpropoxysilane, phenylpropoxysilane, triethylpropoxy Silane, trivinylpropoxysilane, methyldivinylpropoxysilane, allyldimethylpropoxysilane, 3-methacryloxypropyldimethylpropoxysilane, 3-acryloxypropyldimethylpropoxysilane, styryldimethylpropoxysilane, trimethylisopropoxysilane, vinyldimethylisopropoxysilane Silane, dimethylisopropoxysilane, phenyldimethylisopropoxy Sisilane, phenylisopropoxysilane, triethylisopropoxysilane, trivinylisopropoxysilane, methyldivinylisopropoxysilane, allyldimethylisopropoxysilane, 3-methacryloxypropyldimethylisopropoxysilane, 3-acryloxypropyldimethylisopropoxysilane And styryldimethylisopropoxysilane.

Next, when X of the compound represented by the general formula (9) is hydrogen, that is, the following general formula (9-2)
R ² ₃ Si-H (9-2)
(However, R ² is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ² is the same or different from each other. In the case of), a cocoon structure-containing curable silicone copolymer represented by the general formula (1-1), wherein R ⁴ in the terminal Y ¹ is a hydrogen atom, That is, in the presence of a catalyst, hydrogen silane represented by the above general formula (9-2) in the range of 2 to 100 moles per mole of the curable silicone copolymer having a silanol terminal cage structure is present in the presence of a catalyst By carrying out dehydrogenation condensation in a solvent in which one or both of the solvents are combined, a cage structure-containing curable silicone copolymer having a structural unit represented by the general formula (1-2) can be obtained. Here, about the preferable usage-amount of hydrogen silane, it is 2-30 mol with respect to 1 mol of cage structure containing curable silicone copolymers which have a structural unit represented by General formula (1-1). Is good. In addition, about the method of dehydrogenation condensation, in the manufacturing method of the cage structure containing curable silicone copolymer which has a structural unit represented by general formula (1-1), the silanol represented by general formula (7-2) is shown. Those listed in the example of dehydrogenative condensation of the group-containing cage-type siloxane compound and the dihydrogensilane represented by the general formula (8-3) or α, ω-dihydrogensiloxane can be used.

  Dehydrocondensation of the silanol group-containing cage-type siloxane compound represented by the general formula (7-2) and the dihydrogensilane or α, ω-dihydrogensiloxane represented by the general formula (8-3) Thus, only when obtaining a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (1-1), the general formula (9) By adding the alkoxysilane represented by -1) and reacting it, a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (1-2) can be obtained.

  Specific examples of the hydrogen silane represented by the general formula (9-2) are trimethyl silane, vinyl dimethyl silane, phenyl dimethyl silane, triethyl silane, trivinyl silane, methyl divinyl silane, allyl dimethyl silane, 3-methacryl acrylate. Roxypropyldimethylsilane, 3-acryloxypropyldimethylsilane, styryldimethylsilane, dimethylpropylsilane, dimethylisopropylsilane, t-butyldimethylsilane, benzyldimethylsilane, tripropylsilane, tributylsilane, diphenylvinylsilane, triphenylsilane, etc. Can be mentioned.

Next, when X of the compound represented by the general formula (9) is chlorine, that is, the following general formula (9-3)
R ² ₃ Si-Cl (9-3)
(However, R ² is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ² is the same or different from each other. In the case of), a cocoon structure-containing curable silicone copolymer represented by the general formula (1-1), wherein R ⁴ in the terminal Y ¹ is a hydrogen atom, That is, the chlorosilane represented by the above general formula (9-2) in the range of 2 to 100 mol per 1 mol of the silanol terminal cocoon structure-containing curable silicone copolymer is used in the presence of a catalyst in the presence of a nonpolar solvent and an ether solvent. By conducting dehydrogenative condensation in a solvent in which one or both of them are combined, a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (1-2) can be obtained. Here, about the preferable usage-amount of chlorosilane, it is good that it is 2-30 mol with respect to 1 mol of soot structure containing curable silicone copolymers which have a structural unit represented by General formula (1-1). . In addition, about the method of dehydrochlorination condensation, the silanol group represented by general formula (7-2) in the manufacturing method of the cocoon structure containing curable silicone copolymer which has a structural unit represented by general formula (1-1) The examples of the dehydrochlorination condensation of the containing cage-type siloxane compound and the dichlorosilane represented by the general formula (8-4) or α, ω-dichlorosiloxane can be used.

  A silanol group-containing cage-type siloxane compound represented by the general formula (7-2) and a dichlorosilane or α, ω-dichlorosiloxane represented by the general formula (8-4) are subjected to dehydrochlorination condensation to obtain a general formula ( Only in the case of obtaining a cocoon structure-containing curable silicone copolymer having a structural unit represented by 1-1), the general formula (9-1) can be added to the reaction system without taking out the general formula (1-1). By adding and reacting the alkoxysilane represented, a cage-structure-containing curable silicone copolymer having a structural unit represented by the general formula (1-2) can be obtained.

  Specific examples of the chlorosilane represented by the general formula (9-3) include trimethylchlorosilane, vinyldimethylchlorosilane, dimethylchlorosilane, phenyldimethylchlorosilane, phenylchlorosilane, triethylchlorosilane, trivinylchlorosilane, methyldivinylchlorosilane, and allyldimethylchlorosilane. , 3-methacryloxypropyldimethylchlorosilane, 3-acryloxypropyldimethylchlorosilane, styryldimethylchlorosilane, dimethylpropylchlorosilane, dimethylisopropylchlorosilane, t-butyldimethylchlorosilane, benzyldimethylchlorosilane, tripropylchlorosilane, tributylchlorosilane, diphenylvinylchlorosilane And triphenylchlorosilane.

  Moreover, in this invention, either the hydrosilylation catalyst or the radical initiator is mix | blended with the soot structure containing curable silicone copolymer represented by General formula (1), or both a hydrosilylation catalyst and a radical initiator are combined. You may make it mix | blend and obtain a curable resin composition. And a hardened | cured material (molded object) can be obtained by thermosetting or photocuring this curable resin composition and carrying out hydrosilylation or radical polymerization. Further, in addition to the hydrosilylation catalyst and the radical initiator, a compound having a hydrogen atom on a silicon atom or a compound having an unsaturated group in the molecule may be further blended to obtain a curable resin composition. That is, for the purpose of obtaining a molded body by curing a curable resin, and for the purpose of improving the physical properties of the obtained molded body, hydrosilylation catalyst, thermal polymerization initiator, thermal polymerization accelerator, A curable resin composition can be obtained by blending a photopolymerization initiator, a photoinitiator assistant, a sensitizer, and the like.

  In the curable resin composition, the compound having a hydrogen atom on the silicon atom used together with the cocoon structure-containing curable silicone copolymer represented by the general formula (1) can be hydrosilylated in at least one molecule. Oligomers and monomers having hydrogen atoms on silicon atoms. Among these, examples of the oligomer having a hydrogen atom on a silicon atom include polyhydrogensiloxanes, polydimethylhydrosiloxysiloxanes and copolymers thereof, and siloxanes whose ends are modified with dimethylhydrosiloxy. Examples of monomers having a hydrogen atom on a silicon atom include cyclic siloxanes such as tetramethylcyclotetrasiloxane and pentamethylcyclopenta, dihydrodisiloxanes, trihydromonosilanes, dihydromonosilanes, and monohydromonosilanes. And dimethylsiloxysiloxanes, and two or more of these may be mixed.

  Further, in the curable resin composition, the compound having an unsaturated group used together with the cocoon structure-containing curable silicone copolymer represented by the general formula (1) has a weight of about 2 to 20 structural units. It is roughly divided into a reactive oligomer that is a coalescence and a low-molecular-weight and low-viscosity reactive monomer. Moreover, it divides roughly into the monofunctional unsaturated compound which has one unsaturated group, and the polyfunctional unsaturated compound which has two or more.

  Among these, reactive oligomers include polyvinylsiloxanes, polydimethylvinylsiloxysiloxanes and copolymers thereof, siloxanes modified with dimethylvinylsiloxy at the ends, epoxy acrylates, epoxidized acrylates, urethane acrylates, unsaturated Examples include polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, and polystyrylethyl methacrylate. These include monofunctional unsaturated compounds and polyfunctional unsaturated compounds.

  Examples of the reactive monofunctional monomer include vinyl-substituted silicon compounds such as triethylvinylsilane and triphenylvinylsilane, cyclic olefins such as cyclohexene, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n- Examples include hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, and the like.

  Examples of reactive polyfunctional monomers include vinyl-substituted silicon compounds such as tetravinylsilane and divinyltetramethyldisiloxane, vinyl-substituted cyclic silicon compounds such as tetramethyltetravinylcyclotetrasiloxane and pentamethylpentavinylcyclopentasiloxane, and bis (trimethylsilyl). ) Acetylene derivatives such as acetylene and diphenylacetylene, cyclic polyenes such as norbornadiene, dicyclopentadiene and cyclooctadiene, vinyl-substituted cyclic olefins such as vinylcyclohexene, divinylbenzenes, diethynylbenzenes, trimethylolpropane diallyl ether, penta Erythritol triallyl ether, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol Diglycidyl ether diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dimethylol-tricyclodecane diacrylate 1,3-dimethacryloxymethyl-1,1,3,3-tetramethyldisiloxane, 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1 Acrylates such as 1,3-diacryloxymethyl-1,1,3,3-tetramethyldisiloxane, 1,3-di (3-acryloxypropyl) -1,1,3,3-tetramethyldisiloxane Can be illustrated.

  As the compound having an unsaturated group in the molecule, various reactive oligomers and monomers other than those exemplified above can be used. These reactive oligomers and monomers may be used alone or in combination of two or more.

  The compound having a hydrogen atom on the silicon atom and the compound having an unsaturated group in the molecule used in the present invention may be used alone or in combination of two or more.

  As described above, the curable resin composition of the present invention includes a soot structure-containing curable silicone copolymer represented by the general formula (1), a hydrosilylation catalyst and a radical initiator, and if necessary, on a silicon atom. It is obtained by compounding a compound containing a hydrogen atom or a compound having an unsaturated group. And the molded object of this invention is obtained by shape-hardening this curable resin composition. That is, a cured product can be obtained by hydrosilylation curing and radical polymerization of the curable resin composition.

  When the hydrosilylation catalyst is blended, the amount added is preferably 1 to 1000 ppm, more preferably 20 to 500 ppm as a metal atom with respect to the weight of the curable resin. Moreover, when mix | blending a photoinitiator or a thermal-polymerization initiator as a radical initiator, the addition amount is good to set it as the range of 0.1-10 weight part with respect to 100 weight part of curable resin, and 0.1-5 weight It is more preferable to use the range of parts. If this addition amount is less than 0.1 parts by weight, curing will be insufficient and the strength and rigidity of the resulting molded product will be low. On the other hand, when it exceeds 10 parts by weight, there is a possibility that problems such as coloring of the molded product may occur. Further, the hydrosilylation catalyst and the radical initiator may be used alone or in combination of two or more.

  Hydrosilylation catalysts include platinum chloride, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone complexes, chloroplatinic acid and olefin complexes, platinum and vinylsiloxane complexes, and dicarbonyldichloroplatinum. And platinum group metal catalysts such as palladium catalysts and rhodium catalysts. Among these, from the viewpoint of catalytic activity, chloroplatinic acid, a complex of chloroplatinic acid and olefins, and a complex of platinum and vinylsiloxane are preferable. These may be used alone or in combination of two or more.

  As the photopolymerization initiator used when the curable resin composition is a photocurable resin composition, a compound such as an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, or acylphosphine oxide-based compound is preferably used. Can do. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone, etc. can do. Moreover, the photoinitiator adjuvant and sensitizer which show an effect in combination with a photoinitiator can also be used together.

  As thermal polymerization initiators used for the above purpose, various types such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, etc. The organic peroxide can be suitably used. Specifically, cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, t-butylperoxy-2-ethyl Although hexanoate etc. can be illustrated, it is not restrict | limited at all to this. These thermal polymerization initiators may be used alone or in combination of two or more.

  Various additives can be added to the curable resin composition without departing from the object of the present invention. Various additives include organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, Crosslinking agents, dispersion aids, resin components and the like can be exemplified.

  The molded body composed of the cocoon structure-containing curable silicone copolymer represented by the general formula (1) of the present invention is obtained by heating or lighting a curable resin composition containing either a hydrosilylation catalyst, a radical polymerization initiator, or both. It can be produced by curing by irradiation. When a cured product (molded article) is produced by heating, the molding temperature can be selected from a wide range from room temperature to around 200 ° C., depending on the selection of the thermal polymerization initiator and accelerator. In this case, a cured product (molded product) having a desired shape can be obtained by polymerization and curing in a mold or on a steel belt. More specifically, all of general molding methods such as injection molding, extrusion molding, compression molding, transfer molding, calendar molding, and cast (casting) molding are applicable.

  Moreover, when manufacturing hardened | cured material (molded object) by light irradiation, a molded object can be obtained by irradiating the ultraviolet rays with a wavelength of 100-400 nm and the visible light with a wavelength of 400-700 nm. The wavelength of the light to be used is not particularly limited, but near ultraviolet light having a wavelength of 200 to 400 nm is particularly preferably used. The lamps used as ultraviolet light sources include low-pressure mercury lamps (output: 0.4 to 4 W / cm), high-pressure mercury lamps (40 to 160 W / cm), ultra-high pressure mercury lamps (173 to 435 W / cm), metal halide lamps (80 ˜160 W / cm), pulse xenon lamp (80 to 120 W / cm), electrodeless discharge lamp (80 to 120 W / cm), and the like. Each of these ultraviolet lamps is characterized by its spectral distribution, and is therefore selected according to the type of photoinitiator used.

  As a method of obtaining a cured product (molded body) by light irradiation, for example, it is injected into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass, and irradiated with ultraviolet rays by the above-described ultraviolet lamp. A method of producing a molded body of a desired shape by performing polymerization and curing and removing from the mold, or when not using a mold, for example, a doctor blade or a roll-shaped coater on a moving steel belt Examples thereof include a method for producing a sheet-like molded article by applying the curable resin composition of the present invention and polymerizing and curing with the above-described ultraviolet lamp. Furthermore, in this invention, you may use combining the method of obtaining the molding by heating and light irradiation.

  If the manufacturing method of the cage structure containing curable silicone copolymer of this invention is used, molecular weight can be arbitrarily controlled and the material design according to the objective will be attained. That is, a copolymer having a cage structure incorporated in the main chain can be obtained by condensing a cage silsesquioxane compound containing an alkoxyl group or a silanol group. From the curable resin composition containing the obtained copolymer, a cured product excellent in transparency and heat resistance can be obtained, and the obtained molded product is a transparent member having a light weight and high impact strength. For example, it can be used as a glass substitute material for optical applications such as lenses, optical discs, optical fibers, and flat panel display substrates, as well as window materials for various transport machines and houses, and has a high industrial utility value. .

Examples of the present invention will be described below.
In addition, the meaning of the abbreviation used below is as follows. That is, Me: methyl group, Et: ethyl group, Ph: phenyl group.

Reference Example 1: [alkoxyl-containing cage-type siloxane compound _{A [(EtO) MeRSiO 1/2]} 1 - [PhSiO 3/2] 8 - [O 1/2 Et] Synthesis of ₁ (7-1A) (where R Is a 3-methacryloxypropyl group)]
The following synthesis example uses the method described in Japanese Patent Publication No. 40-15989, and manufactures a cage-type octaphenylsilsesquioxane having the structural formula (C ₆ H ₅ SiO _3/2 ) ₈ It is an example. The reaction vessel was charged with 2500 ml of toluene and 525 g of phenyltrichlorosilane and cooled to 0 ° C. An appropriate amount of water was added dropwise and stirred until hydrolysis was complete. After washing the hydrolysis product with water, 83 ml of a commercially available 30% benzyltrimethylammonium hydroxide solution was added, and the mixture was heated to reflux for 4 hours. The whole was then cooled and left for about 96 hours. The slurry obtained after the lapse of time was heated again to the reflux temperature for 24 hours, then cooled and filtered to obtain 375 g of octaphenylsilsesquioxane as a white powder.

Next, 1000 ml of toluene, 1.23 g of tetramethylammonium hydroxide (13.5 mmol, 4.9 g as a 25% methanol solution), 203 g (197 mmol) of octaphenylsilsesquioxane, and a reaction vessel equipped with a Dinsterk and a condenser tube, and 3-Methacryloxypropyldiethoxymethylsilane (51.2 g, 197 mmol) was added, and the mixture was heated at 80 ° C. for 1 hour to distill off methanol. The mixture was further heated to 100 ° C. and returned to room temperature after 2 hours to complete the reaction. In the reaction solution, it was judged that the white powder of octaphenylsilsesquioxane disappeared and the reaction was completely progressed. The reaction solution was neutralized with 10% aqueous citric acid solution, washed with water, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 197 g of an alkoxyl group-containing cage-type siloxane compound A as a colorless and transparent viscous liquid with a yield of 78%. The obtained alkoxyl group-containing cage-type siloxane compound A was confirmed by GPC and NMR measurement to be represented by the following formula (7-1A).
_{[(EtO) MeRSiO 1/2] 1} - [PhSiO 3/2] 8 - [O 1/2 Et] 1 (7-1A)
(Where R is a 3-methacryloxypropyl group)

Reference Example 2: [silanol-containing cage-type siloxane compound _{A [(HO) MeRSiO 1/2]} 1 - [PhSiO 3/2] 8 - [O 1/2 H] Synthesis of ₁ (7-2A) (where R Is a 3-methacryloxypropyl group)]
A reaction vessel equipped with a dropping funnel was charged with 500 ml of 2-propanol, 350 ml of toluene, and 61.5 g (47.5 mmol) of the alkoxyl group-containing cage-type siloxane compound (7-1A) obtained in Reference Example 1 above. To the reaction solution, 1.4 g of 2% hydrochloric acid (HCl: 1 mmol, H2O: 105 mmol) was added dropwise at room temperature, and the mixture was stirred at room temperature for 24 hours. The reaction solution was neutralized with an aqueous sodium hydrogen carbonate solution, washed with water, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 53.5 g of a silanol group-containing cage-type siloxane compound A as a colorless transparent viscous liquid in a yield of 91%. It was confirmed that the obtained silanol group-containing cage-type siloxane compound A is represented by the following formula (7-2A) from GPC and NMR measurement.
_{[(HO) MeRSiO 1/2] 1} - [PhSiO 3/2] 8 - [O 1/2 H] 1 (7-2A)
(Where R is a 3-methacryloxypropyl group)

Reference Example 3: [Alkoxyl group-containing cage-type siloxane compound B [(EtO) Me ₂ SiO _1/2 ] _1- [H ₂ C═CH—SiO _3/2 ] _10- [O _1/2 Et] ₁ (7-1B )
This synthesis example uses a method described in Japanese Patent Application Laid-Open No. 2004-143449 filed earlier, and is a cage-type polyvinyl syl having the structural formula (H ₂ C═CH—SiO _3/2 ) _n. This is a production example of sesquioxane.
A reaction vessel was charged with 750 ml of toluene, 425 ml of 2-propanol, and 186 g of a 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). While stirring, a solution of 125 ml of toluene and 251 g of vinyltrimethoxysilane was added dropwise to the reaction vessel at room temperature over 3 hours. After completion of the dropping, the mixture was stirred at room temperature for 2 hours, and then the stirring was stopped and the mixture was allowed to stand for 1 day. The reaction solution was neutralized with a 10% aqueous citric acid solution, washed with saturated brine, dehydrated with anhydrous magnesium sulfate, and concentrated to obtain 103 g of a hydrolyzed polycondensate of vinyltrimethoxysilane.

Next, 1100 g of the vinyltrimethoxysilane hydrolyzed polycondensate obtained above, 2000 ml of toluene, and 17.2 g of 5% TMAH aqueous solution were placed in a reaction vessel equipped with a Din Stark and a cooling tube, and water was distilled off at 120 ° C. Reflux heating was performed for 3 hours. After cooling to room temperature, neutralized with 10% aqueous citric acid solution, washed with saturated brine, dehydrated and concentrated with anhydrous magnesium sulfate, 97 g of caged polyvinylsilsesquioxane was obtained. The obtained cage-type polyvinylsilsesquioxane has a structure formula (H ₂ C = CH—SiO _3/2 ) _n of n = by mass spectrometry using GPC and liquid chromatography atmospheric pressure ionization analyzer (LC / APCI-MS). It was confirmed to be a vertical vinyl siloxane mixture mainly containing 8, 10, 12, 14 and n = 10 on average.

The same operation as in Reference Example 1 was carried out using 250 ml of toluene, 390 mg of tetramethylammonium hydroxide (4.3 mmol, 1.55 g as a 25% methanol solution), and the above-described vertical vinylsiloxane mixture (H ₂ C═CH—SiO _{3 / 2} ) _n (however, n = 8, 10, 12, 14 included mainly and averaged n = 10) 50.0 g (63 mmol as n = 10) and dimethyldimethoxysilane 9.4 g (63 mmol) were changed to charge amount As a result, 50.1 g of an alkoxyl group-containing cage-type siloxane compound B was obtained as a colorless transparent viscous liquid with a recovery rate of 84%. It was confirmed that the alkoxyl group-containing cage-type siloxane compound B is represented by the following formula (7-1B) from GPC and NMR measurement.
_{[(EtO) Me 2 SiO 1/2} ] 1 - [H2C = CH-SiO 3/2] 10 - [O 1/2 Et] 1 (7-1B)

Reference example 4: [silanol group-containing cage-type siloxane compound B [(HO) Me ₂ SiO _1/2 ] _1- [H ₂ C = CH—SiO _3/2 ] _10- [O _1/2 H] ₁ (7-2B )
A reaction vessel equipped with a dropping funnel was charged with 200 ml of 2-propanol, 170 ml of toluene, and 25.0 g (27 mmol) of the alkoxyl group-containing cage-type siloxane compound B obtained in Reference Example 3, and tetramethylammonium hydroxide 6.5% was added to the reaction solution. A mixed solution of g (71.5 mmol, 26 g as a 25% methanol solution), ion-exchanged water 1.5 g (83 mmol) and 2-propanol 150 ml was added dropwise, and the mixture was stirred at room temperature for 3 hours. To the reaction solution was added 20 ml of toluene, stirred, and then neutralized with a 10% aqueous citric acid solution, washed with saturated brine, dehydrated with anhydrous magnesium sulfate, and concentrated to obtain 21.2 of silanol group-containing cage-type siloxane compound B. g, Yield 92%. It was confirmed that the obtained silanol group-containing cage-type siloxane compound B is represented by the following formula (7-2B) from GPC and NMR measurement.
_{[(HO) Me 2 SiO 1/2} ] 1 - [H2C = CH-SiO 3/2] 10 - [O 1/2 H] 1 (7-2B)

[Example 1]
Under a nitrogen atmosphere, in a reaction vessel equipped with a dropping funnel and a condenser, 15 ml of toluene, 9.0 g (7 mmol) of the alkoxyl group-containing cage-type siloxane compound A (Formula 7-1A) obtained in Reference Example 1 above, and hydroxylation Tetramethylammonium 4 mg (0.044 mmol, 153 mg as a 2.5% methanol solution) was charged. While stirring the reaction solution at 70 ° C., 4.6 g of silanol-terminated polydimethylsiloxane (DMS-S12: Mn (number average molecular weight) = 400-700: Asmax Co., Ltd.) was added dropwise from a dropping funnel over 3 hours. After further stirring for 3 hours, the mixture was cooled to room temperature. The reaction solution was neutralized with 10% aqueous citric acid solution, washed with water, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 12.5 g of cocoon structure-containing curable silicone copolymer A as a colorless and transparent viscous liquid. As a result of measuring GPC of the obtained cocoon structure-containing curable silicone copolymer A, it was found that the weight average molecular weight (Mw) was 96768. Further, signals attributable to phenyl group, methyl group, ethoxy group, and 3-methacryloxypropyl group were observed from 1H-NMR. Therefore, the cocoon structure-containing curable silicone copolymer A obtained above has R ¹ is a phenyl group, R ² is a methyl group and a 3-methacryloxypropyl group in the general formula (1-1). The ratio was confirmed to be methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8, m = 52.5. Among, Z is R ³ in the general formula (2) is a methyl group and p = 7.2, also, Y ¹ is R ¹ in the general formula (3) or general formula (4) or general formula (5) A phenyl group, R ² is a methyl group and a 3-methacryloxypropyl group, and the ratio thereof is methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8 And R ⁴ was an ethyl group and hydrogen.

[Example 2]
In a nitrogen atmosphere, a reaction vessel equipped with a dropping funnel and condenser was charged with 15 ml of toluene, 1.2 g (8 mmol) of dimethyldiethoxysilane, and 4 mg of tetramethylammonium hydroxide (0.044 mmol, 153 mg as a 2.5% methanol solution). did. While stirring the reaction solution at 70 ° C., a solution obtained by dissolving 8.6 g (7 mmol) of the silanol group-containing cage-type siloxane compound A (formula 7-2A) obtained in Reference Example 2 from the dropping funnel in 5 ml of toluene for 3 hours. It was dripped over. After further stirring for 3 hours, the mixture was cooled to room temperature. The reaction solution was neutralized with 10% aqueous citric acid solution, washed with water, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 9.0 g of cocoon structure-containing curable silicone copolymer B as a colorless and transparent viscous liquid. As a result of measuring GPC of the obtained cocoon structure-containing curable silicone copolymer B, the weight average molecular weight (Mw) was 16708. Further, signals attributable to phenyl group, methyl group, ethoxy group, and 3-methacryloxypropyl group were observed from 1H-NMR. Therefore, the obtained cocoon structure-containing curable silicone copolymer B has the ratio R ¹ in the general formula (1-1) is a phenyl group, R ² is a methyl group and a 3-methacryloxypropyl group. Was methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8, and m = 12.7. Among, Z is R ³ in the general formula (2) is a methyl group and p = 1.1, Y ¹ is the general formula (3) or general formula (4) or R ¹ of the general formula (5) is a phenyl group R ² is a methyl group and a 3-methacryloxypropyl group, and the ratio is methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8, R ⁴ was an ethyl group and hydrogen.

[Example 3]
Under a nitrogen atmosphere, in a reaction vessel equipped with a dropping funnel and a condenser tube, 15 ml of toluene, 2.3 g of hydrogen-terminated polydimethylsiloxane (DMS-H03: Mn = 400-500: Asmax Corporation), 364 mg of N, N-diethylhydroxyamine (4.1 mmol) was charged. While stirring the reaction solution, a solution prepared by dissolving 6.3 g (5 mmol) of the silanol group-containing cage-type siloxane compound A (formula 7-2A) obtained in Reference Example 2 in 5 ml of toluene was added dropwise over 5 hours from the dropping funnel. The mixture was further stirred at 50 ° C. for 3 hours. After cooling to room temperature, the reaction solution was neutralized with 10% aqueous citric acid solution, washed with water, and dehydrated with anhydrous magnesium sulfate. By filtering off anhydrous magnesium sulfate and concentrating, 8.1 g of a cocoon structure-containing curable silicone copolymer B was obtained as a colorless and transparent viscous liquid. As a result of measuring GPC of the obtained cocoon structure-containing curable silicone copolymer C, the weight average molecular weight (Mw) was 45213. From 1H-NMR, signals attributable to phenyl, methyl and 3-methacryloxypropyl groups were observed. Therefore, the obtained cocoon structure-containing curable silicone copolymer C has the ratio R ¹ in the general formula (1-1) is a phenyl group, R ² is a methyl group and a 3-methacryloxypropyl group. Was methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8, m = 26.8. Among, Z is R ³ in the general formula (2) is a methyl group and p = 6.1, Y ¹ is the general formula (3) or general formula (4) or R ¹ of the general formula (5) is a phenyl group R ² is a methyl group and a 3-methacryloxypropyl group, and the ratio is methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8, R ⁴ was hydrogen.

[Example 4]
Under a nitrogen atmosphere, a reaction vessel equipped with a dropping funnel and a condenser was charged with 1.96 g of methyldichlorosilane and 16 ml of (17 mmol) pyridine. While stirring the reaction solution, a solution prepared by dissolving 10.5 g (8.5 mmol) of the silanol group-containing cage-type siloxane compound A (formula 2-2A) obtained in Reference Example 2 from the dropping funnel in 77 mL of pyridine was added over 1 hour. The solution was added dropwise and further stirred at 50 ° C. for 3 hours. Thereafter, the mixture was cooled to room temperature, 100 ml of toluene and 50 ml of water were added, and the organic layer and the aqueous layer were separated. After extraction of the organic layer, this was washed 3 times with distilled water and twice with saturated brine, and dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 10.4 g of a curable structure-containing silicone copolymer D as a colorless and transparent viscous liquid. As a result of measuring GPC of the obtained cocoon structure-containing curable silicone copolymer D, the weight average molecular weight (Mw) was 19228. From 1H-NMR, signals attributable to phenyl, methyl and 3-methacryloxypropyl groups were observed. Therefore, the obtained cocoon structure-containing curable silicone copolymer D has a ratio of R ¹ is a phenyl group, R ² is a methyl group and a 3-methacryloxypropyl group in the general formula (1-1). Is methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8, m = 13.9. Of these, Z is R ³ in the general formula (2) and is a methyl group and hydrogen, and the ratio thereof is methyl group / hydrogen = 1/1, p = 2, and Y ¹ is the general formula (3 ) Or general formula (4) or general formula (5), R ¹ is a phenyl group, R ² is a methyl group and a 3-methacryloxypropyl group, and the ratio is methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8 and R ⁴ was hydrogen.

[Example 5]
Under a nitrogen atmosphere, a reaction vessel equipped with a dropping funnel and a condenser tube was charged with 5.0 g of the cocoon structure-containing curable silicone copolymer D obtained in Example 4 and 16 ml of pyridine. While stirring the reaction solution, a solution of 5.0 g (42 mmol) of dimethylvinylchlorosilane in THF (20 ml) was added dropwise over 30 minutes at room temperature and stirred for 2 hours. After stirring for 2 hours, 30 mL of toluene and 30 mL of distilled water were added, and the organic layer and the aqueous layer were separated. After extraction of the organic layer, this was washed 3 times with distilled water and twice with saturated brine, and dehydrated over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 4.8 g of a cocoon structure-containing curable silicone copolymer E as a colorless and transparent viscous liquid. As a result of measuring GPC of the obtained cocoon structure-containing curable silicone copolymer E, the weight average molecular weight (Mw) was 19538. From 1H-NMR, signals attributable to phenyl, methyl and 3-methacryloxypropyl groups were observed. Therefore, the obtained cocoon structure-containing curable silicone copolymer E has the ratio R ¹ in the general formula (1-2) is a phenyl group, R ² is a methyl group and a 3-methacryloxypropyl group. Is methyl group / 3-methacryloxypropyl group = 1/1, a = 1, b = 1, n = 8, m = 139. Among these, Z is R ³ in the general formula (2) and p = 2, Y ² is R ^{2 in the} general formula (6) is a methyl group and a vinyl group, and the ratio is methyl group / vinyl. The group was 2/1.

[Example 6]
Under a nitrogen atmosphere, in a reaction vessel equipped with a dropping funnel and a condenser tube, 15 ml of toluene, 9.4 g (10 mmol) of an alkoxyl group-containing cage-type siloxane compound B (Formula 7-1B) obtained in Reference Example 3 above, and hydroxylation Tetramethylammonium 4 mg (0.044 mmol, 153 mg as a 2.5% methanol solution) was charged. While stirring the reaction solution at 70 ° C., 4.6 g of silanol-terminated polydimethylsiloxane (DMS-S12: Mn (number average molecular weight) = 400-700: Asmax Co., Ltd.) was added dropwise from a dropping funnel over 3 hours. After further stirring for 3 hours, the mixture was cooled to room temperature. The reaction solution was neutralized with 10% aqueous citric acid solution, washed with water, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 12.3 g of a cocoon structure-containing curable silicone copolymer F as a colorless and transparent viscous liquid. As a result of measuring GPC of the obtained cocoon structure-containing curable silicone copolymer F, it was found that the weight average molecular weight (Mw) was 45634. From 1H-NMR, signals attributed to methyl, ethoxy and vinyl groups were observed. Therefore, the obtained cocoon structure-containing curable silicone copolymer F has the following formula (1-1): R ¹ is a vinyl group, R ² is a methyl group, and a = 1, b = 1, n = 10 and m = 34.5. Among, Z is in the general formula (2) R ³ is a methyl group and p = 7.2,, Y ¹ is R ¹ is a vinyl group of the general formula (3) or general formula (4) or formula (5) R ² was a methyl group, a = 1, b = 1, n = 8, and R ⁴ was an ethyl group and hydrogen.

[Example 7]
Under a nitrogen atmosphere, a reaction vessel equipped with a dropping funnel and a condenser was charged with 2.2 g of dimethyldichlorosilane and 16 ml of (17 mmol) pyridine. While stirring the reaction solution, a solution obtained by dissolving 7.5 g (8.5 mmol) of silanol group-containing cage-type siloxane compound B (formula 2-2B) obtained in Reference Example 4 from 77 in a pyridine 77 mL from a dropping funnel was taken for 1 hour. The solution was added dropwise and further stirred at 50 ° C. for 3 hours. Thereafter, the mixture was cooled to room temperature, and a solution of 4.3 g (40 mmol) of trimethylchlorosilane in pyridine (20 ml) was added dropwise from the dropping funnel over 30 minutes at room temperature, followed by stirring for 2 hours. After stirring for 2 hours, 100 mL of toluene and 30 mL of distilled water were added, and the organic layer and the aqueous layer were separated. After extraction of the organic layer, this was washed 3 times with distilled water and twice with saturated brine, and dehydrated over anhydrous magnesium sulfate. By filtering off anhydrous magnesium sulfate and concentrating, 7.1 g of cocoon structure-containing curable silicone copolymer G was obtained as a colorless and transparent viscous liquid. As a result of measuring GPC of the obtained cocoon structure-containing curable silicone copolymer G, it was found that the weight average molecular weight (Mw) was 36098. Further, signals attributed to vinyl group and methyl group were observed from 1H-NMR. Therefore, the obtained cocoon structure-containing curable silicone copolymer G has the following formula (1-2): R ¹ is a vinyl group, R ² is a methyl group, and a = 1, b = 1, n = 10 and m = 35 were confirmed. Among these, Z is R ³ in the general formula (2) and p = 2, and Y ² is R ^{1 in the} general formula (6).

[Example 8]
The cocoon structure-containing curable silicone copolymer A obtained in Example 1 above: 100 parts by weight, and 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator: 1.0 part by weight Were mixed to obtain a transparent curable resin composition.

Next, the curable resin composition obtained above was cast (cast) to a thickness of 0.4 mm using a roll coater, and 2000 mJ / cm ² using a 30 W / cm high-pressure mercury lamp. A sheet-like ridge structure-containing curable silicone resin molded product having a predetermined thickness was obtained by curing with the accumulated exposure amount.

[Example 9]
100 parts by weight of cocoon structure-containing curable silicone copolymer B obtained in Example 2 above, and 5.0 parts by weight of dicumyl peroxide (Nippon Yushi Co., Ltd., Park Mill D) as a thermal polymerization initiator were mixed and transparent. A curable resin composition was obtained.

Next, using a roll coater, the curable resin composition obtained above was cast (cast) so as to have a thickness of 0.4 mm, and a 30 W / cm high-pressure mercury lamp was used, and 2000 mJ / cm ² Curing was performed with the integrated exposure amount, followed by heating at 140 ° C. for 1 hour and 180 ° C. for 1 hour to obtain a sheet-like ridge structure-containing curable silicone resin molded product having a predetermined thickness.

[Example 10]
Cured structure-containing curable silicone copolymer C obtained in Example 3 above: 100 parts by weight, 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane: 50 parts by weight Parts, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator: 1.5 parts by weight, and dicumyl peroxide (Nippon Yushi Co., Ltd. Park Mill D) as a thermal polymerization initiator: 5.0 parts by weight were mixed to obtain a transparent curable resin composition.

Next, using a roll coater, the curable resin composition obtained above was cast (cast) so as to have a thickness of 0.4 mm, and a 30 W / cm high-pressure mercury lamp was used, and 2000 mJ / cm ² Curing was carried out at the integrated exposure amount, followed by heating at 140 ° C. for 1 hour and at 180 ° C. for 1 hour to obtain a sheet-like ridge structure-containing curable silicone resin molding having a predetermined thickness.

[Example 11]
Cured structure-containing curable silicone copolymer D obtained in Example 4 above: 100 parts by weight, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane: 10 parts by weight 0.5 parts by weight of a platinum-vinylsiloxane complex (SIP 6830.3 manufactured by Amax Co., Ltd.) and 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator By mixing, a transparent curable resin composition was obtained.

Next, using a roll coater, the curable resin composition obtained above was cast (cast) to a thickness of 0.4 mm, heated at 80 ° C. for 1 hour, and then 30 W / cm high-pressure mercury. Using a lamp, the sheet was cured with an integrated exposure amount of 2000 mJ / cm ² to obtain a sheet-like ridge structure-containing curable silicone resin molded product having a predetermined thickness.

[Example 12]
Cured structure-containing curable silicone copolymer E obtained in Example 5: 100 parts by weight, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane: 20 parts by weight , Platinum-vinylsiloxane complex (AMAX Co., Ltd., SIP6830.3) 0.5 parts by weight, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator: 1.5 parts by weight, and Dicumyl peroxide (Nippon Yushi Co., Ltd. Park Mill D): 5.0 parts by weight was mixed as a thermal polymerization initiator to obtain a transparent curable resin composition.

Next, using a roll coater, the curable resin composition obtained above was cast (cast) so as to have a thickness of 0.4 mm, and a 30 W / cm high-pressure mercury lamp was used, and 2000 mJ / cm ² Cured with integrated exposure, then heated at 100 ° C. for 1 hour, 140 ° C. for 1 hour, and 180 ° C. for 1 hour to obtain a sheet-like ridge structure-containing curable silicone resin molded product having a predetermined thickness .

[Example 13]
The cocoon structure-containing curable silicone copolymer F obtained in Example 6 above: 100 parts by weight and dicumyl peroxide (Nippon Yushi Co., Ltd. Park Mill D): 10 parts by weight as a thermal polymerization initiator were mixed, and transparent A curable resin composition was obtained.

  Next, using a roll coater, the curable resin composition obtained above was cast (cast) so as to have a thickness of 0.4 mm, and was 100 ° C for 1 hour, 140 ° C for 1 hour, and 180 ° C. Was heated for 1 hour to obtain a sheet-shaped ridge structure-containing curable silicone resin molded product having a predetermined thickness.

[Example 14]
籠 structure-containing curable silicone copolymer G obtained in Example 7: 100 parts by weight, 1,3,5,7-tetramethylcyclotetrasiloxane: 160 parts by weight, and platinum-vinylsiloxane complex (Amax Co., Ltd.) Manufactured SIP6830.3) 1.5 parts by weight were mixed to obtain a transparent curable resin composition.

  Next, using a roll coater, the curable resin composition obtained above was cast (cast) so as to have a thickness of 0.4 mm, and was 100 ° C for 1 hour, 140 ° C for 1 hour, and 180 ° C. Was heated for 1 hour to obtain a sheet-shaped ridge structure-containing curable silicone resin molded product having a predetermined thickness.

[Example 15]
籠 structure-containing curable silicone copolymer G obtained in Example 7: 100 parts by weight, 1,3,5,7-tetramethylcyclotetrasiloxane: 100 parts by weight, platinum-vinylsiloxane complex (manufactured by Amax Co., Ltd.) SIP 6830.3) 1.0 parts by weight and 5.0 parts by weight of dicumyl peroxide (Nippon Yushi Co., Ltd. Park Mill D) as a thermal polymerization initiator were mixed to obtain a transparent curable resin composition.

  Next, using a roll coater, the curable resin composition obtained above was cast (cast) to a thickness of 0.4 mm, heated at 80 ° C. for 1 hour, 100 ° C. for 1 hour, 140 ° C. By heating at 180 ° C. for 1 hour and at 180 ° C. for 1 hour, a sheet-like ridge structure-containing curable silicone resin molded article having a predetermined thickness was obtained.

[Comparative Example 1]
100 parts by weight of dicyclopentanyl diacrylate (Kyoeisha Chemical Co., Ltd. light acrylate DCP-A) and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals): 2.0 weight Parts were mixed to obtain a transparent curable resin composition.

Next, using a roll coater, the curable resin composition obtained above was cast (cast) so as to have a thickness of 0.4 mm, and a 30 W / cm high-pressure mercury lamp was used, and 2000 mJ / cm ² A sheet-like molded body having a predetermined thickness was obtained by curing with the integrated exposure amount.

[Heat resistance test]
The physical properties of the cured products obtained from Examples 8 to 15 and Comparative Example 1 and the 400 nm transmittance after a heat resistance test (heated at 230 ° C. for 3 hours) were measured with a spectrophotometer. The results are shown in Table 1. The elastic modulus and elongation at break were measured according to the tensile test conditions described in JIS K 7127 (shape 100 x 25 x x 0.4 mm, distance between chucks 50 mm, speed 5 mm / min), and average values ( n = 5).

  As is clear from Table 1, the cured products obtained in Examples 8 to 15 are all excellent in flexibility because the tensile elastic modulus is low and the elongation at break is high compared to the cured product of Comparative Example 1. It can be seen that a cured product is obtained. Moreover, the cured products obtained in Examples 8 to 15 were superior to the comparative examples in terms of transmittance, and the transmittance after the heat resistance test was particularly superior to that of the cured product of Comparative Example 1.

Claims (7)

The following general formula (1)
^{_{Y- [Z- (O 1/2 -R 2}} 2 SiO 1/2) a - (R 1 SiO 3/2) n - (O 1/2) b] m -Z-Y (1)
[However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and in R ¹ or R ² , each substituent is Although they may be the same or different from each other, at least one of R ¹ contained in one molecule is any of a group having a vinyl group, a (meth) acryloyl group , an allyl group or an oxirane ring. is there. Moreover, a and b are numbers 0-3, satisfy | fill the relationship of 1 <= a + b <= 4, n shows the number of 8-14, m shows the number of 1-2000. Furthermore, Z is the following general formula (2)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. And p is a divalent group represented by 0 to 30), and Y is any monovalent group selected from the following general formulas (3) to (6). is there.
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [O _1/2 ]-(3)
[R ⁴ O _1/2 ] _b- [R ¹ SiO _3/2 ] _n- [O _1/2 -R ² ₂ SiO _1/2 ]-(4)
(R ⁴ O _1/2 ) − (5)
(R ² ₃ SiO _1/2 ) − (6)
(However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group, or an oxirane ring, and each substituent in R ¹ or R ² May be the same or different from each other, R ⁴ is any one selected from a hydrogen atom, a methyl group, or an ethyl group, a and b are a number from 0 to 3, and n is from 8 to 14) A cocoon structure-containing curable silicone copolymer having a structural unit represented by the following formula : The following general formula (7)
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [O _1/2 R ⁴ ] (7)
(However, R ¹ and R ² are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and R ⁴ is a hydrogen atom, a methyl group or an ethyl group. In R ¹ , R ² or R ⁴ , each substituent may be the same or different from each other, but at least one of R ¹ contained in one molecule is a vinyl group, (meth) A group having an acryloyl group , an allyl group, or a group having an oxirane ring, and a and b are numbers from 0 to 3, satisfying the relationship of 1 ≦ a + b ≦ 4, and n is 8 An alkoxyl group or silanol group-containing cage-type siloxane compound represented by the following general formula (8):

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. X is a hydroxyl group, a hydrogen atom, a chlorine atom or an alkoxyl group, X may be the same or different from each other, and p represents a number of 0 to 30). Condensation reaction with a compound, or a reaction product obtained by condensation reaction is further represented by the following general formula (9)
R ² ₃ Si-X (9)
(However, R ² is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ² is the same or different from each other. In addition, X is a hydroxyl group, a hydrogen atom, a chlorine atom, or an alkoxyl group, and the compound represented by the following general formula (1)
^{_{Y- [Z- (O 1/2 -R 2}} 2 SiO 1/2) a - (R 1 SiO 3/2) n - (O 1/2) b] m -Z-Y (1)
[ However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group or an oxirane ring, and in R ¹ or R ² , each substituent is Although they may be the same or different from each other, at least one of R ¹ contained in one molecule is any of a group having a vinyl group, a (meth) acryloyl group , an allyl group or an oxirane ring. is there. Further, a and b are numbers from 0 to 3, satisfying the relationship of 1 ≦ a + b ≦ 4, n represents a number from 8 to 14, and m represents a number from 1 to 2000. Furthermore, Z is the following general formula (2)

(However, R ³ is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a group having a (meth) acryloyl group , an allyl group or a group having an oxirane ring, and R ³ is the same or different from each other. And p is a divalent group represented by 0 to 30), and Y is any monovalent group selected from the following general formulas (3) to (6). is there.
[(R ⁴ O) R ² ₂ SiO _1/2 ] _a- [R ¹ SiO _3/2 ] _n- [O _1/2 ]-(3)
[R ⁴ O _1/2 ] _b- [R ¹ SiO _3/2 ] _n- [O _1/2 -R ² ₂ SiO _1/2 ]-(4)
(R ⁴ O _1/2 ) − (5)
(R ² ₃ SiO _1/2 ) − (6)
(However, R ¹ and R ² are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group , an allyl group, or an oxirane ring, and each substituent in R ¹ or R ² May be the same or different from each other, R ⁴ is selected from a hydrogen atom, a methyl group or an ethyl group, a and b are a number from 0 to 3, and n is a number from 8 to 14.) A cocoon structure-containing curable silicone copolymer having a structural unit represented by the following formula:   The compound represented by the general formula (8) in the range of 0.5 to 10 moles is subjected to a condensation reaction with respect to 1 mole of the alkoxyl group or silanol group-containing cage-type silsesquioxane compound represented by the general formula (7). The method for producing a cocoon structure-containing curable silicone copolymer according to claim 2, wherein:   The compound represented by the general formula (8) in the range of 0.5 to 10 mol and 2 to 100 mol with respect to 1 mol of the alkoxyl group or silanol group-containing cage silsesquioxane compound represented by the general formula (7) The method for producing a cocoon structure-containing curable silicone copolymer according to claim 2, wherein the compound represented by the general formula (9) in the range of (2) is subjected to a condensation reaction.   A curable resin composition obtained by blending either or both of a hydrosilylation catalyst and a radical initiator with the cocoon structure-containing curable silicone copolymer according to claim 1.   6. The curable resin composition according to claim 5, wherein either or both of a hydrosilylatable compound having a hydrogen atom on at least one silicon atom and a compound having an unsaturated group in the molecule are further blended.   A molded product obtained by molding and curing the curable resin composition according to claim 5.