JP2010116464A - Crosslinkable silicon compound, method for producing the same, crosslinkable composition, siloxane polymer, silicone membrane, silicon compound used as raw material of the crosslinkable silicon compound, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone membrane containing a silsesquioxane skeleton in a main chain of a silicon-based polymer and excellent in heat resistance and a technology associated with the same. <P>SOLUTION: A crosslinkable silicon compound having crosslinkable functional groups comprising a silsesquioxane group which may have a crosslinkable functional group which can be added to silicon of other compounds and a siloxane group which may have the crosslinkable functional group is provided, and a polymer is provided by crosslinking in the compound. Also, a silicon compound containing a silsesquioxane group used as a raw material of the crosslinkable silicon compound is provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a crosslinkable silicon compound, a method for producing the same, a crosslinkable composition containing the same, a siloxane polymer and a silicone film obtained by crosslinking the same, a silicon compound as a raw material thereof, and a method for producing the same.

A polymer containing a silsesquioxane skeleton has been attracting attention from various fields because it has a unique structure and is expected to have a unique effect. As such a polymer containing a silsesquioxane skeleton, a silicon-based polymer having a silsesquioxane skeleton in the main chain is known (for example, see Patent Document 1). This silicon-based polymer can be used for films, sheets, and molded articles having excellent transparency, film-forming properties, and the like. However, since the silicon-based polymer has thermoplasticity, application to a field requiring heat resistance of the molded body is limited. As described above, the silicon-based polymer still has room for examination in terms of heat resistance of the molded body.
JP 2006-22207 A

  The present invention provides a silicone film containing a silsesquioxane skeleton in the main chain of a silicon-based polymer and having excellent heat resistance, and a technique related thereto.

  The present invention provides a crosslinkable siloxane polymer in which secondary crosslinking is enabled by adding a reactive functional group to a silsesquioxane skeleton or a silicon-based polymer containing the skeleton, and the terminal of the crosslinkable siloxane polymer is A crosslinked, silicone film formed of all siloxane polymer is provided. That is, the present invention provides inventions represented by the following [1] to [22].

[1] A silsesquioxane group represented by the following formula (1) or (2), one or both of a group represented by the following formula (3) and a group represented by the following formula (4), A crosslinkable silicon compound comprising:

In formula (1) and formula (2), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
In formulas (1) to (4), R ¹ is independently a crosslinkable functional group that can be added to silicon of another compound, alkyl having 1 to 40 carbon atoms, and any hydrogen is independently halogen. Alternatively, aryl having 6 to 20 carbon atoms which may be replaced with alkyl having 1 to 20 carbon atoms, or any hydrogen in aryl may be independently replaced with halogen or alkyl having 1 to 20 carbon atoms. Represents ~ 20 arylalkyl;
In the formula (4), R ² is independently a hydroxyl group, the crosslinkable functional group, an alkyl having 1 to 40 carbon atoms, and any hydrogen may be independently replaced with a halogen or an alkyl having 1 to 20 carbon atoms. Represents aryl having 6 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms in which any hydrogen in aryl may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently —O
-May be replaced by cycloalkylene having 5 to 20 carbon atoms or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, —CH═. It may be replaced by CH— or C 5-20 cycloalkylene; and one or both of R ¹ and R ² contain one or more of the crosslinkable functional groups.

[2] The crosslinkable silicon compound according to [1] represented by the following formula (5).

Wherein (5), m represents an integer of 0 to 300 independently; n represents an integer of 1 to 1,000; R ⁰ is the same as R ⁰ in the formula (1) and (2) ; R ¹ is the same as R ¹ in the formula (1) to (4); including and, R ¹ is one or more of the crosslinkable functional groups.

[3] The crosslinkable silicon compound according to [1] or [2], wherein the crosslinkable functional group is one or both of hydrogen and alkenyl having 2 to 40 carbon atoms.

[4] The crosslinkable silicon compound according to any one of [1] to [3], wherein R ⁰ is phenyl.

[5] The method represented by [1], comprising reacting a compound represented by the following formula (6) with one or both of a compound represented by the following formula (7) and a compound represented by the following formula (8): The manufacturing method of the crosslinkable silicon compound of description. However, one or both of R ¹ and R ^{2 in} the following formulas (6) to (8) contain one or more crosslinkable functional groups.

In formula (6),
R ⁰ represents aryl having 5 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
R ³ is independently hydrogen, —Si— (R ² ) ₂ —OH, or — (Si— (R ² ) ₂ —O) ₁ —Si— (R ² ) ₂ —OH (l is independently 0 Represents an integer of ˜30;
R ¹ and R ² are independently the crosslinkable functional group, or alkyl having 1 to 40 carbon atoms, and arbitrary hydrogen may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms. 20 aryl, or any hydrogen in aryl independently represents halogen or C 7-20 arylalkyl optionally substituted with halogen or C 1-20 alkyl;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, carbon number May be replaced by 5-20 cycloalkylene or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, —CH═. It may be replaced with CH- or cycloalkylene having 5 to 20 carbon atoms.

In formula (7),
k independently represents an integer of 0 to 30;
R ¹ is the same as R ^{1 in} formula (6);
R ⁴ is independently the crosslinkable functional group, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, alkoxyl having 1 to 15 carbon atoms, oxime having 1 to 15 carbon atoms, or substituent. An optionally substituted amino, an optionally substituted amide having 1 to 15 carbon atoms, an optionally substituted aminoxy, or an optionally substituted carbon number 2 Represents -15 vinyl alcohol residues;
Carbon number of the substituent in amino and aminoxy having a substituent is 1-15.

In the formula (8), h represents 3 to 6; R ¹ is the same as R ^{1 in the} formula (6).

[6] The method for producing a crosslinkable silicon compound according to [5], comprising reacting the compound represented by the formula (6) with the compound represented by the formula (7).

[7] The method for producing a crosslinkable silicon compound according to [5], comprising reacting the compound represented by the formula (6) with the compound represented by the formula (8).

[8] The method includes reacting the compound represented by the formula (6) with the compound represented by the formula (7) and the compound represented by the formula (8) [5] The manufacturing method of the crosslinkable silicon compound as described in 2. above.

[9] A siloxane polymer obtained from the crosslinkable silicon compound according to any one of [1] to [4] and a crosslinkable compound capable of causing a crosslinking reaction with the crosslinkable silicon compound.

[10] The crosslinkable silicon compound has a hydroxyl group, and the crosslinkable compound is a condensed crosslinkable silicon compound having three or more groups or atoms that cause a condensation reaction with a hydroxyl group in the crosslinkable silicon compound. The siloxane polymer according to [9].

[11] The crosslinkable silicon compound is a first crosslinkable silicon compound having hydrogen as the crosslinkable functional group, and the crosslinkable compound is an alkenyl having 2 to 40 carbon atoms as the crosslinkable functional group. [2] The siloxane polymer according to [9], which is a second crosslinkable silicon compound having

[12] A crosslinkable composition comprising the crosslinkable silicon compound according to any one of [1] to [4] and a crosslinkable compound capable of causing a crosslinking reaction with the crosslinkable silicon compound.

[13] The crosslinkable silicon compound has a hydroxyl group, and the crosslinkable compound is a condensed crosslinkable silicon compound having three or more groups or atoms that cause a condensation reaction with a hydroxyl group in the crosslinkable silicon compound. The crosslinkable composition according to [12].

[14] The crosslinkable silicon compound is a first crosslinkable silicon compound having hydrogen as the crosslinkable functional group, and the crosslinkable compound is an alkenyl having 2 to 40 carbon atoms as the crosslinkable functional group. The crosslinkable composition according to [12], wherein the crosslinkable composition is a second crosslinkable silicon compound.

[15] The crosslinkable composition according to [14], further comprising a hydrosilylation catalyst.

[16] A silicone film obtained by curing a film of the crosslinkable composition according to any one of [12] to [15].

[17] A silicon compound represented by the following formula (10).

In the formula (10), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms; R ⁵ independently represents the crosslinkable functional group.

[18] The silicon compound according to [17], wherein the crosslinkable functional group is one or both of hydrogen and alkenyl having 2 to 40 carbon atoms.

[19] The silicon compound according to [17] or [18], wherein R ⁰ is phenyl.

[20] The silicon compound according to any one of [17] to [19], comprising reacting a compound represented by the following formula (11) with a compound represented by the following formula (12): how to.

In Formula (11), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms.

In formula (12), R ⁵ represents the crosslinkable functional group, and X represents halogen or hydrogen.

[21] The method for producing a silicon compound according to [20], wherein the crosslinkable functional group is one or both of hydrogen and alkenyl having 2 to 40 carbon atoms.

[22] The method for producing a silicon compound according to [20] or [21], wherein R ⁰ is phenyl.

The present invention provides a crosslinkable silicon compound that is capable of secondary crosslinking by providing a reactive functional group to a silsesquioxane skeleton or a silicon-based polymer containing the same, and the crosslinkable silicon compound is crosslinked. To provide a cured silicone film. The present invention can provide a silicone film having a silsesquioxane skeleton in the main chain of a silicon polymer and having excellent heat resistance. In addition, the present invention provides a method for producing a crosslinkable silicon compound that is excellent from the viewpoint of practical use, thereby facilitating application of the siloxane polymer and silicone film to the actual material by crosslinking of the crosslinkable silicon compound. . Applications of the siloxane polymer and silicone film include optical applications (resin, film, LED sealing material, contact lens).

The crosslinkable silicon compound of the present invention includes a silsesquioxane group represented by the following formula (1) or (2), a group represented by the following formula (3), and a group represented by the following formula (4). One or both of. The crosslinkable silicon compound may be one type or two or more types.

In Formula (1) and Formula (2), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms. Any two of R ⁰ may be the same or different. R ⁰ is preferably phenyl from the viewpoint of obtaining various characteristics such as optical characteristics and the ease of synthesis.

In formulas (1) to (4), R ¹ is independently a crosslinkable functional group that can be added to silicon of another compound, alkyl having 1 to 40 carbon atoms, and any hydrogen is independently halogen. Alternatively, aryl having 6 to 20 carbon atoms which may be replaced with alkyl having 1 to 20 carbon atoms, or any hydrogen in aryl may be independently replaced with halogen or alkyl having 1 to 20 carbon atoms. Represents ~ 20 arylalkyl.

In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be. In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, It may be replaced with cycloalkylene having 5 to 20 carbon atoms or phenylene. Further, in the alkylene of the arylalkyl, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, — CH = CH- or C5-C20 cycloalkylene may be substituted.

  The crosslinkable functional group is a functional group bonded to silicon in the crosslinkable silicon compound that can be added to silicon in other compounds. The crosslinkable functional groups may all be the same or different in one crosslinkable silicon compound. As said crosslinkable functional group, hydrogen or a C2-C40 alkenyl is mentioned, for example, As a specific group at this time, a C2-C40 alkenyl or hydrogen is mentioned, for example. The crosslinkable functional group is preferably hydrogen or vinyl from the viewpoint of ease of synthesis.

R ¹ may all be the same or different. R ¹ excluding the crosslinkable functional group is preferably methyl, for example, from the viewpoint of ease of synthesis.

In Formula (4), R ² is independently a hydroxyl group, the crosslinkable functional group, the alkyl having 1 to 40 carbon atoms, or any hydrogen being independently replaced by halogen or alkyl having 1 to 20 carbon atoms. The above aryl having 6 to 20 carbon atoms, or any hydrogen in aryl may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms. R ² may be all the same as or different from R ¹ . R ² excluding the crosslinkable functional group is preferably methyl, for example, from the viewpoint of ease of synthesis.

One or both of R ¹ and R ² contain one or more of the crosslinkable functional groups. In the crosslinkable silicon compound, the crosslinkable functional groups may be arranged uniformly or may be arranged unevenly. The number of the crosslinkable functional groups in the crosslinkable silicon compound can be appropriately determined according to desired physical properties and applications of the siloxane polymer that is a cross-linked product of the crosslinkable functional groups. For example, from the viewpoint of increasing the mechanical strength of the siloxane polymer film, the number of crosslinkable functional groups is preferably 1 to 60, more preferably 1 to 30 per 10,000 molecular weight. More preferably, it is 16.

  Examples of the crosslinkable silicon compound include a compound comprising a silsesquioxane group having the crosslinkable functional group and a siloxane group not having the crosslinkable functional group, or a silsesquioxane having no crosslinkable functional group. Examples thereof include a compound comprising an oxane group and a siloxane group having a crosslinkable functional group, and a compound comprising a silsesquioxane group having the crosslinkable functional group and a siloxane group having the crosslinkable functional group. Examples of the siloxane group having a crosslinkable functional group include a group comprising a group of the formula (3) having the crosslinkable functional group and a group of the formula (4) having no crosslinkable functional group, A group comprising a group of formula (3) having no functional group and a group of formula (4) having the crosslinkable functional group, and a group of formula (3) having the crosslinkable functional group and the crosslink And a group comprising a group of formula (4) having a functional functional group.

  The molecular weight of the crosslinkable silicon compound is preferably 2,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight (Mw), and 10,000 to 50,000. More preferably. The number of silsesquioxane groups in the crosslinkable silicon compound is preferably 1 to 8 and more preferably 4 to 8 per 10,000 molecular weight from the viewpoint of obtaining a high hardness siloxane polymer by crosslinking. Preferably, it is 6-8.

More specifically, examples of the crosslinkable silicon compound include compounds represented by the following formula (5). R ¹ in formula (5) contains one or more of the crosslinkable functional groups.

In formula (5), m independently represents an integer of 0 to 300, and n represents an integer of 1 to 1,000. m is preferably 0 to 300, and preferably 1 to 100, from the viewpoint of the ease of synthesis and the effect of the ratio of the silsesquioxane moiety and the siloxane moiety on the physical properties of the compound of formula (5). Is more preferable, and it is more preferable that it is 2-30. Further, n is preferably 1 to 1,000, more preferably 3 to 200, and more preferably 5 to 100, from the viewpoint of ease of synthesis and physical properties of the siloxane polymer after crosslinking. Further preferred.

The crosslinkable silicon compound is obtained by reacting a compound represented by the following formula (6) with one or both of a compound represented by the following formula (7) and a compound represented by the following formula (8). It is done.

In Formula (6), R ⁰ is the same as R ^{0 in} Formulas (1) and 2. In Formula (6), R ³ is independently hydrogen, —Si— (R ² ) ₂ —OH, or — (Si— (R ² ) ₂ —O) ₁ —Si— (R ² ) ₂ —OH. (L independently represents an integer of 0 to 30). In Formula (6), R ¹ and R ² are the same as R ¹ and R ^{2 in} Formulas (1) to (4), respectively. L in R ³ of formula (6) is preferably 1 to 9, more preferably 1 to 5, and still more preferably 1 to 3, from the viewpoint of ease of synthesis and the like.

In the formula (7), k independently represents an integer of 0 to 30, R ¹ is the same as R ^{1 in the} formula (6), R ⁴ is independently the crosslinkable functional group, Alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, alkoxyl having 1 to 15 carbon atoms, oxime having 1 to 15 carbon atoms, optionally having amino, having a substituent It represents an optionally substituted amide having 1 to 15 carbon atoms, an aminoxy optionally having substituent (s), or a vinyl alcohol residue having 2 to 15 carbon atoms optionally having substituent (s). Carbon number of the substituent in amino and aminoxy having a substituent is 1-15.

K in R ³ of the formula (7) is preferably 0 to 9, more preferably 0 to 5, and further preferably 1 to 3, from the viewpoint of availability as a compound. .

The substituent which R ⁴ may have is a compound represented by the formula (6) and the formula (7) or a compound represented by the formula (6) to (8). In the synthesis by the equilibration reaction, a substituent that acts as a terminal terminator during the equilibration reaction, or a substituent that can generate silanol by hydrolysis and bond to the silsesquioxane moiety through a siloxane bond. As such substituents, for example, substituents that function as a terminal terminator include the crosslinkable functional group and alkyl, and substituents that generate silanol by hydrolysis include, for example, acyl, methoxy and the like. Examples include alkoxyl and oxime.

In the formula (8), h represents 3 to 6; R ¹ is the same as R ¹ in the formula (6). H in Formula (8) is preferably 3 or 4 from the viewpoint of easy availability of the compound.

  For example, the reaction between the compound represented by the formula (6) and the compound represented by the formula (7) generates a crosslinkable silicon compound represented by the formula (5). This reaction is represented by the following reaction formula. This reaction is usually performed at 50 to 150 ° C. in the presence of a strong acid or in the presence of a base such as triethylamine. M in the formula (5) can be determined by the type of the chain siloxane. N in the formula (5) is adjusted depending on the reaction conditions (temperature, concentration of the compound represented by the formula (6), etc.). According to this reaction, the crosslinkable silicon compound (5) in which the silsesquioxane group which may have a crosslinkable functional group and the siloxane group which may have a crosslinkable functional group are alternately arranged. Can be obtained.

  In the above reaction, it is preferable to use a solvent. As a solvent, a solvent that can dissolve both the compound represented by the formula (6) and the compound represented by the formula (7), and a solvent that does not condense with these compounds or the crosslinkable functional group. Anything is fine. Examples of such solvents include hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane and cyclopentyl methyl ether. And solvent solvents, halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, ester solvents such as ethyl acetate, and lactam solvents such as N-methyl-2-pyrrolidone (NMP). The solvent may be a single solvent or two or more solvents.

Moreover, the said crosslinkable silicon compound separates the water which generate | occur | produces in the system at 50-150 degreeC, the compound represented by the said Formula (6), and the compound represented by the said Formula (8). It can also be obtained by reacting. The reaction between the compound represented by the formula (6) and the compound represented by the formula (8) is represented by the following reaction formula. According to this reaction, a crosslinkable silicon compound in which a silsesquioxane group which may have a crosslinkable functional group and a siloxane group which may have a crosslinkable functional group are arranged irregularly is obtained. Obtainable.

In this reaction, a disiloxane compound can be used as a terminal terminator. In this case, the crosslinkable silicon compound comprises a compound represented by the formula (6), a compound represented by the formula (8), and a compound represented by the formula (7) at 50 to 150 ° C. It is obtained by reacting with The reaction of the compound represented by the formula (6) with the compound represented by the formula (8) and the compound represented by the formula (7) is represented by the following reaction formula. According to this reaction, the silsesquioxane group which may have a crosslinkable functional group and the siloxane group which may have a crosslinkable functional group are irregularly arranged and crosslinkable at the terminal. A crosslinkable silicon compound which may have a functional group can be obtained.

The above reaction using the compound represented by the formula (8) as a raw material is a reaction called an equilibration reaction, and a strong acid or a strong base is usually used as a catalyst. In the method for producing a crosslinkable silicon compound in the present invention, a strong acid is preferable as the catalyst in consideration of the stability during the reaction of silsesquioxane in each of the reactions described above. Examples of such a catalyst include hydrochloric acid, sulfuric acid, fluorosulfuric acid, trifluoromethanesulfonic acid, activated clay, and sulfonic acid ion exchange resin. Of these, trifluoromethanesulfonic acid, activated clay, and sulfonic acid ion exchange resins are more preferable.

In the above reaction, it is preferable to use a solvent. Any solvent that can dissolve both the compound represented by the formula (6) and the compound represented by the formula (8) as a solvent and does not react with the acid or base compound used as a catalyst. Good. Examples of such solvents include hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, and cyclopentyl methyl ether. And halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride. The solvent may be a single solvent or two or more solvents.

Among the compounds represented by the formula (6), a compound represented by the following formula (10), which is a compound in which R ¹ is the crosslinkable functional group, is a compound represented by the following formula (11): It can be obtained by reacting a compound represented by the following formula (12). In the formulas (10) and (11), R ⁰ is the same as R ^{0 in the} formulas (1) and (2), respectively. In the formulas (10) and (12), R ⁵ is independently the bridge. Represents a functional group.

This reaction is usually performed at −10 to 30 ° C. in the presence of a base such as triethylamine. In these reactions, it is preferable to use a solvent. The solvent is a solvent that can dissolve both the compound represented by the formula (11) and the compound represented by the formula (12), and the silicon compound of the formula (10) or the crosslinkable functional group. Any solvent that does not condense with the group may be used. Examples of such solvents include hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, diethyl ether, tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, and the like. And ether solvents, halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, ester solvents such as ethyl acetate, and lactam solvents such as N-methyl-2-pyrrolidone (NMP). The solvent may be a single solvent or two or more solvents.

  The siloxane polymer of the present invention is obtained from the crosslinkable silicon compound and a crosslinkable compound capable of causing a crosslinking reaction with the crosslinkable silicon compound.

  The crosslinkable compound may be one type or two or more types, may be a silicon compound, or may be a non-silicon compound such as a normal organic compound. The crosslinkable compound may be a compound that crosslinks with the crosslinkable functional group of the crosslinkable silicon compound, or may be a compound that crosslinks with another portion of the crosslinkable silicon compound. The crosslinkable compound can be determined based on the type of the crosslinkable silicon compound and the form of crosslinking with the crosslinkable silicon compound.

For example, when the crosslinkable silicon compound has a hydroxyl group (for example, R ² is a hydroxyl group or a compound represented by the formula (5)), the crosslinkable compound includes It is possible to use a condensation-crosslinking silicon compound having 3 or more groups or atoms that cause a condensation reaction with the hydroxyl group. Examples of such a condensation-crosslinking silicon compound include methyltrimethoxysilane, methyltris (methylethylketoxime) silane, and methyltriacetoxysilane. In the case of using the condensed crosslinkable silicon compound, for example, the crosslinkable silicon compound can be crosslinked by placing the crosslinkable composition at room temperature in an atmosphere of water such as normal air.

  For example, when the crosslinkable silicon compound is the first crosslinkable silicon compound having hydrogen as a crosslinkable functional group, the crosslinkable compound contains alkenyl having 2 to 40 carbon atoms as the crosslinkable functional group. The 2nd crosslinkable silicon compound which has can be used.

  Furthermore, the crosslinkable compound may be a compound that reacts with a crosslinkable functional group or other portion in the crosslinkable silicon compound by another reaction mechanism such as radical polymerization. Examples of such a crosslinkable compound include compounds having an unsaturated hydrocarbon group such as a vinyl group when the crosslinkable silicon compound has an alkenyl having 2 to 40 carbon atoms as a crosslinkable functional group. Examples of such compounds include acrylic monomers such as methacrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, butyl acrylate, 2-hydroxyethyl acrylate, and vinyl monomers such as vinyl acetate. Can be mentioned.

  The ratio of the crosslinkable compound to the crosslinkable silicon compound as a component of the siloxane polymer is 1 to 100 with respect to 100 parts by weight of the crosslinkable silicon compound from the viewpoint of the physical properties of the resulting siloxane polymer and silicone film. It is preferable that it is, it is more preferable that it is 2-50, and it is further more preferable that it is 5-20.

  The weight average molecular weight of the siloxane polymer is preferably 2,000 to 1,000,000, and preferably 3,000 to 200,000 from the viewpoint of the ease of synthesis of the raw material compound and the physical properties of the obtained siloxane polymer. More preferably, it is 5,000-100,000.

  The crosslinkable composition of the present invention contains the crosslinkable silicon compound and the crosslinkable compound. Since the crosslinkable silicon compound has the crosslinkable functional group, for example, a mixture of two or more crosslinkable silicon compounds each having one or more of hydrogen and alkenyl groups as the crosslinkable functional group. Can be cured by a crosslinking reaction such as a hydrosilylation reaction.

  Further, for example, when the crosslinkable silicon compound has a hydroxyl group, it can be crosslinked and cured by using the condensation crosslinkable silicon compound. In the case of using a condensation crosslinkable silicon compound, the crosslinkable silicon compound and the crosslinkable compound may be crosslinked only by crosslinking by the condensation reaction with the condensation crosslinkable silicon compound, or in addition to a crosslinking reaction such as a hydrosilylation reaction. Furthermore, the crosslinkable silicon compound and the crosslinkable compound may be crosslinked by a condensation reaction with the condensation crosslinkable silicon compound.

  The ratio of the crosslinkable compound to the crosslinkable silicon compound in the crosslinkable composition is 1 with respect to 100 parts by weight of the crosslinkable silicon compound from the viewpoint of the characteristics of the siloxane polymer and silicone film obtained by crosslinking and curing. It is preferable that it is -40, It is more preferable that it is 3-25, It is further more preferable that it is 5-15.

  The crosslinkable composition may further contain a solvent. Such a solvent is preferably a solvent that can dissolve both the crosslinkable silicon compound and the crosslinkable compound and that does not condense with the crosslinkable silicon compound or the crosslinkable compound. Examples of such solvents include hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF) and dioxane, and chloride. Examples thereof include halogenated hydrocarbon solvents such as methylene and carbon tetrachloride, and ester solvents such as ethyl acetate. The solvent may be a single solvent or two or more solvents.

  The content of the solvent is preferably an amount such that the content of the crosslinkable silicon compound and the crosslinkable compound is 20 to 80% by weight, for example, from the viewpoint of applicability, and an amount of 30 to 70% by weight. It is more preferable that the amount is 40 to 60% by weight.

  Moreover, the said crosslinkable composition may further contain the adjuvant for the bridge | crosslinking by a crosslinkable functional group. Such an auxiliary agent can be determined based on the type of the crosslinkable functional group. For example, a crosslinkable composition containing a first crosslinkable silicon compound having hydrogen as a crosslinkable functional group and a second crosslinkable silicon compound having alkenyl having 2 to 40 carbon atoms as a crosslinkable functional group. In that case, in addition to the solvent described above, a hydrosilylation catalyst may be further contained.

  As the hydrosilylation catalyst, a platinum catalyst usually used in a hydrosilyl reaction can be used. Examples of such a platinum catalyst include chloroplatinic acid and karsted catalyst. In the crosslinkable composition, the content of the hydrosilylation catalyst is preferably 0.1 to 1,000 ppm, more preferably 0.5 to 200 ppm, and further preferably 1 to 50 ppm. .

The silicone film of the present invention is formed by curing the film of the crosslinkable composition. The film | membrane of a crosslinkable composition can be formed by the well-known method apply | coated to a board | substrate or a sheet | seat. Further, the curing of the film of the crosslinkable composition can be determined based on the conditions for crosslinking with the crosslinkable functional group. For example, when the crosslinkable functional group is hydrogen and alkenyl having 2 to 40 carbon atoms, the silicone film can be formed by heating the crosslinkable composition or the film thereof to 50 to 150 ° C. for 1 to 15 hours.

  For example, when the crosslinkable silicon compound is a compound of the formula (5), the silicone film of the present invention has a main chain formed of silanols in which siloxane chains and silsesquioxane are alternately arranged. It is comprised by the crosslinked material of a crosslinkable siloxane polymer. Such a silicone film has excellent effects in various physical properties such as solubility, heat resistance, mechanical strength, optical permeability, gas permeability, dielectric constant, flame retardancy, adhesiveness, workability, and a wide range of applications. Expected to be used.

  For example, the application of electrical / electronic materials in the silicone film of the present invention includes coating agents for substrates such as metal elution prevention films, gas barrier films, antireflection films, liquid sealants, light emitting diode sealing materials, interlayer insulating films, dirt Examples include a coating agent for prevention, an optical element such as a microlens, a light guide plate, and an optical waveguide material, a display substrate, and a printed wiring board. Also, it is expected to be used for optical resins, optical films, contact lenses and the like.

  The crosslinkable silicon compound and silicon compound in the present invention can be confirmed by the molecular weight by GPC or the presence of peaks of silsesquioxane part and siloxane part by NMR. Further, the siloxane polymer and the silicone film in the present invention can be confirmed by, for example, changes in heat resistance and solubility in a solvent when produced from a raw material containing the crosslinkable silicon compound. For example, the formation of the siloxane polymer and silicone film in the present invention can be confirmed by not melting when heated to 120 ° C. or by the product being insoluble in acetone.

In addition, the weight average molecular weight of each of the aforementioned compounds in the present invention can be determined by GPC, and more specifically can be determined under the following conditions.
<GPC measurement conditions>
The measurement conditions for GPC measurement are shown below. <Measurement conditions>
Column: Tosoh Co., Ltd. TSKgel G4000HXL + TSKgel G3000HXL + TSKgel G2000HXL + TSKgel G2500HXL, 4 in series Mobile phase: THF
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Detector: RI
Molecular weight standard sample: polystyrene with known molecular weight

  Hereinafter, in the following formulas showing examples of the present invention, “Ph” represents phenyl.

Example 1 Synthesis of DD (Vi) OH (Formula (III))

  A sampling tube, a thermometer protection tube, and a dropping funnel were connected to the 2 L flask, and the flask was purged with nitrogen. Then, 1 L of tetrahydrofuran and 36.5 g of triethylamine were placed in the flask. After putting 53 g of vinyltrichlorosilane (formula (II)) in the flask, the internal temperature was cooled to around 5 ° C. in an ice water bath. While taking care that the internal temperature of the flask did not exceed 15 ° C, DD-ONa (formula (I)) a 68.7 g powder that had been dried in advance was added little by little. After the addition of DD-ONa, the mixture was stirred as it was for 2 hours, and then stirred overnight at room temperature. The reaction was stopped by adding 250 mL of pure water to the flask while taking care not to allow the internal temperature of the flask to exceed 15 ° C. by cooling again in an ice water bath.

  The obtained reaction liquid was extracted, transferred to a 3 L flask, 500 mL of ethyl acetate was added and stirred, and the lower layer was extracted. After adding pure water and stirring, the lower layer was extracted. This water washing operation was performed until the pH of the upper layer was 6 to 7, and the organic phase was further washed with water three times. During the water washing operation, ethyl acetate was added as appropriate to maintain good layer separation. The upper layer was extracted, and the solvent was distilled off with an evaporator to obtain 88.4 g of a pasty crude product.

  80 mL of ethyl acetate was added to the crude product to dissolve the crude product. 200 mL of heptane was added to the obtained solution, ethyl acetate was distilled off from the solution with an evaporator, and the precipitated solid was collected by filtration. The obtained solid was washed with heptane and dried under reduced pressure to obtain 59.5 g of a white solid. It was confirmed by NMR analysis and the like that the obtained white solid was the target product (formula (III)).

Example 2 Synthesis of DD (H) OH (Formula (V))

  A sampling tube, a thermometer protection tube, and a dropping funnel were connected to the 2 L flask, and after the inside of the flask was replaced with nitrogen, 1 L of tetrahydrofuran and 21.9 g of triethylamine were placed in the flask. After putting 22.6 g of trichlorosilane (formula (IV)) in the flask, the internal temperature of the flask was cooled to around 5 ° C. in an ice water bath. While taking care so that the internal temperature of the flask does not exceed 15 ° C., 71.0 g of a previously dried DD-ONa (formula (I)) powder was added little by little. After the addition of DD-ONa, the mixture was stirred as it was for 2 hours, and then stirred overnight at room temperature. The solution was cooled again in an ice water bath, and the reaction was stopped by adding 250 mL of pure water to the flask, taking care not to let the internal temperature of the flask exceed 15 ° C.

  The obtained reaction liquid was extracted, transferred to a 3 L flask, 500 mL of ethyl acetate was added and stirred, and the lower layer was extracted. After adding pure water and stirring, the lower layer was extracted. This water washing operation was performed until the pH of the upper layer was 6 to 7, and the resulting organic phase was washed with water three times. During the water washing operation, acetone was appropriately added to keep the layer separation good. The upper layer and the emulsion layer were extracted, and the solvent was distilled off using an evaporator, thereby obtaining 127.3 g of a pasty crude product.

  The crude product was dissolved in ethyl acetate, the insoluble matter was removed by filtration, and ethyl acetate was distilled off with an evaporator to obtain 49.2 g of a white solid. It was confirmed by NMR analysis and the like that the obtained white solid was the target product (formula (V)).

[Synthesis Example 1] Synthesis of DD (Me) siloxane polymer (formula (VIII))

  A 200 mL flask was equipped with a condenser, a stirrer, and a thermometer protection tube, and the inside of the flask was replaced with nitrogen. DD (Me) OH (formula (VI)) 20 g, D4 (formula (VII)) 15 g, RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation) 1.75 g, dehydrated toluene 200 mL in a flask I put it in. The mixture was heated and stirred at 110 ° C. for 72 hours, cooled, and after cooling, RCP-160M was filtered off, activated carbon was added to the obtained filtrate, and the mixture was stirred and filtered. Thereafter, 27.7 g of a white viscous liquid was obtained by distilling off the solvent and low boiling point from the obtained filtrate with an evaporator. NMR and GPC analysis revealed that the obtained white viscous liquid was the target product (formula (VIII)), and was a polymer formed by randomly binding each constituent unit in formula (VIII). The number average molecular weight Mn of the target product was 33,000, and the weight average molecular weight Mw was 41,900. Moreover, n / m was 9.6 from Si-NMR of the target product. When calculated from this ratio and the number average molecular weight Mn, n was 17 and m was 167.

[Example 3] Synthesis of DD (Vi) -Si3 (formula (IX))

  A thermometer protection tube and a sampling tube were connected to the 500 mL flask, and the inside of the flask was purged with nitrogen. In the flask, 20 g of DD (Vi) OH (formula (III)) obtained in Example 1, 80 g of cyclopentyl methyl ether (CPME), and 20 g of triethylamine were placed. While maintaining the internal temperature of the flask at around 0 ° C., 4.6 g of 1,5-dichlorohexamethyltrisiloxane (DCHMTS) was added dropwise. After stirring for 24 hours at room temperature, 200 mL of pure water was added to stop the reaction. The resulting reaction solution was neutralized by adding aqueous hydrochloric acid, and washed with water by adding acetone. After extracting the upper layer, the solvent was distilled off by an evaporator to obtain a crude product.

  Acetone was added to the crude product, and the resulting insoluble matter was removed by filtration under reduced pressure. Then, CPME was added to the obtained filtrate, and acetone was distilled off by an evaporator. This solution was added to hexane to precipitate, and the precipitated white viscous product was dissolved in acetone, and the solvent was distilled off with an evaporator to obtain 12.3 g of white candy-like powder. NMR analysis showed that the obtained white candy-like powder was the target product (formula (IX)). By GPC analysis, it was found that Mw of the obtained white candy-like powder was 8,350.

[Example 4] Synthesis of DD (Me) OH + SiH-containing siloxane polymer (formula (XII))

A cooling tube, a stirrer, and a thermometer protection tube were set in a 200 mL flask, and the inside of the flask was purged with nitrogen. DD (Me) OH having Mw of 41,900 (formula (VIII)) 5.34 g, D′ 4 (formula (X)) 0.52 g, M′M ′ (formula (XI)) 0.05 g, RCP- 160M
0.29 g and 30 mL of dehydrated toluene were placed in the flask, and the mixture was heated and stirred at 100 ° C. for 15 hours. After cooling, RCP-160M was filtered, and the solvent and low-boiling components were distilled off from the obtained filtrate with an evaporator to obtain 6.75 g of a white viscous liquid. From the NMR analysis and the GPC analysis, the obtained white viscous liquid is a target product (formula (XII)), which is a polymer in which each constituent unit in formula (XII) is bonded at random, and has the formula (XII) It was found that p = 293, q = 46, and r = 31. By GPC analysis, it was found that the obtained white viscous liquid had Mn = 61,000 and Mw = 16,000.

[Example 5] Synthesis of DD (Me) OH + SiH-containing siloxane polymer (formula (XV))

  A cooling tube, a stirrer, and a thermometer protection tube were set in a 200 mL flask, and the inside of the flask was purged with nitrogen. DD (Me) OH with Mw of 41,900 (formula (VIII)) 5.35 g, DV4 (formula (XIII)) 0.69 g, DVDS (formula (XIV)) 0.06 g, RCP-160M 0.36 g, 50 mL of dehydrated toluene was placed in the flask, and heated and stirred at 110 ° C. for 15 hours. After cooling, RCP-160M was filtered, and the solvent and low-boiling components were distilled off from the obtained filtrate with an evaporator to obtain 6.0 g of a white viscous liquid. From the NMR analysis, the obtained white viscous liquid is the target product (formula (XV)), and is a polymer in which each constituent unit in formula (XV) is randomly bonded. In formula (XV), p = 288, q = 54, r = 36. GPC analysis showed that the obtained white viscous liquid had Mn = 69,900 and Mw = 146,000.

[Example 6] Synthesis of DD (Me) OH + Vi group-containing siloxane polymer (formula (XVIII))

  A 50 mL flask was purged with nitrogen, and DD (Me) -SiOH (formula (XVII)) in which m in formula (VIII) is 1 and n is 2, 0.50 g (0.37 mmol), side chain vinyl silicone (Formula (XVI), Mw = about 6000) 2.25 g (0.18 mmol), RCP-160M 0.0275 g (1% by weight of substrate) as a catalyst, 5 mL of toluene dehydrated in advance with a molecular sieve are placed in a flask. It was. The internal temperature of the flask was raised to 80 ° C., and the mixture was stirred with heating for 15 hours.

  After completion of the reaction, RCP-160M was removed by filtration, and the solvent was distilled off from the obtained filtrate under reduced pressure to obtain a polymer. From the GPC analysis, it was found that the obtained polymer had Mn = 3,840 and Mw = 6,000. From the NMR of the obtained polymer, the obtained polymer is the target product (formula (XVIII)), which is a polymer in which each constituent unit in formula (XVIII) is randomly bonded, and the DD site is a siloxane polymer. It was found that the polymer contained one, i.e., r = 1 in formula (XVIII) and p = 17 and q = 16 in formula (XVIII).

[Example 7] Production of DD-containing cured product In a screw tube, 1 g of the polymer obtained in Example 4 (formula (XII)), 1 g of the polymer obtained in Example 5 (formula (XV)), and 2 g of toluene. Then, 5 μL of platinum catalyst (Calstead catalyst) was added and dissolved uniformly. The solution obtained was put in a Teflon (registered trademark) Petri dish, and after toluene was volatilized in an oven at 80 ° C., it was cured by heating at 150 ° C. for 1 hour to obtain a colorless transparent crosslinked film. .

[Thermal stability test]
Regarding the stability of the polymer obtained in Example 4, the polymer obtained in Example 5, and the crosslinked film obtained in Example 7 against thermal decomposition, TG (thermogravimetric) -DTA (differential thermal analysis) measurement was performed. The weight loss at 5% weight loss (Td5) and 800 ° C. was examined. The conditions for TG-DTA measurement are shown below. The results are shown in the table below.
Measuring device: simultaneous differential thermothermal weight measuring device EXSTAR6000 TG / DTA6300 (manufactured by Seiko Instruments Inc.)
Bread: Pt
Standard sample: Aluminum oxide (10 mg)
Sample mass: about 10mg
Temperature program: 25-800 ° C
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen

  It was found that a crosslinked film excellent in thermal stability can be obtained by curing by a hydrosilylation reaction between the hydrogen group of the polymer obtained in Example 4 and the vinyl group of the polymer obtained in Example 5. .

  The cured product of a curable silicon compound having a silsesquioxane group has optical properties, electrical properties, heat resistance, and gas permeability as compared with ordinary silicon compounds such as siloxane and its polymers. In some cases, it exhibits unique characteristics in various characteristics such as mechanical strength. Therefore, the curable silicon compound having a silsesquioxane group and a cured product thereof are more effectively used in the fields of transparent films such as lenses and protective films, and electrical and optical sealing materials. Be expected.

Claims (22)

Crosslinking comprising a silsesquioxane group represented by the following formula (1) or (2) and one or both of a group represented by the following formula (3) and a group represented by the following formula (4) Silicon compounds.

(In Formula (1) and Formula (2), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
In formulas (1) to (4), R ¹ is independently a crosslinkable functional group that can be added to silicon of another compound, alkyl having 1 to 40 carbon atoms, and any hydrogen is independently halogen. Alternatively, aryl having 6 to 20 carbon atoms which may be replaced with alkyl having 1 to 20 carbon atoms, or any hydrogen in aryl may be independently replaced with halogen or alkyl having 1 to 20 carbon atoms. Represents ~ 20 arylalkyl;
In the formula (4), R ² is independently a hydroxyl group, the crosslinkable functional group, an alkyl having 1 to 40 carbon atoms, and any hydrogen may be independently replaced with a halogen or an alkyl having 1 to 20 carbon atoms. Represents aryl having 6 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms in which any hydrogen in aryl may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, carbon number May be replaced by 5-20 cycloalkylene or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, —CH═. It may be replaced by CH— or C 5-20 cycloalkylene; and one or both of R ¹ and R ² contain one or more of the crosslinkable functional groups. ) The crosslinkable silicon compound of Claim 1 represented by following formula (5).

(In the formula (5), m represents an integer of 0 to 300 independently; n represents an integer of 1 to 1,000; R ⁰ is the same as R ⁰ in the formula (1) and (2) There; R ¹ is the same as R ¹ in the formula (1) to (4); including and, R ¹ is one or more of the crosslinkable functional group).   The crosslinkable silicon compound according to claim 1 or 2, wherein the crosslinkable functional group is one or both of hydrogen and alkenyl having 2 to 40 carbon atoms. The crosslinkable silicon compound according to any one of claims 1 to 3, wherein R ⁰ is phenyl. The bridge | crosslinking of Claim 1 including making the compound represented by following formula (6) react one or both of the compound represented by following formula (7) and the compound represented by following formula (8). A crosslinkable functional group that can be added to silicon of another compound in which one or both of R ¹ and R ² in formulas (6) to (8) are one or more. Including).

(In Formula (6),
R ⁰ represents aryl having 5 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
R ³ is independently hydrogen, —Si— (R ² ) ₂ —OH, or — (Si— (R ² ) ₂ —O) ₁ —Si— (R ² ) ₂ —OH (l is independently 0 Represents an integer of ˜30;
R ¹ and R ² are independently the crosslinkable functional group, or alkyl having 1 to 40 carbon atoms, and arbitrary hydrogen may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms.
20 aryl, or any hydrogen in aryl independently represents halogen or C 7-20 arylalkyl optionally substituted with halogen or C 1-20 alkyl;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, carbon number May be replaced by 5-20 cycloalkylene or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, —CH═. It may be replaced with CH- or cycloalkylene having 5 to 20 carbon atoms. )

(In formula (7),
k independently represents an integer of 0 to 30;
R ¹ is the same as R ^{1 in} formula (6);
R ⁴ is independently the crosslinkable functional group, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, alkoxyl having 1 to 15 carbon atoms, oxime having 1 to 15 carbon atoms, or substituent. An optionally substituted amino, an optionally substituted amide having 1 to 15 carbon atoms, an optionally substituted aminoxy, or an optionally substituted carbon number 2 Represents -15 vinyl alcohol residues;
In amino and aminoxy having a substituent, the substituent has 1 to 15 carbon atoms. )

(In formula (8), h represents 3 to 6; R ¹ is the same as R ^{1 in} formula (6).)   The method for producing a crosslinkable silicon compound according to claim 5, comprising reacting the compound represented by the formula (6) with the compound represented by the formula (7).   The method for producing a crosslinkable silicon compound according to claim 5, comprising reacting the compound represented by the formula (6) with the compound represented by the formula (8).   The compound represented by the formula (6) is reacted with the compound represented by the formula (7) and the compound represented by the formula (8). A method for producing a crosslinkable silicon compound.   The siloxane polymer obtained from the crosslinkable silicon compound as described in any one of Claims 1-4, and the crosslinkable compound which can produce a crosslinking reaction with this crosslinkable silicon compound.   The crosslinkable silicon compound has a hydroxyl group, and the crosslinkable compound is a condensed crosslinkable silicon compound having three or more groups or atoms that cause a condensation reaction with a hydroxyl group in the crosslinkable silicon compound. 9. The siloxane polymer according to 9. The crosslinkable silicon compound is a first crosslinkable silicon compound having hydrogen as a crosslinkable functional group that can be added to silicon of another compound, and the crosslinkable compound is The siloxane polymer according to claim 9, which is a second crosslinkable silicon compound having an alkenyl having 2 to 40 carbon atoms. A crosslinkable composition comprising the crosslinkable silicon compound according to any one of claims 1 to 4 and a crosslinkable compound capable of causing a crosslinking reaction with the crosslinkable silicon compound.   The crosslinkable silicon compound has a hydroxyl group, and the crosslinkable compound is a condensed crosslinkable silicon compound having three or more groups or atoms that cause a condensation reaction with a hydroxyl group in the crosslinkable silicon compound. 13. The crosslinkable composition according to 12. The crosslinkable silicon compound is a first crosslinkable silicon compound having hydrogen as a crosslinkable functional group that can be added to silicon of another compound, and the crosslinkable compound is It is a 2nd crosslinkable silicon compound which has a C2-C40 alkenyl, The crosslinkable composition of Claim 12 characterized by the above-mentioned. The crosslinkable composition according to claim 14, further comprising a hydrosilylation catalyst.   A silicone film obtained by curing a film of the crosslinkable composition according to any one of claims 12 to 15. A silicon compound represented by the following formula (10).

(In the formula (10), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms; R ⁵ can be independently added to silicon of other compounds. Represents a crosslinkable functional group.)   The silicon compound according to claim 17, wherein the crosslinkable functional group is one or both of hydrogen and alkenyl having 2 to 40 carbon atoms. The silicon compound according to claim 17 or 18, wherein R ⁰ is phenyl. The method to manufacture the silicon compound as described in any one of Claims 17-19 including reacting the compound represented by following formula (11), and the compound represented by following formula (12).

(In the formula (11), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms.)

(In formula (12), R ⁵ represents a crosslinkable functional group that can be added to silicon of another compound, and X represents halogen or hydrogen.)   The method for producing a silicon compound according to claim 20, wherein the crosslinkable functional group is one or both of hydrogen and alkenyl having 2 to 40 carbon atoms. The method for producing a silicon compound according to claim 20 or 21, wherein R ⁰ is phenyl.