Siloxane polymers and crosslinked materials having silanol groups

Abstract

To provide a siloxane polymer capable of providing a cross-linked body having a low thermal expansion coefficient in a temperature range of 50°C to 180°C, and to provide the cross-linked body having the low thermal expansion coefficient in the temperature range of 50°C to 180°C.SOLUTION: A siloxane polymer comprises a repeating unit represented by a formula (1). In the formula, R0 is independently 6-20C aryl or 5-6C cycloalkyl; R1 is independently a hydrogen atom, 6-20C aryl, 5-6C cycloalkyl, 7-40C arylalkyl, or 1-40C alkyl; R2 and R3 are each independently 6-20C aryl, 5-6C cycloalkyl, 7-40C arylalkyl, or 1-40C alkyl; p represents a real number of 1 or more; x represents a real number of 1-30; and y1+y2 represents a real number of 1-30, provided that y2 is 0 or more but less than 30.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to siloxane polymers and crosslinked products having silanol groups. [Background technology]

[0002] Polymers containing silsesquioxane with a cage-like structure are attracting attention from various fields due to their unique structure and the resulting unique effects. Among such polymers containing a silsesquioxane skeleton, silicon-based polymers with a silsesquioxane skeleton in the main chain are known (see, for example, Patent Document 1). Furthermore, by introducing crosslinkable functional groups into silicon compounds with a silsesquioxane skeleton having a cage-like structure in the main chain to form crosslinked polymers, silicone films with excellent heat resistance have been developed (Patent Document 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2006-33307 [Patent Document 2] Japanese Patent Publication No. 2010-116464 [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention aims to provide a siloxane polymer that can provide a crosslinked body having a low coefficient of thermal expansion in the temperature range of 50°C to 180°C, and a crosslinked body having a low coefficient of thermal expansion in the temperature range of 50°C to 180°C. [Means for solving the problem]

[0005] The inventors of this invention successfully synthesized a novel siloxane polymer having silanol groups by reacting a silsesquioxane compound with a compound containing a linear siloxane structure to produce a siloxane polymer containing hydroxyl groups in the main chain, and then converting the hydrosilyl groups of the siloxane polymer to silanol groups. Furthermore, they discovered that by crosslinking this silanol-containing siloxane polymer, a crosslinked material having a thermal expansion coefficient of less than 200 ppm / K in the temperature range of 50°C to 180°C can be obtained, thus completing the present invention.

[0006] In other words, embodiments of the present invention include the following configurations. [1] A siloxane polymer comprising a repeating unit represented by formula (1). [ka] In the above formula, R 0 This independently represents an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, wherein any hydrogen atom in the aryl group having 6 to 20 carbon atoms or the cycloalkyl group having 5 to 6 carbon atoms may be independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms; R 1 The aryl group independently represents a hydrogen atom, a carbon-6 to carbon-20 aryl group, a carbon-5 to carbon-6 cycloalkyl group, a carbon-7 to carbon-40 arylalkyl group, or a carbon-1 to carbon-40 alkyl group, and in the carbon-6 to carbon-20 aryl group, the carbon-5 to carbon-6 cycloalkyl group, and the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom independently represents a fluorine atom or a carbon-1 to carbon-1 alkyl group. It may be replaced with 20 alkyl groups, and in the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom of the alkylene may be replaced with a fluorine atom, and any -CH2- may be independently replaced with -O-, -CH=CH-, or a cycloalkylene having 5 to 20 carbon atoms, and in the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH2- may be independently replaced with -O- or a cycloalkylene having 5 to 20 carbon atoms; R 2 and R 3Each of these independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. In the aryl groups having 6 to 20 carbon atoms, the cycloalkyl groups having 5 to 6 carbon atoms, and the aryl groups having 7 to 40 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the arylalkyl groups having 7 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a cycloalkylene group having 5 to 20 carbon atoms. In the alkyl groups having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a cycloalkylene group having 5 to 20 carbon atoms. p represents a real number greater than or equal to 1; x represents a real number between 1 and 30; y1 + y2 represents a real number between 1 and 30, and y2 is between 0 and 30 (inclusive).

[0007] [2] A siloxane polymer composition comprising the siloxane polymer described in [1], a crosslinking agent, and a transition metal catalyst. [3] The siloxane polymer composition according to [2] that gives a crosslinked material in which the maximum value of the coefficient of linear expansion calculated in the range from 50°C to 180°C in 10°C increments is less than 200 ppm / K. [4] The siloxane polymer composition according to [2] or [3] that gives a crosslinked material having a glass transition temperature of 0°C or higher. [5] The crosslinking density n, calculated from the following formula (α), is 150 mol / m³. 3 A siloxane polymer composition according to any one of claims [1] to [4], which provides a crosslinked material having the above characteristics. n = E' / 3RT···(α) n: Crosslink density (mol / m 3 E': Storage modulus (Pa), R: Gas constant ((Pa·m)) 3 ) / (K mol)), T: temperature (K) A crosslinked body obtained by crosslinking a siloxane polymer composition described in any of [6] [2] to [5]. [7] The crosslinked product according to [6], wherein the maximum value of the linear expansion coefficient calculated in the range from 50°C to 180°C at intervals of 10°C is less than 200 ppm / K. [8] The crosslinked product according to [6] or [7], wherein the glass transition temperature is 0°C or higher. [9] The crosslinked product according to any one of [6] to [8], wherein the crosslinking density n determined by the following formula (α) is 150 mol / m 3 or more. n = E’ / 3RT ··· (α) n: crosslinking density (mol / m 3 ), E’: storage modulus (Pa), R: gas constant ((Pa·m 3 ) / (K·mol)), T: temperature (K)

[0008]

[10] A method for producing a siloxane polymer containing a repeating unit represented by formula (1), comprising a step of converting a hydrosilyl group of a siloxane polymer containing a repeating unit represented by formula (1’) into a silanol group in the presence of a transition metal catalyst.

Chemical formula

[11] A method for producing a siloxane polymer comprising a repeating unit represented by formula (1) as described in

[10] , wherein the transition metal catalyst is a palladium catalyst. [Effects of the Invention]

[0009] The present invention provides a siloxane polymer that can provide a crosslinked body having a low coefficient of thermal expansion in the temperature range of 50°C to 180°C, and a crosslinked body having a low coefficient of thermal expansion in the temperature range of 50°C to 180°C. A crosslinking body having a coefficient is provided. [Modes for carrying out the invention]

[0010] The embodiments of the present invention will be described in detail below, but the following description is merely an example (representative example) of the embodiments of the present invention, and the present invention is not limited in any way to these. Furthermore, the embodiments of the present invention can be combined as appropriate. The terms used herein are defined as follows: Alkyl and alkylene may be linear or branched groups. This is true even when any hydrogen in these groups is replaced with a halogen or a cyclic group, or when any -CH2- is replaced with -O-, -CH=CH-, cycloalkylene, cycloalkenylene, phenylene, etc. In this invention, "any" means that not only the position but also the number of groups is arbitrary. When there are multiple groups, each may be replaced with a different group. For example, when two -CH2- in an alkyl group are replaced with -O- and -CH=CH-, it represents an alkoxyalkenyl or alkenyloxyalkyl group. In this case, any of the alkoxy, alkenylene, alkenyl, and alkylene groups may be linear or branched groups. However, when it is stated that any -CH2- is replaced with -O-, it does not mean that multiple consecutive -CH2- are replaced with -O-. In other words, for example, -CH2-CH2- cannot be replaced with -OO-.

[0011] 1. Siloxane polymer A siloxane polymer, which is one embodiment of the present invention (hereinafter also referred to as "the siloxane polymer of the present invention"), is characterized by containing a repeating unit represented by formula (1). [ka] In the above formula, R 0 This independently represents an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, wherein any hydrogen atom in the aryl group having 6 to 20 carbon atoms or the cycloalkyl group having 5 to 6 carbon atoms may be independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms; R 1 Each of the following independently represents a hydrogen atom, a carbon-6 to carbon-20 aryl group, a carbon-5 to carbon-6 cycloalkyl group, a carbon-7 to carbon-40 arylalkyl group, or a carbon-1 to carbon-40 alkyl group; in the carbon-6 to carbon-20 aryl group, the carbon-5 to carbon-6 cycloalkyl group, and the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom may be independently replaced by a fluorine atom or a carbon-1 to carbon-20 alkyl group; in the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or a carbon-5 to carbon-20 cycloalkylene group; in the carbon-1 to carbon-40 alkyl group, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a carbon-5 to carbon-20 cycloalkylene group; R 2 and R 3 Each of these independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. In the aryl groups having 6 to 20 carbon atoms, the cycloalkyl groups having 5 to 6 carbon atoms, and the aryl groups having 7 to 40 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the alkyl groups having 7 to 40 carbon atoms, any hydrogen atom may be replaced by a fluorine atom, and any -C H2- may be independently replaced by -O-, -CH=CH-, or a cycloalkylene having 5 to 20 carbon atoms, and in the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a cycloalkylene having 5 to 20 carbon atoms; p represents an integer greater than or equal to 1; x represents an integer between 1 and 30; y1 + y2 represents an integer between 1 and 30, and y2 is between 0 and 30 (inclusive).

[0012] (R 0 ) R 0 This independently represents an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms. Examples of aryl compounds having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyrenyl, crisenyl, naphthacenyl, and perilenyl. Among these, phenyl, naphthyl, anthryl, and phenanthryl are preferred, and phenyl, naphthyl, and anthryl are more preferred. Examples of cycloalkyl compounds with 5 to 6 carbon atoms include cyclopentyl and cyclohexyl. The aryl group having 6 to 20 carbon atoms and the cycloalkyl group having 5 to 6 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. R 0 The compound is preferably phenyl or cyclohexyl.

[0013] (R 1 ) R 1 The terms independently represent a hydrogen atom, an aryl group with 6 to 20 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, or an alkyl group with 1 to 40 carbon atoms. Aryls with 6 to 20 carbon atoms and cycloalkyls with 5 to 6 carbon atoms are R 0 The same examples as those explained earlier can be cited. Examples of arylalkyls having 7 to 40 carbon atoms include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, and 5-phenylpentyl. Examples of alkyl groups having 1 to 40 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl, iso-pentyl, tert-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl, and octadecyl. In the aryl group having 6 to 20 carbon atoms, the cycloalkyl group having 5 to 6 carbon atoms, and the aryl group having 7 to 40 carbon atoms, any hydrogen atom of the aryl group may be independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the alkyl group having 7 to 40 carbon atoms, any hydrogen atom of the alkyl group may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or a cycloalkylene group having 5 to 20 carbon atoms. In the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a cycloalkylene group having 5 to 20 carbon atoms. R 1 The element is preferably selected from a hydrogen atom, phenyl, cyclohexyl, and alkyl groups having 1 to 5 carbon atoms, and more preferably selected from alkyl groups having 1 to 5 carbon atoms.

[0014] (R 2 , R 3 ) R 2 and R 3 Each of these independently represents an aryl group with 6 to 20 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, or an alkyl group with 1 to 40 carbon atoms. Aryls with 6 to 20 carbon atoms and cycloalkyls with 5 to 6 carbon atoms are R 0 What was explained above Similar examples can be given. As for arylalkyls with 7 to 40 carbon atoms, R 1 The same examples as those explained earlier can be cited. Examples of alkyl groups with 1 to 40 carbon atoms include R 1 The same examples as those explained earlier can be cited. In the aryl group having 6 to 20 carbon atoms, the cycloalkyl group having 5 to 6 carbon atoms, and the aryl group having 7 to 40 carbon atoms, any hydrogen atom of the aryl group may be independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the alkyl group having 7 to 40 carbon atoms, any hydrogen atom of the alkyl group may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or a cycloalkylene group having 5 to 20 carbon atoms. In the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a cycloalkylene group having 5 to 20 carbon atoms. R 2 The alkyl group is preferably selected from phenyl, cyclohexyl, and alkyl groups having 1 to 5 carbon atoms, and more preferably selected from alkyl groups having 1 to 5 carbon atoms. R 3 The alkyl group is preferably selected from phenyl, cyclohexyl, and alkyl groups having 1 to 5 carbon atoms, and more preferably selected from alkyl groups having 1 to 5 carbon atoms.

[0015] (p, x, y1, y2) In the repeating unit represented by equation (1), p represents a real number greater than or equal to 1; x represents a real number between 1 and 30; y1 + y2 represents a real number between 1 and 30, and y2 is greater than or equal to 0 and less than 30. By adjusting p, x, y1, and y2, the physical properties of the crosslinked material obtained by crosslinking the siloxane polymer of the present invention can be controlled. p represents a real number greater than or equal to 1. From the viewpoint of manufacturing and handling, p is preferably 20 or less, more preferably 8 or less. From the viewpoint of facilitating the manufacturing and handling of the crosslinked product obtained by crosslinking siloxane polymers, p is 1 or greater, preferably 4 or less, more preferably 2 or less. x represents a real number between 1 and 30. From the viewpoint of manufacturing and handling, x is preferably 20 or less, more preferably 8 or less. If the glass transition temperature of the crosslinked body obtained by crosslinking siloxane polymers is to be higher, it is preferably 1 or higher, more preferably 2 or higher, preferably 4 or less, and more preferably 3 or less. Also, if the crosslink density is to be higher, it is preferably 2 or higher, more preferably 4 or higher. y1+y2 represents a real number between 1 and 30, and y2 is between 0 and less than 30. From the viewpoint of manufacturing and handling, y1+y2 is preferably 20 or less, more preferably 8 or less. As described later, the siloxane polymer of the present invention can be manufactured by converting hydrosilyl groups to silanol groups. Therefore, by adjusting the conversion ratio of hydrosilyl groups to silanol groups, the glass transition temperature, crosslink density, thermal expansion coefficient, viscoelasticity, mechanical properties, etc., can be controlled. When all hydrosilyl groups are converted to silanol groups, y2=0. To increase the glass transition temperature and crosslink density of the crosslinked body obtained by crosslinking the siloxane polymer, it is preferable to increase y1, i.e., the proportion of silanol groups, and y1 is preferably 1 or more, more preferably 2 or more. Here, in the siloxane polymer according to one embodiment of the present invention, the repeating unit represented by formula (1) is not limited to one type, but may include multiple different repeating units. The synthesis method of the siloxane polymer described later is equilibrium polymerization, and p, x, y1, and y2 are expressed as average values. If p is 1, the values ​​of x and y1+y2 may be expressed as decimals. The ratio of x and y1+y2 can be controlled by the raw material charging ratio during polymerization in the manufacturing method described later. For example, in the examples described later, if you want to increase the silsesquioxane units, you should charge more compound α, and if you want to increase the chain-like siloxane units, you should charge more D4 or D'4. In addition, the ratio of x and y1+y2 can be controlled by the concentration of the reaction solution, the concentration and type of catalyst, the temperature conditions, and the reaction time. Furthermore, an increase in silsesquioxane units (p) makes the crosslinked material harder, but Too many rusesquioxane units make the crosslinked material brittle. On the other hand, increasing the number of linear siloxane units (x, y1, y2) increases flexibility, resulting in a flexible crosslinked material. However, too many linear siloxane units can also cause the surface of the crosslinked material to become sticky and reduce its strength.

[0016] The ends of the siloxane polymer containing the repeating unit represented by formula (1) according to the present invention are not particularly limited. Furthermore, in the siloxane polymer of the present invention, the mass % occupied by the repeating unit represented by formula (1) is usually 10% or more, preferably 30% or more, more preferably 50% or more, particularly preferably 70% or more, and usually less than 100%, preferably 99% or less. That is, units other than the repeating unit represented by formula (1) may be included in a range that does not significantly impair the effects of the present invention. Examples of such units include -(CH2-CH2)-, -(CH=CH)-, and -(O-SiMe2-C6H4-SiMe2)-. The weight-average molecular weight (Mw) of the siloxane polymer containing the repeating unit represented by formula (1) according to the present invention is not particularly limited, but is preferably 2,000 or more, more preferably 10,000 or more, preferably 10,000,000 or less, and more preferably 1,000,000 or less. The weight-average molecular weight is determined by calculating the chromatogram obtained by gel permeation chromatography (GPC) using a calibration curve obtained with molecular weight standard samples, as described in the examples below.

[0017] 2. Method for producing siloxane polymers A siloxane polymer containing a repeating unit represented by formula (1) according to one embodiment of the present invention is obtained by reacting a silsesquioxane compound with a compound containing a linear siloxane structure to produce a siloxane polymer containing a repeating unit represented by formula (1') having a hydroxyl group in the main chain, and converting the hydrosilyl group of the siloxane polymer containing the repeating unit represented by formula (1') to a silanol group, for example, in the presence of a transition metal catalyst. [ka] In the above equation (1'), R 0 ~R 3 p, x, y1, and y2 are R in equation (1), respectively. 0 ~R 3 These correspond to p, x, y1, and y2.

[0018] The method for producing the siloxane polymer represented by formula (1') is not particularly limited, but it can be suitably produced by a manufacturing method including, for example, the following steps (I) or (II). ru. (I): A compound represented by formula (a), a compound represented by formula (b), and a compound represented by formula (c) A process of reacting a compound with another compound. (II): A step of reacting a silicon compound represented by formula (a) with a silicon compound represented by formula (b) and a compound represented by formula (d) having a hydrosilyl group. Furthermore, in step (I) or (II) above, the compound represented by formula (e) is added and reacted. The ends may be sealed by doing so. In step (I) or step (II) above, tetrahydrofuran, toluene, ethyl acetate Solvents such as sulfuric acid may be used. It is preferable to carry out the reaction in the presence of an acid such as sulfuric acid. It is also preferable to carry out the reaction under an inert atmosphere such as nitrogen (N2). Furthermore, it is preferable to carry out the reaction while stirring.

[0019] [ka]

[0020] (The compound represented by formula (a)) In siloxane polymers, the silsesquioxane units originate from the compound represented by formula (a). [ka] In the above formula, R 0R independently represents an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, and in the aryl group having 6 to 20 carbon atoms and the cycloalkyl group having 5 to 6 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms; 1 Each of the following independently represents a hydrogen atom, a carbon-6 to carbon-20 aryl group, a carbon-5 to carbon-6 cycloalkyl group, a carbon-7 to carbon-40 arylalkyl group, or a carbon-1 to carbon-40 alkyl group. In the carbon-6 to carbon-20 aryl group, the carbon-5 to carbon-6 cycloalkyl group, and the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom may be independently replaced by a fluorine atom or a carbon-1 to carbon-20 alkyl group. In the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or a carbon-5 to carbon-20 cycloalkylene group. In the carbon-1 to carbon-40 alkyl group, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a carbon-5 to carbon-20 cycloalkylene group. Specific R 0 , R 1 (R) 0 ), (R 1 Examples include those explained in the section on ). The compound represented by formula (a) can be synthesized, for example, by referring to the description in Japanese Patent Publication No. 2006-022207, and the compounds shown below are preferred.

[0021] [ka]

[0022] (The compound represented by formula (b)) The compound represented by formula (b) can be used to introduce chain-like siloxane units into a siloxane polymer. [ka] In the above formula, R 2Independently, represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. In the aryl groups having 6 to 20 carbon atoms, the cycloalkyl groups having 5 to 6 carbon atoms, and the aryl groups having 7 to 40 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the alkyl groups having 7 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a cycloalkylene group having 5 to 20 carbon atoms. 'a' represents an integer between 3 and 30. From the viewpoint of producing siloxane polymers, it is preferably between 3 and 20, and more preferably between 3 and 10. Specific R 2 (R) 2 , R 3 Examples include those described in the section on ). The same applies to preferred embodiments. Examples of compounds represented by formula (b) include 2,2,4,4,6,6-hexamethyl. Cyclotrisiloxane, 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane, 2,2,4,4,6,6-hexaethylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-triethyl-2,4,6-tripropylcyclotrisiloxane, 2,2,4,4,6,6-hexapropylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris(1-methylethyl)cyclotrisiloxane, 2,4,6-triethyl-2,4,6-tris(1-methylethyl)cyclo Trisiloxane 2,2,4,4,6,6-Hexakis(1-methylethyl)cyclotrisiloxane, 2,4,6-Tributyl-2,4,6-Trimethylcyclotrisiloxane, 2,4,6-Tributyl-2,4,6-Triethylcyclotrisiloxane, 2,2,4,4,6,6-Hexabutylcyclotrisiloxane, 2,4,6-Trimethyl-2,4,6-Tris(1,1-dimethylethyl)cyclotrisiloxane, 2,46-Triethyl-2,4,6-Tris(1,1-dimethylethyl)cyclotrisiloxane, 2,4,6-Tris(1,1-dimethylethyl) (Tyl)-2,4,6-tripropylcyclotrisiloxane, 2,2,4,4,66-hexakis(1,1-dimethylethyl)cyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris(trifluoromethyl)cyclotrisiloxane, 2,2,4,4,6,6-hexakis(trifluoromethyl)cyclotrisiloxane, 2,2,4,4,6,6-hexakis(1,1,2,2,2-pentafluoroethyl)cyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 2 ,2,4,4,6,6-Hexakis(3,3,3-trifluoropropyl)cyclotrisiloxane, 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane, 2,2,4,4,6,6-Hexaphenylcyclotrisiloxane, 2,4,6-Tricyclohexyl-2,4,6-trimethylcyclotrisiloxane, 2,2,4,4,6,6-Hexacyclohexylcyclotrisiloxane, 2,2,4,4,6,6-Hexavinylcyclotrisiloxane, 2,4,6-Trimethyl-2,4,6-Trivinylcyclotrisiloxane, 2,2,4,4,6,6,8,8-Octamethylcyclotetrasiloxane, 2,4,6,8-Tetraethyl-2,4,6,8-Tetramethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-Octaethylcyclotrisiloxane, 2,4,6,8-Tetramethyl-2,4,6,8-Tetrapropylcyclotetrasiloxane, 2,4,6,8-Tetraethyl-2,4,6,8-Tetrapropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-Octapropylcyclotetrasiloxane, 2,4,6,8-Tetramethyl-2,4,6,8-Tetramethyl( 1-Methylethyl)cyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetrakis(1-methylethyl)cyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis(1-methylethyl)cyclotetrasiloxane, 2,4,6,8-tetrabutyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetrabutyl-2,4,6,8-tetraethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octabutylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6, 8-Tetrakis(1,1-dimethylethyl)cyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetrakis(1,1-dimethylethyl)cyclotetrasiloxane, 2,4,6,8-tetrakis(1,1-dimethylethyl)-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis(1,1-dimethylethyl)cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(trifluoromethyl)cyclotetrasiloxane, 2,2,4,4,6,6,8, 8-Octakis(trifluoromethyl)cyclotetrasiloxane, 2,2,4,4,6,6,8,8-Octakis(1,1,2,2,2-pentafluoroethyl)cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3,3,3-trifluoropropyl)cyclotetrasiloxane, 2,2,4,4,6,6,8,8-Octakis(3,3,3-trifluoropropyl)cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-Octaphenylcyclotetrasiloxane, 2,4,6,8-Tetracyclohexyl-2,4,6,8-Tetramethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-Octacyclohexylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-Octavinylcyclotetrasiloxane, 2,4,6,8-Tetramethyl-2,4,6,8-Tetravinylcyclotetrasiloxane Xane, 2,6-diethynyl-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8,10,10-decamethylcyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8,10-pentamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,8,10,10-decaethylcyclotrisiloxane, 2,4,6,8.10-Pentamethyl-2,4,6,8-Pentapropylcyclopentasiloxane, 2,4,6,8,10-Pentaethyl-2,4,6,8,10-Pentapropylcyclopentasiloxane, 2,2,4,4,6,6,8,8,8,10,10-Decapropylcyclopentasiloxane, 2,4,6,8,10-Pentamethyl-2,4,6,8,10-Pentakis(1-Methylethyl)cyclopentasiloxane, 2,4,6,8,10-Pentaethyl-2,4,6,8,10-Pentakis(1-methylethyl)cyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-Dekakis(1-methylethyl)cyclopentasiloxane, 2,4,6,8,10-Pentabutyl-2,4,6,8,10-Pentamethylcyclopentasiloxane, 2,4,6,8,10-Pentabutyl-2,4,6,8,10-Pentabutyl Taethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-Decabutylcyclopentasiloxane, 2,4,6,8,10,10-Pentamethyl-2,4,6,8,10,10-Pentakis(1,1-dimethylethyl)cyclopentasiloxane, 2,4,6,8,10-Pentaethyl-2,4,6,8,10-Pentakis(1,1-dimethylethyl)cyclopentasiloxane, 2, 4,6,8,10-Pentakis(1,1-dimethylethyl)-2,4,6,8,10-Pentapropylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-Dekakis(1,1-dimethylethyl)cyclopentasiloxane, 2,4,6,8,10-Pentamethyl-2,4,6,8-Pentakis(trifluoromethyl)cyclopentasiloxane, 2,2,4,4,6,6,8,8,10.10-Dekakis(trifluoromethyl)cyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-Dekakis(1,1,2,2,2-pentafluoroethyl)cyclopentasiloxane, 2,4,6,8,10,10-pentamethyl-2,4,6,8-pentakis(3,3,3-trifluoropropyl)cyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-Dekakis(3,3,3-trifluoropropyl)cyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8-pentaphenyl Examples include cyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decaphenylcyclopentasiloxane, 2,4,6,8,10-pentacyclohexyl-2,4,6,8,10-pentamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decacyclohexylcyclopentasiloxane, 2,2,4,4,6,6,8,8,8,10,10-decavinylcyclopentasiloxane, and 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinylcyclopentasiloxane, among which R. 2 Low molecular weight cyclic siloxanes in which the atom is an alkyl group having 1 to 40 carbon atoms are preferred, and cyclic siloxanes such as hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are more preferred, with octamethylcyclotetrasiloxane being particularly preferred from the viewpoint of availability, cost, and handling.

[0023] (The compound represented by formula (c)) A hydrosilyl group can be introduced into the siloxane polymer (1') using the compound represented by formula (c). [ka] In formula (c), R 3Each of the following independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms; in the aryl groups having 6 to 20 carbon atoms, the cycloalkyl groups having 5 to 6 carbon atoms, and the aryl groups having 7 to 40 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms; in the aryl groups having 7 to 40 carbon atoms, the alkyl groups may have any hydrogen atom independently replaced by a fluorine atom, and any -CH2- may have any -O-, -CH=CH-, or a cycloalkylene group having 5 to 20 carbon atoms; in the alkyl groups having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may have any -O- or a cycloalkylene group having 5 to 20 carbon atoms; b represents an integer between 1 and 40. R 3 (R) 2 , R 3 The same explanation as in the section for ) applies. Examples of compounds represented by formula (c) include 2,4,6-trimethylcyclotrisiloxane, 2,4,6-triethylcyclotrisiloxane, 2,4,6-tris(1-methylethyl)cyclotrisiloxane, tripropylcyclotrisiloxane, 2,4,6-tris(1,1-dimethylethyl)cyclotrisiloxane, 2,4,6-tris(1,1-dimethylethyl)cyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, and 2,4,6,8,10-pentaethylcyclopentasiloxane.

[0024] (The compound represented by formula (d)) For example, a hydrosilyl group can be introduced into the siloxane polymer (1') using the compound represented by formula (d). [ka] In formula (d), R 2 , R3 and R 4 Each of the following independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms; in the aryl groups having 6 to 20 carbon atoms, the cycloalkyl groups having 5 to 6 carbon atoms, and the aryl groups having 7 to 40 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms; in the aryl groups having 7 to 40 carbon atoms, the alkyl groups may have any hydrogen atom independently replaced by a fluorine atom, and any -CH2- may have any -O-, -CH=CH-, or a cycloalkylene group having 5 to 20 carbon atoms; in the alkyl groups having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may have any -O- or a cycloalkylene group having 5 to 20 carbon atoms; c and d represent integers between 1 and 40. R 2 , R 3 and R 4 (R) 2 , R 3 The same explanation as in the section for ) applies. Examples of compounds represented by formula (d) include 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,5,7,7,7-nonamethyltetrasiloxane, 1,1,1,3,5,5,5-heptaphenyltrisiloxane, 1,1,1,3,5,5,7,7,7-nonaphenyltetrasiloxane, Gelest HMS-031, HMS-071, HMS-151, HMS-301, HMS-501, HAM-301, and (when d=1): Gelest HMS-991, HMS-992, HMS-993.

[0025] (The compound represented by formula (e)) The ends of the siloxane polymer (1) can be encapsulated using the compound represented by formula (e). [ka] In formula (e), R2 and R 4 Each of these independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. In the aryl groups having 6 to 20 carbon atoms, the cycloalkyl groups having 5 to 6 carbon atoms, and the aryl groups having 7 to 40 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the arylalkyl groups having 7 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a cycloalkylene group having 5 to 20 carbon atoms. In the alkyl groups having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or a cycloalkylene group having 5 to 20 carbon atoms. e represents an integer between 1 and 1000. R 2 and R 4 (R) 2 , R 3 The same explanation as in the section for ) applies. Examples of compounds represented by formula (e) include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexaphenyldisiloxane, octaphenyltrisiloxane, decaphenyltetrasiloxane, and Gelest DMA-T07R.

[0026] (A process of converting hydrosilyl groups in a siloxane polymer containing repeating units represented by formula (1') to silanol groups.) A method for producing a siloxane polymer containing a repeating unit represented by formula (1), comprising the step of converting the hydrosilyl groups of the siloxane polymer containing the repeating unit represented by formula (1') to silanol groups in the presence of a transition metal catalyst, is also an embodiment of the present invention. This process converts all or some of the hydrogen atoms of the hydrosilyl groups into hydroxyl groups, yielding a siloxane polymer containing repeating units represented by formula (1) that include silanol groups. When all hydrosilyl groups are converted into silanol groups, y² = 0 in the siloxane polymer containing repeating units represented by formula (1). The conversion rate of hydrosilyl groups to silanol groups can be controlled, for example, by adjusting the time, solution concentration, and catalyst concentration of this process. In this process, for example, the hydrosilyl groups of a siloxane polymer containing repeating units represented by formula (1') are converted to silanol groups as follows: The siloxane polymer containing repeating units represented by formula (1') containing hydrosilyl groups is dissolved in a solvent and added dropwise to a mixture of solvent, water, and catalyst while stirring. After hydrogen generation is complete, the reaction mixture is aged. Then, the catalyst is removed using a filter aid, etc., an organic solvent such as ethyl acetate is added, the mixture is separated, and the organic layer is dried with sodium sulfate. Next, the sodium sulfate is removed, the solution is concentrated under reduced pressure, reprecipitation is performed with heptane, and the resulting precipitate is vacuum dried to obtain the target product. Examples of transition metal catalysts include palladium catalysts, platinum catalysts, rhodium catalysts, ruthenium catalysts, copper catalysts, and rhenium catalysts, with palladium catalysts being preferred. Examples of palladium catalysts include palladium hydroxide / carbon catalysts and palladium / carbon catalysts, with palladium hydroxide / carbon catalysts being preferred from the viewpoint of reaction efficiency. The amount of catalyst is not particularly limited, but from the viewpoint of reactivity and yield, 1 to 30 mol% relative to the substrate is preferred. The reaction solvent used in this process is not particularly limited as long as it is a solvent that does not participate in the reaction. Examples include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate and ethyl acetate; and ether solvents such as THF, diethyl ether, and cyclopentyl methyl ether. Among these, solvents that are miscible with water are preferred, and THF is particularly preferred. The amount of solvent used is not particularly limited, but from the viewpoint of reactivity and workability, it is preferable to use it so that the solid content concentration (solid content concentration = 100 × weight of non-solvent substances / total weight of reaction solution) is 1% by mass or more and 50% by mass or less. The amount of water to be added is not particularly limited, but from the viewpoint of miscibility with the solvent, it is preferable to add 1% to 15% by mass relative to the solvent. The reaction time is not particularly limited, but if the reaction time is too long, condensation of silanol groups (-SiOH) may occur, or an exchange reaction of H and OH may occur between the hydrosilyl group (SiH) and the silanol group (SiOH). Therefore, from the viewpoint of ensuring yield and preventing the formation of high molecular weight, the reaction time is preferably 15 minutes to 24 hours. The reaction temperature is not particularly limited, but is preferably 1°C or higher, more preferably 5°C or higher, preferably 50°C or lower, and more preferably 40°C or lower. Specifically, in this process, for example, a siloxane polymer containing repeating units represented by formula (1') including hydrosilyl groups is stirred in a mixed solvent of tetrahydrofuran and water using a palladium hydroxide / carbon catalyst under an inert atmosphere, thereby converting all or some of the hydrogens of the hydrosilyl groups to hydroxyl groups, and a siloxane polymer containing repeating units represented by formula (1) including silanol groups can be obtained.

[0027] 3.Crosslinked body A crosslinked body according to one embodiment of the present invention is a crosslinked body obtained by crosslinking a siloxane polymer containing repeating units represented by the above formula (1) (hereinafter also referred to as "the crosslinked body of the present invention"). The crosslinked body of the present invention will be described below.

[0028] 3.1 Method for manufacturing crosslinked material A method for producing a crosslinked siloxane polymer containing repeating units represented by formula (1) according to one embodiment of the present invention (hereinafter also referred to as "the method for producing a crosslinked siloxane polymer of the present invention") is not particularly limited as long as it is a method in which a crosslinked silanol group of a siloxane polymer containing repeating units represented by formula (1) is crosslinked to obtain a crosslinked siloxane polymer, but it is preferable that it includes a heat treatment step. Such a production method includes, for example, preparing a siloxane polymer composition containing a siloxane polymer containing repeating units represented by formula (1), a crosslinking agent and a catalyst, coating the siloxane polymer composition onto a substrate, and heating to crosslink it. More specifically, a siloxane polymer containing repeating units represented by formula (1) is dissolved in a solvent such as toluene, a crosslinking agent and a catalyst are added thereto, and the mixture is stirred to prepare a siloxane polymer composition. After degassing the siloxane polymer composition, it is coated onto a substrate and heated in an oven at 70°C for 20 minutes, 100°C for 1 hour, and 200°C for 2 hours. After cooling, the film formed on the substrate is peeled off and crosslinked. The body can be obtained as a self-supporting membrane (film).

[0029] (Siloxane polymer composition) The present invention provides a method for producing a crosslinked material that preferably involves preparing and using a siloxane polymer composition (hereinafter also referred to as "siloxane polymer composition") containing a siloxane polymer with repeating units represented by formula (1), a crosslinking agent, and a catalyst. The siloxane polymer composition may contain a solvent. The composition can be prepared by mixing a siloxane polymer with repeating units represented by formula (1), a crosslinking agent, and a catalyst. For example, a siloxane polymer with repeating units represented by formula (1) can be dissolved in a solvent, a crosslinking agent and a catalyst can be added thereto, and the mixture can be stirred to obtain a solution that is the siloxane polymer composition. From the viewpoint of uniformity of the resulting crosslinked material, it is preferable to degas the siloxane polymer composition before applying it to a coating.

[0030] (Crosslinking agent) The crosslinking agent used in this embodiment is not particularly limited as long as it reacts with a silanol group, but from the viewpoint of handling and availability, a siloxane compound containing an alkoxysilyl group is preferred. Examples of crosslinking agents include methyl silicate, ethyl silicate, and mixtures of methyl silicate and ethyl silicate. Methyl silicate is represented by the following formula. [ka] In the above formula, m is 2 to 100, preferably 2 to 50, more preferably 4 to 10, and even more preferably 4 to 5. Examples of commercially available products include MKC® Silicate MS51, MS56, MS57, MS56S (manufactured by Mitsubishi Chemical Corporation); Ethyl Silicate 28, Ethyl Silicate 40, Ethyl Silicate 48, EMS-485, Methyl Silicate 51, and Methyl Silicate 53 (manufactured by Colcoat Co., Ltd.). One type of crosslinking agent may be used, or two or more types may be used. The amount of crosslinking agent added is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, relative to the siloxane polymer, and usually 20% by mass or less, preferably 10% by mass or less, and even more preferably 5% by mass or less. When two or more crosslinking agents are used, it is preferable that the total content is within the above range.

[0031] (catalyst) The catalyst used in this embodiment may be appropriately selected depending on the crosslinking agent. For example, when a siloxane compound containing an alkoxysilyl group is used as the crosslinking agent, organometallic compounds containing metals such as tin, titanium, zirconium, zinc, and bismuth; acidic compounds; basic compounds, etc., can be used. Examples of such metal compounds include organotin catalysts such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxide, and tin octanoate; and alkoxytitanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and titanium tetraacetylacetonate. Examples of acidic compounds include phosphoric acid, toluenesulfonic acid, sulfuric acid, nitric acid, acetic acid, and ammonium compounds. A prime example is fuzzy acid. Examples of basic compounds include triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]nona-5-ene, 1,8-diazabicyclo[5.4.0]unde-7-ene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, and N-ethylmorpholinine. One type of catalyst may be used, or two or more types may be used. The amount of catalyst added is typically 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and typically 10% by mass or less, preferably 5% by mass or less, and even more preferably 3% by mass or less, relative to the siloxane polymer. When two or more catalysts are used, it is preferable that the total content be within the above range.

[0032] (solvent) The siloxane polymer composition used in this embodiment may contain a solvent. From the viewpoint of handling the siloxane polymer composition, it is preferable to adjust the viscosity of the siloxane polymer composition using a solvent. The solvent used in the siloxane polymer composition is not particularly limited as long as it can dissolve the siloxane polymer containing the repeating unit represented by formula (1). Preferred solvents include hydrocarbon solvents such as butane, hexane, heptane, octane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and anisole; ether solvents such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran (THF), and dioxane; halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride; ester solvents such as ethyl acetate; glycol ester solvents such as propylene glycol monomethyl ether acetate (PGMEA); nitrogen-containing solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and pyridine; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and ketone solvents such as acetone and methyl ethyl ketone. Preferably, the solvents are toluene, mesitylene, anisole, tetrahydrofuran, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, and 2-(2-ethoxyethoxy)ethyl acetate, and more preferably toluene and propylene glycol monomethyl ether acetate (PGMEA). One solvent may be used, or two or more solvents may be used. The solvent may also be dehydrated before use. The amount of solvent used is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more, and usually 1000% by mass or less, preferably 500% by mass or less, relative to the siloxane polymer containing the repeating unit represented by formula (1).

[0033] (Heating process) A method for crosslinking a siloxane polymer containing repeating units represented by formula (1) is heat treatment. The heat treatment process can be carried out by coating the substrate with the siloxane polymer composition and then heating it using an oven or the like. The temperature and time of the heat treatment process are not particularly limited as long as the siloxane polymer containing the repeating units represented by formula (1) can be converted into the desired crosslinked body. The siloxane polymer crosslinked and cured by the heat treatment can be peeled off the substrate as a film-like crosslinked body after cooling. The substrate is not particularly limited as long as it can withstand the temperature of the heat treatment process and the crosslinked body formed on the substrate can be peeled off the substrate and removed as a self-supporting film. Examples include glass substrates such as quartz, barium borosilicate glass, and aluminoborosilicate glass; calcium fluoride substrates; metal oxide substrates such as ITO (indium tin oxide); ceramic substrates; polycarbonate (PC) films, silicone films, and polyethylene terephthalate (PET) films. Plastic films such as aluminum, polyethylene naphthalate (PEN) film, cycloolefin polymer (COP) film, polypropylene film, polyethylene film, acrylic polymer film, polyvinyl alcohol film, triacetylcellulose film, and polyimide (PI) film; fluororesin substrates such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA); laminated substrates coated with fluororesin on glass, etc.; and metal substrates such as SUS and copper can be used.

[0034] 3.2 Physical properties of the bridged structure A crosslinked material obtained by crosslinking a siloxane polymer containing repeating units represented by formula (1) has a lower coefficient of thermal expansion, a higher crosslink density, and a higher glass transition temperature (Tg) compared to a siloxane polymer that does not contain silanol groups.

[0035] 3.2.1 Glass transition temperature In dynamic viscoelasticity measurements using DMA, the temperature at the peak top of the loss modulus (E) is used. The crosslinked material of this embodiment preferably has a glass transition temperature of 0°C or higher, and more preferably 30°C or higher. Dynamic viscoelasticity measurements using DMA can be performed using, for example, the Hitachi High-Tech Science DMS6100 under the following measurement conditions. 1℃ / min, sample area 10mm x 1mm Load 10mN, measurement frequency 10 Hz

[0036] 3.2.2 Crosslink density Generally, the storage modulus of the rubbery, flat region of a crosslinked polymer increases with increasing crosslink density. This phenomenon allows us to approximate the apparent crosslink density n from the storage modulus of the rubbery, flat region using the following equation. n≒E' / 3RT n: Crosslink density (mol / m 3 E': Storage modulus (Pa), R: Gas constant ((Pa·m)) 3 ) / (K mol)), T: temperature (K) From the viewpoint of heat resistance, siloxane polymer films with a high crosslink density are required. The crosslinked material of this embodiment has a crosslink density n of 150 mol / m², which can be determined from the above formula (α). 3 Preferably, it is 250 mol / m² or higher. 3 This is preferable.

[0037] 3.2.3 Coefficient of linear expansion (CTE) The coefficient of linear expansion is measured by thermomechanical analysis (TMA). In the crosslinked body of this embodiment having repeating units represented by equation (1), the maximum value of the coefficient of linear expansion calculated in the range from 50°C to 180°C in 10°C increments (i.e., 50°C to 60°C, 60°C to 70°C, 70°C to 80°C, 80°C to 90°C, 90°C to 100°C, 100°C to 110°C, 110°C to 120°C, 120°C to 130°C, 130°C to 140°C, 140°C to 150°C) in the first scan (first heating, heating rate: 5°C / min) in the temperature range of 50°C to 180°C is preferably less than 200 ppm / K, and more preferably 190 ppm / K or less. The coefficient of thermal expansion using TMA can be measured using, for example, the Hitachi High-Tech Science SS / TMA6100 under the following measurement conditions. Tensile mode, 5°C / min, length 20 mm, cross-sectional area 0.3 mm² 2 Load 9.8 mN [Examples]

[0038] The present invention will be described in more detail below with reference to examples, but this description will not limit the scope of the present invention.

[0039] The reagents used in the examples are shown below. Toluene (Special Grade): Manufactured by Fujifilm Wako Pure Chemical Corporation Toluene (super-dehydrated): Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Tetrahydrofuran (primary grade): Manufactured by Fujifilm Wako Pure Chemical Corporation D4 (Octamethylcyclotetrasiloxane): Manufactured by Tokyo Chemical Industry Co., Ltd. D'4 (2,4,6,8-tetramethylcyclotetrasiloxane): Manufactured by Tokyo Chemical Industry Co., Ltd. Kyoward (registered trademark) 500 SN (synthetic hydrotalcite): Manufactured by Kyowa Chemical Industry Co., Ltd. Heptane (first grade): Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Ethyl acetate (super-dehydrated): Manufactured by Fujifilm Wako Pure Chemical Corporation Sulfuric acid (special grade): Manufactured by Kanto Chemical Co., Ltd. Palladium hydroxide / carbon (approximately 50% water-moistened): Manufactured by Tokyo Chemical Industry Co., Ltd. Sodium sulfate (anhydrous): Fujifilm Wako Pure Chemical Corporation MKC (Registered Trademark) Silicate MS51: Manufactured by Mitsubishi Chemical Corporation Dibutyltin didilaureate (DBTL): Manufactured by Tokyo Chemical Industry Co., Ltd. PDMS: Gelest DMS-S42 [ka] Compound (α) was synthesized by reacting the following compounds (4) and (5), followed by hydrolysis (see, for example, paragraph 0032 of Japanese Patent Publication No. 2006-022207). [ka]

[0040] GPC Gel Permeation Chromatography <Measurement conditions> Column: Showa Denko Co., Ltd. Shodex KF-804L 300 x 8.0 mm Showa Denko Corporation Shodex KF-805L 300 x 8.0 mm, 2 in series. Mobile phase: THF Flow rate: 1.0ml / min Temperature: 40℃ Detector: RI Molecular weight standard sample: Polymethyl methacrylate resin (PMMA) with known molecular weight

[0041] DMA Dynamic Viscoelasticity Measurement <Measurement conditions> Hitachi High-Tech Science DMS6100 1℃ / min, sample area 10mm x 1mm Load 10mN, measurement frequency 10 Hz

[0042] TMA thermomechanical analysis <Measurement conditions> Hitachi High-Tech Science SS / TMA6100 Tensile mode, 5°C / min, length 20 mm, cross-sectional area 0.3 mm² 2 Load 9.8 mN

[0043] [Synthesis Example 1] [ka]

[0044] Add 50g of compound (α), 15.6g of D4, 2.54g of D', and 104.6g of toluene to a 500 mL four-necked round-bottom flask, and use a thermometer, reflux condenser, mechanical stirrer, and toluene. A Luvas was set up and nitrogen was flowed through it. 1.6 g of sulfuric acid was added while stirring. After stirring at reflux temperature for about 1 hour, it was allowed to cool to below 80°C and aged at 80°C for 3 hours. Heating and stirring were stopped, water was added, and the reaction solution was washed several times with water. Acid was removed by treatment with Kyoward 500, and after filtration, the filtrate was concentrated at 50°C. The concentrated filtrate was reprecipitated with heptane, and the precipitate was vacuum dried to obtain 44.6 g of a white solid (A). The molecular weight was measured by GPC, and the weight-average molecular weight Mw was 123,000, and the polydispersity Mw / Mn = 3.8. 1 SiH The existence of the base was confirmed. 29 The average values ​​of (x, x') and (y, y') obtained by Si-NMR measurement were 3.1 and 1.0, respectively. ( 1 H-NMR results) 1 H-NMR(400MHz, CO(CD3)2)δ: 7.18~7.66(Ph), 4.77~4.86(Si-H), 0.28~0.43(O3SiMe), -0.02~0.13(O2SiMe2). ( 29 Si-NMR results) 29 Si-NMR(99MHz, THF-d8)δ: 7.35~10.1( Me3 M 1 ), -18.3~-21.9( Me2 D 2 ), -34.8~-36.2( H,Me D 2 ) -64.0 to -65.2 ( Me T 3 ), -78.7~-79.9( Ph T 3 ).

[0045] [Example 1-1] [ka]

[0046] Add 34 mL of THF, 7 mL of pure water, and 69 mg of palladium hydroxide / carbon to a 50 mL three-neck round-bottom flask, set a thermometer, stir with a magnetic stirrer, and flow nitrogen. Dropwise add a 20 mL solution of 10 g of polymer (A) in THF and stir overnight at room temperature. Add ethyl acetate to the reaction solution and filter the palladium hydroxide / carbon using celite. After liquid separation, dry the organic layer with sodium sulfate and concentrate it under reduced pressure. After reprecipitation with heptane, dry the precipitate under vacuum to obtain 9.8 g of a white solid (B). The molecular weight was measured by GPC, and the weight average molecular weight Mw was 113,600, and the polydispersity Mw / Mn = 3.5. From the appearance of the signal of the SiOH group by 1H-NMR, 1 From the appearance of the signal of 29 D H,Me at around -35 ppm by 29Si-NMR measurement, it was confirmed that the conversion rate from SiH to SiOH was 25%. 2 ( ( 1 1H-NMR measurement results) 1 1H-NMR (400 MHz, CO(CD3)2) δ: 7.15~7.64 (Ph), 4.73~4.82 (Si-H), 6.27 (Si-OH, broad), 0.25~0.39 (O3SiMe), -0.04~0.12 (O2SiMe2). ( 29 29Si-NMR measurement results) 29 29Si-NMR (99 MHz, CO(CD3)2) δ: -17.8~-21.6 ( M e2 D 2 ), -34.3~-35.9 ( H,Me D 2 ), -55.5~-56.8 ( Me T 2 ), -63.5~-64.7 ( Me T 3 ), -78.4~-79.2 ( Ph T 3 ).

[0047] [Synthesis Example 2] We synthesized a siloxane polymer that lacks OH groups in its side chains and only has terminal OOH groups. [ka]

[0048] 20 g of compound (α), 47.5 g of D, and 44.4 g of toluene were added to a 200 mL four-necked round-bottom flask. A thermometer, reflux condenser, mechanical stirrer, and oil bath were set up, and nitrogen was flowed through. 2.07 g of sulfuric acid was added while stirring. After stirring at reflux temperature for 1 hour, the mixture was allowed to cool to 80°C and aged at 80°C for 4 hours. Heating and stirring were stopped, water was added, and the reaction solution was washed several times with water. Acid was removed by treatment with Kyoward 500, and after filtration, the filtrate was concentrated at approximately 50°C. The filtrate was reprecipitated with heptane, and then vacuum dried to obtain 10.3 g of white solid (C). The molecular weight was measured by GPC, and the weight-average molecular weight Mw was 30,000, with a polydispersity of Mw / Mn = 1.7. 1 The average value of (x,x') from the 1H-NMR spectrum was 3.9. ( 1 H-NMR measurement results) 1 H-NMR(400MHz, CO(CD3)2)δ: 7.11~7.63(Ph), 5.03~5.05(Si-OH), 0.25~0.38(O3SiMe), -0.07~0.12(O2SiMe2). ( 29 Si-NMR measurement results) 29 Si-NMR(99MHz, CO(CD3)2)δ: -12.2~-13.7( M e2 D 1 ), -18.1~-21.6( Me2 D 2 ), -55.1( Me T 2 ), -64.2~-64.7( Me T 3 ), -78.6~-79.3( Ph T 3 ).

[0049] [Example 2-1, Comparative Examples 2-1~2-2] Using the compositions listed in Table 1, polymer B obtained in Example 1-1, polymer C obtained in Synthesis Example 2, and polymer D, which is a commercially available PDMS, were each dissolved in dehydrated toluene. MS-51 and dibutyltin dilaurate were added, and the mixture was stirred to prepare the compositions of Example 2-1 and Comparative Examples 2-1 to 2-2. After degassing the obtained siloxane polymer compositions, the solutions were cast onto a substrate and heated and crosslinked in an oven at 70°C for 20 minutes, 100°C for 1 hour, and 200°C for 2 hours. After cooling, the film was peeled off the substrate to obtain the crosslinked body.

[0050] The following properties were determined: Glass transition temperature: In dynamic viscoelasticity measurements using DMA, the temperature at which the loss modulus (E) peaks. Apparent crosslink density: The apparent crosslink density was calculated from the storage modulus of the rubbery flat region using the following formula. n=E' / 3RT n: Crosslink density (mol / m 3 E': Storage modulus (Pa), R: Gas constant ((Pa·m)) 3 ) / (K mol)), T: temperature (K) Coefficient of linear expansion (CTE): Measured by TMA. The maximum value of the coefficient of thermal expansion calculated from the TMA results of the 1st scan (first heating, heating rate: 5°C / min) in the temperature range of 50°C to 180°C, in 10°C increments from 50°C to 180°C.

[0051] [Table 1]

[0052] By forming a film from a siloxane polymer having hydroxyl groups at the pendant position of the polymer using a crosslinking agent, it is possible to increase the glass transition temperature and apparent crosslink density compared to the comparative example, and significantly reduce the coefficient of thermal expansion. The coefficient of thermal expansion of silicone is usually higher than 200 ppm / K, so a lower coefficient means that expansion is suppressed more effectively than with ordinary silicone films. Therefore, when used as a substrate on which wiring is mounted, expansion can be suppressed even when heat is applied during the manufacturing process, preventing the wiring from breaking. [Industrial applicability]

[0053] The crosslinked material obtained by crosslinking the siloxane polymer according to the present invention has a low coefficient of thermal expansion and a high glass transition temperature, and is particularly suitable for use as an electronic component.

Claims

1. A siloxane polymer containing repeating units represented by formula (1) and having a weight-average molecular weight of 10,000 or more. 【Chemistry 1】 In the above formula, R ０ Each independently represents an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, wherein any hydrogen atom in the aryl group having 6 to 20 carbon atoms or the cycloalkyl group having 5 to 6 carbon atoms may be independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms; R １ Independently, each represents a hydrogen atom, a carbon-6 to carbon-20 aryl group, a carbon-5 to carbon-6 cycloalkyl group, a carbon-7 to carbon-40 arylalkyl group, or a carbon-1 to carbon-40 alkyl group. In the carbon-6 to carbon-20 aryl group, the carbon-5 to carbon-6 cycloalkyl group, and the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom may be independently replaced by a fluorine atom or a carbon-1 to carbon-20 alkyl group. In the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom may be replaced by a fluorine atom, and any -CH ２ The - group may be independently replaced by -O-, -CH=CH-, or a cycloalkylene having 5 to 20 carbon atoms, and in the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH ２ The - can be independently replaced by -O- or a cycloalkylene having 5 to 20 carbon atoms; R ２ and R ３ Each of these independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. In the aryl groups having 6 to 20 carbon atoms, the cycloalkyl groups having 5 to 6 carbon atoms, and the aryl groups having 7 to 40 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the alkylene groups having 7 to 40 carbon atoms, any hydrogen atom may be replaced by a fluorine atom, and any -CH ２ The - group may be independently replaced by -O-, -CH=CH-, or a cycloalkylene having 5 to 20 carbon atoms, and in the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH ２ The - can be independently replaced by -O- or a cycloalkylene having 5 to 20 carbon atoms; p represents a real number between 1 and 20; x represents a real number between 1 and 30; y1 + y2 represents a real number between 1 and 30, where y1 is 2 or greater and y2 is between 0 and 30 (inclusive).

2. A siloxane polymer composition comprising the siloxane polymer, crosslinking agent, and transition metal catalyst described in claim 1.

3. The siloxane polymer composition according to claim 2, which provides a crosslinked body in which the maximum value of the coefficient of linear expansion calculated in the range from 50°C to 180°C in 10°C increments is less than 200 ppm / K.

4. The siloxane polymer composition according to claim 2 or 3, which provides a crosslinked material having a glass transition temperature of 0°C or higher.

5. The crosslinked polymer having a crosslinking density n determined by the following formula (α) of 150 mol / m ３ or more, the siloxane polymer composition according to any one of claims 2 to 4. n=E' / 3RT...(α) n: crosslinking density (mol / m ３ ), E': Storage modulus (Pa), R: Gas constant ((Pa·m) ３ ) / (K mol)), T: temperature (K)

6. A crosslinked body obtained by crosslinking the siloxane polymer composition according to any one of claims 2 to 5.

7. The crosslinked body according to claim 6, wherein the maximum value of the coefficient of linear expansion calculated in the range from 50°C to 180°C in 10°C increments is less than 200 ppm / K.

8. The crosslinked body according to claim 6 or 7, wherein the glass transition temperature is 0°C or higher.

9. The crosslinking density n, calculated from the following formula (α), is 150 mol / m³. ３ The crosslinked body according to any one of claims 6 to 8. n=E' / 3RT...(α) n: crosslinking density (mol / m ３ ), E': Storage modulus (Pa), R: Gas constant ((Pa·m) ３ ) / (K mol)), T: temperature (K)

10. A method for producing a siloxane polymer containing a repeating unit represented by formula (1) and having a weight-average molecular weight of 10,000 or more, comprising the step of converting the hydrosilyl groups of a siloxane polymer containing a repeating unit represented by formula (1') to silanol groups in the presence of a transition metal catalyst. 【Chemistry 2】 In the above formula, R ０ Each independently represents an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, wherein any hydrogen atom in the aryl group having 6 to 20 carbon atoms or the cycloalkyl group having 5 to 6 carbon atoms may be independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms; R １ Independently, each represents a hydrogen atom, a carbon-6 to carbon-20 aryl group, a carbon-5 to carbon-6 cycloalkyl group, a carbon-7 to carbon-40 arylalkyl group, or a carbon-1 to carbon-40 alkyl group. In the carbon-6 to carbon-20 aryl group, the carbon-5 to carbon-6 cycloalkyl group, and the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom may be independently replaced by a fluorine atom or a carbon-1 to carbon-20 alkyl group. In the carbon-7 to carbon-40 arylalkyl group, any hydrogen atom may be replaced by a fluorine atom, and any -CH ２ The - group may be independently replaced by -O-, -CH=CH-, or a cycloalkylene having 5 to 20 carbon atoms, and in the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH ２ The - can be independently replaced by -O- or a cycloalkylene having 5 to 20 carbon atoms; R ２ and R ３ Each of these independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. In the aryl groups having 6 to 20 carbon atoms, the cycloalkyl groups having 5 to 6 carbon atoms, and the aryl groups having 7 to 40 carbon atoms may have any hydrogen atom independently replaced by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the alkylene groups having 7 to 40 carbon atoms, any hydrogen atom may be replaced by a fluorine atom, and any -CH ２ The - group may be independently replaced by -O-, -CH=CH-, or a cycloalkylene having 5 to 20 carbon atoms, and in the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH ２ The - can be independently replaced by -O- or a cycloalkylene having 5 to 20 carbon atoms; p represents a real number between 1 and 20; x represents a real number between 1 and 30; y1 + y2 represents a real number between 1 and 30, where y1 is 2 or greater and y2 is between 0 and 30 (inclusive).

11. A method for producing a siloxane polymer containing a repeating unit represented by formula (1) according to claim 10, wherein the transition metal catalyst is a palladium catalyst.

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