Silicon oxide polymers, silicone oxide polymer compositions and molded bodies

Abstract

This invention provides a crosslinkable silica polymer (α') whose main chain contains sesquioxane units, chain silica units, and Si-H groups. A heat-resistant hardened film with Si-H groups as crosslinking points is provided by coating a composition containing this silica polymer (α') onto a substrate and then heat-curing it. One silica polymer (α') has repeating units represented by formulas (1), (2), and (4H), with end groups represented by formulas (5L) and (5R) at its left and right ends.

Description

[Technical Field]

[0001] This invention relates to a novel silicate polymer in which a cage-like silsesquioxane is introduced into the side chain of a silicate polymer comprising a double-deck silsesquioxane (one of the cage-like silsesquioxanes) and a chain-like silicate, a silicate polymer composition containing the same, and a molded article. Furthermore, it relates to a silicate polymer compound as an intermediate for manufacturing the silicate polymer. [Previous Technology]

[0002] Cage-type or bilayer-type silsesquioxanes obtained by hydrolyzing and condensing trialkoxysilanes or trichlorosilanes have a rigid inorganic framework similar to the basic building blocks of silicon dioxide containing Si-O bonds, and have a structure in which organic groups are bonded to each silicon atom. In addition, the organic groups (reactive groups, non-reactive groups) bonded to silicon atoms can be selected according to the purpose of improving affinity with various polymer materials or resin modification caused by reaction, thus becoming a suitable research object in the field of organic-inorganic hybrids.

[0003] In polymers containing a cage-like silsesquioxane backbone in the main chain, heat resistance, transparency, hydrophobicity, etc., which cannot be achieved by using only organic polymers can be greatly improved. Polyimide-based polymers (see Non-Patent Literature 1 and Non-Patent Literature 2), polyazoalkane-based polymers (see Non-Patent Literature 3), polysiloxane-based polymers (see Non-Patent Literature 4), etc. are known.

[0004] Among polymers whose main chain contains a bilayer silsesquioxane backbone, which is one of the cage-like silsesquioxanes, various types are known, including polyimide-based (see Non-Patent Documents 5 and 6), polysiloxane-based (see Patent Documents 1-5, Non-Patent Documents 7-10), polybenzoxazine-based (see Non-Patent Document 11), and polyurethane-based (see Non-Patent Document 12) (see Non-Patent Documents 13 and 14). In particular, in the polysiloxane-based polymers, by introducing crosslinking functional groups into the molecular structure and chemically crosslinking using a crosslinking agent, molded articles with excellent transparency and heat resistance have been developed (see Patent Documents 3-5). [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2010-120901 [Patent Document 2] Japanese Patent Application Publication No. 2006-22207 [Patent Document 3] Japanese Patent Application Publication No. 2008-280420 [Patent Document 4] Japanese Patent Application Publication No. 2010-116464 [Patent Document 5] Japanese Patent Application Publication No. 2010-116462 [Non-Patent Documents]

[0006] [Non-Patent Literature 1] Chemistry Letters, 2014, 43, 1532-1534 [Non-Patent Literature 2] RSC Advances, 2016, 6, 31751-31757 [Non-Patent Literature 3] ACS Macro Letters, 2018, 7, 641-645 [Non-Patent Literature 4] Polymer Chemistry, 2015, 6, 7500-7504 [Non-Patent Literature 5] Macromolecules, 2007, 40, 5698-5705 [Non-Patent Literature 6] Macromolecules, 2008, 41, 3481-3487 [Non-Patent Literature 7] "Macromolecules" 2009, 42, 3309-3315 [Non-Patent Literature 8] "Chemistry Letters" 2012, 41, 622624 [Non-Patent Literature 9] "Polymer" 2017, 127, 8-14 [Non-Patent Literature 10] "Polymer" 2016, 86, 113-119 [Non-Patent Literature 11] "Macromolecules" 2018, 51, 9602-9612 [Non-Patent Literature 12] "Polymer Chemistry" 2013, 4, 1491-1501 [Non-Patent Literature 13] "Current Organic Chemistry" 2017, 21, 2794-2813 [Non-Patent Document 14] "Polymers" 2019, 11, 2098 [Summary of the Invention]

[0007] [The problem the invention aims to solve]

[0008] Flexible electronic components using heat-resistant transparent plastic films on substrates not only offer increased freedom in shape, expanding the design range of the components, but also provide heat resistance during the component manufacturing process. This drives their adoption in next-generation components requiring thinness and lightweight designs, such as smartphones, tablets, and organic electroluminescence (EL) displays. Extensive development is underway not only of transparent polyimides, polyamides, and polyetheretherketones, but also of polymers with cage-like silsesquioxane backbones in their main chains. However, many challenges remain in improving transparency, heat resistance, coefficient of linear expansion, and smoothness.

[0009] For example, Non-Patent Literature 1 and Non-Patent Literature 2 reported the successful synthesis of polyimides with a main chain containing a cage-like silsesquioxane backbone, exhibiting excellent heat resistance (Td5: 483 °C) and low linear expansion (81.3 ppm / K, room temperature to 350 °C), but the transmittance at 360 nm was limited to 80%, and a slight yellow coloration was observed. Non-Patent Literature 6 reported the successful synthesis of polyimides with a main chain containing a bilayer silsesquioxane backbone, one of the cage-like silsesquioxanes, which also exhibited excellent heat resistance (Td5: 500 °C), low dielectric constant (1 MHz: 2.63, 100 KHz: 2.65) or low water absorption (40 °C to 80 °C: <1%), but a yellow coloration suggesting the presence of charge-transfer complexes was observed. Patent documents 3-5 successfully synthesized siloxane polymers with a bilayer silsesquioxane backbone in the main chain. By introducing crosslinking functional groups into the molecular structure and using intermolecular chemical crosslinking or crosslinking agents, colorless, transparent molded bodies with excellent heat resistance (Td5: 467℃~540℃) were developed. However, besides the time required for intermolecular chemical crosslinking or the reaction with crosslinking agents, many technical challenges remain regarding the high transparency (haze: <1%, total light transmittance: >90%) required for flexible electronic components, as well as low linear expansion (<200 ppm). [Means for solving these problems]

[0010] In order to study the manufacture of silicate polymers that do not require chemical crosslinking and contain a bilayered silsesquioxane backbone with high transparency and low linear expansion in the main chain, the inventors have repeatedly and intensively studied their methods. As a result, they discovered that by introducing a cage-like silsesquioxane backbone into the side chains of the silicate polymer, molecular mobility is suppressed and intermolecular cohesion is strengthened. That is, the present invention can solve the aforementioned problems.

[0011] The embodiments of the present invention include the following structures.

[0012] [1] A siloxane polymer having repeating units represented by formula (1) and formula (4), with end groups represented by formula (5L) and formula (5R) at the left and right ends; (formula (5L) represents the end group bonded to the left side of the formula, and formula (5R) represents the end group bonded to the right side; A represents the following structure; R0 independently represents an aryl group with 6 to 20 carbon atoms or a cycloalkyl group with 5 to 6 carbon atoms, wherein any hydrogen atom in the aryl group with 6 to 20 carbon atoms and the cycloalkyl group with 5 to 6 carbon atoms can be independently substituted by a fluorine atom or an alkyl group with 1 to 20 carbon atoms; R1 independently represents a hydrogen atom, 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 group having 6 to 20 carbon atoms, the cycloalkyl group having 5 to 6 carbon atoms, and the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom may be independently substituted 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 may be substituted by a fluorine atom. Any -CH2- may be independently substituted by -O-, -CH=CH-, or an alkyl group having 5 to 20 carbon atoms. In the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently substituted by a fluorine atom. Any -CH2- may be independently substituted by -O- or an alkyl group having 5 to 20 carbon atoms. R2 independently represents hydroxyl, aryl (6-20 carbons), cycloalkyl (5-6 carbons), arylalkyl (7-40 carbons), or alkyl (1-40 carbons). In the aryl group of the 6-20 carbons, the cycloalkyl (5-6 carbons), and the arylalkyl (7-40 carbons), any hydrogen atom may be independently substituted by a fluorine atom or an alkyl group of 1-20 carbons. In the alkyl group of the 7-40 carbons, any hydrogen atom may be substituted by a fluorine atom. Any -CH2- may be independently substituted by -O-, -CH=CH-, or an alkyl group of 5-20 carbons. In the alkyl group of 1-40 carbons, any hydrogen atom may be independently substituted by a fluorine atom. Any -CH2- may be independently substituted by -O- or an alkyl group of 5-20 carbons. R3 independently represents an alkyl group having 1 to 40 carbon atoms, wherein any -CH2- can be independently substituted by -O- or an alkyl group having 5 to 20 carbon atoms.R4 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. In the aryl group with 6 to 20 carbon atoms, the cycloalkyl group with 5 to 6 carbon atoms, and the arylalkyl group with 7 to 40 carbon atoms, any hydrogen atom can be independently substituted by a fluorine atom or an alkyl group with 1 to 20 carbon atoms. In the alkyl group with 7 to 40 carbon atoms, any hydrogen atom can be substituted by a fluorine atom. Any -CH2- can be independently substituted by -O-, -CH=CH-, or an alkyl group with 5 to 20 carbon atoms. In the alkyl group with 1 to 40 carbon atoms, any hydrogen atom can be independently substituted by a fluorine atom. Any -CH2- can be independently substituted by -O- or an alkyl group with 5 to 20 carbon atoms. R5 independently represents hydroxyl, hydrogen, a crosslinking functional group as an alkenyl group having 2 to 40 carbon atoms, an alkyl group having 1 to 40 carbon atoms, a halogen, an acetyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an oxime group having 1 to 15 carbon atoms, an amino group that may have a substituent, an aminoamine group having 1 to 15 carbon atoms that may have a substituent, an aminooxy group having a substituent, or an vinyl alcohol residue having 2 to 15 carbon atoms that may have a substituent, wherein in the amine group and aminooxy group having a substituent, the substituent has 1 to 15 carbon atoms; p represents a real number greater than 1, z represents a positive real number; * indicates a bond position.

[0013] [2] The siloxane polymer as described in [1] further has repeating units represented by formula (2) and / or formula (3); (R2 represents the same R2 as R2 in formula (4) in [1]; x and y represent positive real numbers independently).

[0014] [3] The siloxane polymer as described in item [1] has repeating units represented by formula (2+4) and / or formula (4+2); (R2 represents the same R2 as R2 in formula (4) in item [1]; x and z represent positive real numbers independently).

[0015] [4] The siloxane polymer as described in item [1] or [3] has at least one repeating unit selected from the formula (4+2+3), formula (2+4+3), formula (2+3+4), formula (4+3+2), formula (3+4+2) and formula (3+2+4); (R2 represents the same R2 as R2 in formula (4) in item [1]; x, y and z each independently represent positive real numbers).

[0016] [5] The siloxane polymer as described in any one of items [1] to [4], wherein R2 is independently methyl or phenyl, and R4 is independently phenyl, isobutyl, cyclopentyl, cyclohexyl, trifluoropropyl, nonafluorohexyl or pentafluorophenyl.

[0017] [6] The siloxane polymer as described in any one of items [1] to [5], wherein the weight average molecular weight is 2,000 to 10,000,000.

[0018] [7] A silicate polymer composition comprising a silicate polymer as described in any one of items [1] to [6] and a solvent.

[0019] [8] A molded body is formed by hardening a silicone polymer as described in any one of the items [1] to [6] or a silicone polymer composition as described in the item [7].

[0020] [9] The molded body as described in item [8], wherein the haze value is less than 1%, the thermal decomposition temperature is in the range of 350°C to 450°C, and the coefficient of linear expansion is less than 200 ppm.

[0021]

[10] The molded body as described in item [8] has electrical insulation properties.

[0022]

[11] A molded body comprising: a hardened material formed by hardening a silicone polymer as described in any one of the items [1] to [6] or a silicone polymer composition as described in the item [7], and a substrate covered by the hardened material.

[0023]

[12] The molded body as described in item

[11] , wherein the difference between the haze value of the molded body and the substrate is less than 1%, and the coefficient of linear expansion is less than 200 ppm.

[0024]

[13] The molded article as described in item

[11] has electrical insulation properties. [Effects of the Invention]

[0025] This invention provides a silica polymer containing silsesquioxane units and chain silica units in the main chain and having a cage-like silsesquioxane structure in the side chains, as well as a method for manufacturing the silica polymer. Furthermore, by coating a substrate with a composition obtained by dissolving the silica polymer in an organic solvent, and then peeling it off from the substrate after calcination, a highly transparent, flexible film with a low coefficient of thermal expansion, utilizing the cohesive force (physical crosslinking) of the cage-like silsesquioxanes in the side chains, can be obtained.

Implementation Method

[0027] Hereinafter, embodiments of the present invention will be described in detail. The following description is an example (representative example) of an embodiment of the present invention, and the present invention is not limited by these contents in any way. In addition, embodiments of the present invention may also be suitably combined.

[0028] Furthermore, the terms used in this specification are defined as follows. Alkyl and alkyl groups can be straight-chain or branched groups in any case. This is also true when any hydrogen in these groups is substituted with a halogen or cyclic group, or when any -CH2- is substituted with -O-, -CH=CH-, cycloalkyl, cycloalkenyl, phenyl, etc. The word "any" used in this invention means that not only the position but also the number is arbitrary. Moreover, when there are multiple groups, they can be substituted with different groups respectively. For example, when two -CH2- groups in an alkyl group are substituted with -O- and -CH=CH-, it represents an alkoxyalkenyl or an alkenoxyalkyl group. In the case described, any of the alkoxy, alkenyl, alkenyl, and alkyl groups can be straight-chain or branched groups. Wherein, when it is described as any -CH2- substituted with -O-, a plurality of consecutive -CH2- groups will not be substituted with -O-. That is, for example, -CH2-CH2- will not be replaced by -OO-.

[0029] The siloxane polymer of one embodiment of the present invention has repeating units represented by formulas (1) and (4), and the left and right ends are end groups represented by formulas (5L) and (5R). Furthermore, the term "left and right ends" refers to the appearance when the siloxane polymer of the present invention is represented by a structural formula.

[0030] Equation (5L) represents the end base of the left-hand bond with the formula, Equation (5R) represents the end base of the right-hand bond with the formula, and A represents the following structure.

[0031] The siloxane polymer of the present invention may further have repeating units represented by formula (2) and / or formula (3).

[0032] The symbols in the formula, as described in items [1] to [2], will be described in detail later.

[0033] The siloxane polymer of the present invention has repeating units represented by formulas (1) and (4), which constitute the "main chain". The main chain may further have repeating units represented by formulas (2) and / or (3). Terminal groups represented by formulas (5L) and (5R) are bonded at both ends of the main chain. Formula (5L) represents the terminal group bonded to the left side of the formula, and formula (5R) represents the terminal group bonded to the right side. In these, A in formula (4) serves as a "side chain" bond.

[0034] The side chain represented by A has the following structure.

[0035] 1. "Main Chain" of Silicon Oxide Polymer With regard to the structure of the "main chain" of the silicone oxide polymer of the present invention, an example of its structure is shown. The silicone oxide polymer of the present invention, for example, comprises silicone oxide polymers having a main chain structure represented by the following formulas (main chain 1), (main chain 2-1) to (main chain 2-8), (main chain 3-1) to (main chain 3-12), (main chain 4-1) to (main chain 4-48), and (main chain 5-1) to (main chain 5-36). In these formulas, m represents a real number greater than 1, x', y', and z' each independently have the same meaning as x, y, and z, and the meanings of other symbols are as described in items [1] to [2].

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[0141] 2. "Side Chain" of Silicon Oxide Polymer In this invention, the part of the structure represented by A is referred to as "side chain". Regarding R4 and R3 in side chain A, as described in item [1].

[0142] The side chain represented by A specifically includes the side chains of the structures (A-1) to (A-8) illustrated below.

[0143] In A, R3 is a structure of -CH2CH2CH2- and R4 is a structure of -CH2CH2CF3 (A-1). In

[0144] A, R3 is -CH2CH2CH2- and R4 is a phenyl structure (A-2).

[0145] In A, R3 is -CH2CH2CH2- and R4 is a cyclohexyl group (A-3). In

[0146] A, R3 is -CH2CH2CH2- and R4 is an isobutyl group (A-4).

[0147] In A, R3 is a structure of -CH2CH2- and R4 is a structure of -CH2CH2CF3 (A-5). In

[0148] A, R3 is -CH2CH2- and R4 is a -phenyl structure (A-6). In

[0149] A, R3 is -CH2CH2- and R4 is a cyclohexyl group (A-7). In

[0150] A, R3 is -CH2CH2- and R4 is an isobutyl group (A-8).

[0151] The above lists examples of R3 being -CH2CH2- or -CH2CH2CH2-, but the structure of R3 is not limited to these. Other preferred examples of R3 include -CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-.

[0152] In addition to (A-1) to (A-8) mentioned above, R4 may be a structure of nonafluorohexyl or pentafluorophenyl, or R4 may be a structure having a fluorinated polyether structure.

[0153] 3. Partial Structure of Silicon Oxide Polymer 3-1. (R0) R0 independently represents an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms. Examples of aryl groups having 6 to 20 carbon atoms include phenyl, naphthyl, anthraceneyl, phenanthreneyl, triphenylene, pyreneyl, thionyl, tetraphenyl, perylene, etc. Among these, phenyl, naphthyl, anthraceneyl, and phenanthreneyl are preferred, and phenyl, naphthyl, and anthraceneyl are even more preferred. Examples of cycloalkyl groups having 5 to 6 carbon atoms include cyclopentyl and cyclohexyl. 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 substituted by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. R0 is preferably phenyl or cyclohexyl.

[0154] 3-2. (R1) R1 independently represents a hydrogen atom, 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. Examples of aryl groups having 6 to 20 carbon atoms and cycloalkyl groups having 5 to 6 carbon atoms may be the same groups as those described in R0. Examples of arylalkyl groups 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, isopropyl, n-butyl, dibutyl, isobutyl, tributyl, n-pentyl, dipentyl, isopentyl, tripentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl, and octadecyl. In the aryl group of the 6-20 carbon groups, the cycloalkyl group of the 5-6 carbon groups, and the arylalkyl group of the 7-40 carbon groups, any hydrogen atom may be independently substituted with a fluorine atom or an alkyl group of the 1-20 carbon groups. In the alkyl group of the 7-40 carbon groups, any hydrogen atom may be substituted with a fluorine atom, and any -CH2- may be independently substituted with -O-, -CH=CH-, or an alkyl group of the 5-20 carbon groups. In the alkyl group of the 1-40 carbon groups, any hydrogen atom may be independently substituted with a fluorine atom, and any -CH2- may be independently substituted with -O- or an alkyl group of the 5-20 carbon groups. R1 is preferably selected from hydrogen, phenyl, cyclohexyl, and alkyl groups of the 1-5 carbon groups, and more preferably from alkyl groups of the 1-5 carbon groups.

[0155] 3-3. (R2, R5) R2 and R5 independently represent a hydroxyl group, 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. For aryl groups having 6 to 20 carbon atoms and cycloalkyl groups having 5 to 6 carbon atoms, the same groups as those described in R0 can be listed. For arylalkyl groups having 7 to 40 carbon atoms, the same groups as those described in R1 can be listed. For alkyl groups having 1 to 40 carbon atoms, the same groups as those described in R1 can be listed. In the aryl group of the 6-20 carbon groups, the cycloalkyl group of the 5-6 carbon groups, and the arylalkyl group of the 7-40 carbon groups, any hydrogen atom may be independently substituted with a fluorine atom or an alkyl group of the 1-20 carbon groups. In the alkyl group of the 7-40 carbon groups, any hydrogen atom may be substituted with a fluorine atom, and any -CH2- may be independently substituted with -O-, -CH=CH-, or an alkyl group of the 5-20 carbon groups. In the alkyl group of the 1-40 carbon groups, any hydrogen atom may be independently substituted with a fluorine atom, and any -CH2- may be independently substituted with -O- or an alkyl group of the 5-20 carbon groups. R2 and R5 are preferably selected from phenyl, cyclohexyl, and alkyl groups of the 1-40 carbon groups, and more preferably from alkyl groups of the 1-5 carbon groups.

[0156] 3-4. (p) p represents a real number greater than or equal to 1. From a manufacturing point of view, it is preferable to be greater than or equal to 1 and less than 3000, and even more preferably greater than or equal to 1 and less than 300.

[0157] 3-5. (x, y) x is a value that depends on the amount of repeating units in the siloxane polymer having the structure of formula (2) contained in the main chain, and is 0 when the structure of formula (2) is not included. The content of repeating units of formula (2) varies depending on how much of the part corresponding to the structure is loaded as a raw material for the siloxane polymer, and the physical properties of the siloxane polymer can be controlled by adjusting its amount. The preferred range of x is 0.5 to 10.

[0158] y is a repeating unit (the structure represented by formula (3)) contained in a certain proportion in the intermediate during the manufacturing stage of the siloxane polymer of the present invention, into which side chain A is introduced by an addition reaction (the method for manufacturing the siloxane polymer of the present invention will be described in detail later). Therefore, it is a value that depends on the proportion of the structure into which side chain A is introduced. The value of y is 0 when the entire -Si-H portion of the intermediate has the structure into which side chain A is introduced. The preferred range of y is 0.1 to 8.

[0159] 3-6. (z) z is a value determined by the amount of A structure introduced into the side chain of the siloxane polymer. The preferred range of z is 0.2 to 5.

[0160] 4. Method for Manufacturing Silicon Oxide Polymer The method for manufacturing the silicon oxide polymer of the present invention will be described. First, a silicon oxide polymer with a structure in which the portion represented by A of the silicon oxide polymer of the present invention is substituted with hydrogen atoms is prepared. In this specification, the silicon oxide polymer is referred to as "intermediate (α)". A compound (β) corresponding to the structure of A is introduced into the -Si-H portion of the intermediate (α) by means of an addition reaction, a desorption reaction, or a substitution reaction.

[0161] For example, as shown in the following reaction formula, the compound represented by formula (β) can be introduced into the siloxane polymer intermediate represented by formula (α) by an addition reaction.

[0162]

[0163] The compound (β) corresponds to side chain A. In this example, the terminal double bond undergoes an addition reaction with the silicon atom of the siloxane polymer intermediate (α). In this example, the structure of R3' of compound (β) is a structure obtained by subtracting two carbons from R3 (the two carbons become -CH=CH2 and participate in the addition reaction).

[0164] The compounds (β) corresponding to the side chains A (A-1) to (A-8) are respectively (β-1) to (β-8).

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[0172] In the examples described, compounds β with structures corresponding to R3 of -CH=CH2 and -CH2CH=CH2 are listed. When it is desired to introduce an alkyl group with 4 to 12 carbon atoms as R3, it corresponds to the following groups: -CH2CH2CH=CH2, -CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2.

[0173] The silicate polymers of the present invention can be manufactured by reacting these compounds (β) with silicate polymer intermediates (α) via an addition reaction. A preferred example of the addition reaction is a hydrogenation silicalization reaction using a Karstedt catalyst.

[0174] In addition, when introducing a side chain of R3 as -CH2-, as (β), a compound such as the following can be selected as the starting material.

[0175]

[0176] In addition, when a side chain of R3 is -O- is introduced, the compound represented by compound (β) can be introduced into the siloxane polymer intermediate (α) by means of a dehydrogenation reaction as shown in the following reaction formula.

[0177]

[0178] The compound (βOH) corresponds to side chain A. In this example, the terminal silanol undergoes a dehydrogenation reaction based on the hydrogenated silyl group of the siloxane polymer intermediate (α) and a boron compound catalyst.

[0179] In addition, the silicate polymer of the present invention can be manufactured by a desorption reaction or substitution reaction between a silicate polymer intermediate (αOH) in which a portion of R2 is a hydroxyl group and a compound (β).

[0180]

[0181] The compound (βH) corresponds to side chain A. In this example, the terminal hydrogenated silyl group undergoes a dehydrogenation reaction in the presence of the silanol group of the siloxane polymer intermediate (αOH) and a boron compound catalyst.

[0182]

[0183] The compound (βOH) corresponds to side chain A. In this example, the terminal silanol group undergoes dehydration condensation with the silanol of the siloxane polymer intermediate (αOH) under acidic conditions.

[0184]

[0185] The compound (βCl) corresponds to side chain A. In this example, the terminal chlorosilane undergoes a dehydrochlorination reaction with the silanol group of the siloxane polymer intermediate (αOH). The reaction can be easily promoted by adding a compound with an amine group, such as triethylamine (TEA), or an organic compound that exhibits basicity.

[0186] 4-1-a. Silicon Oxide Polymer Intermediate (α) The silicon oxide polymer intermediate (α) (hereinafter referred to as "intermediate (α)") is useful as a raw material for manufacturing the silicon oxide polymer of the present invention. Furthermore, as described below, the intermediate (α) can also be configured as a raw material for manufacturing intermediate (αOH) by converting hydrogen atoms of Si-H into silanol groups in the presence of a transition metal catalyst. In addition, the intermediate (α) itself is not merely an "intermediate," but becomes a material that can be used after curing. Therefore, the intermediate (α) can also be understood as a useful invention.

[0187] Here, in the case where the intermediate (α) is understood as the invention, it is redefined as a siloxane polymer (α') as shown below.

[0188] [1'] A siloxane polymer (α') having repeating units represented by formula (1), formula (2) and formula (4H), with end groups represented by formula (5L) and formula (5R) at the left and right ends; (formula (5L) represents the end group bonded to the left side of the formula, and formula (5R) represents the end group bonded to the right side; R0 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 and the cycloalkyl group having 5 to 6 carbon atoms can be independently substituted by a fluorine atom or an alkyl group having 1 to 20 carbon atoms; R1 independently represents a hydrogen atom, 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 group having 6 to 20 carbon atoms, the cycloalkyl group having 5 to 6 carbon atoms, and the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom may be independently substituted 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 may be substituted by a fluorine atom. Any -CH2- may be independently substituted by -O-, -CH=CH-, or an alkyl group having 5 to 20 carbon atoms. In the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently substituted by a fluorine atom. Any -CH2- may be independently substituted by -O- or an alkyl group having 5 to 20 carbon atoms. R2 independently represents hydroxyl, aryl (6-20 carbons), cycloalkyl (5-6 carbons), arylalkyl (7-40 carbons), or alkyl (1-40 carbons). In the aryl group of the 6-20 carbons, the cycloalkyl (5-6 carbons), and the arylalkyl (7-40 carbons), any hydrogen atom may be independently substituted by a fluorine atom or an alkyl group of 1-20 carbons. In the alkyl group of the 7-40 carbons, any hydrogen atom may be substituted by a fluorine atom. Any -CH2- may be independently substituted by -O-, -CH=CH-, or an alkyl group of 5-20 carbons. In the alkyl group of 1-40 carbons, any hydrogen atom may be independently substituted by a fluorine atom. Any -CH2- may be independently substituted by -O- or an alkyl group of 5-20 carbons. R5 independently represents hydroxyl, hydrogen, crosslinking functional group as alkenyl group with 2 to 40 carbons, alkyl group with 1 to 40 carbons, halogen, acetyl group with 1 to 15 carbons, alkoxy group with 1 to 15 carbons, oxime group with 1 to 15 carbons, amine group with 1 to 15 carbons that may have substituents, amide group with 1 to 15 carbons that may have substituents, aminooxy group with 2 to 15 carbons that may have substituents, or vinyl alcohol residue with 2 to 15 carbons that may have substituents, wherein the substituent in the amine group and aminooxy group has 1 to 15 carbons; p represents a real number greater than 1, and x and z independently represent positive real numbers; * represents the bond position).

[0189] [2'] The siloxane polymer (α') as described in [1'] has repeating units represented by formula (2+4H) and / or formula (4H+2); (R2 represents the same R2 as R2 in formula (4H) in [1']; x independently represents 0 or a positive real number, and z independently represents a positive real number).

[0190] [3'] The siloxane polymer (α') as described in item [1'] or [2'], wherein R2 is independently methyl or phenyl.

[0191] [4'] The siloxane polymer (α') as described in any one of items [1'] to [3'], wherein the weight average molecular weight is 2,000 to 10,000,000.

[0192] [5'] A silicate polymer composition comprising a silicate polymer (α') as described in any one of items [1'] to [4'] and a solvent.

[0193] [6'] A molded body is formed by hardening a silicone polymer (α') as described in any one of items [1'] to [4'] or a silicone polymer composition as described in item [5'].

[0194] [7'] The molded body as described in item [6'] has electrical insulation properties.

[0195] [8'] A molded body comprising: a hardened material formed by hardening a silica alkane polymer (α') as described in any one of claims [1'] to [4'] or a silica alkane polymer composition as described in claim [5'], and a substrate covered by the hardened material.

[0196] [9'] The molded body as described in item [8'] has electrical insulation properties.

[0197] The invention of the silicate polymer (α') not only provides a silicate polymer (α') containing sesquioxane units and chain silicate units in the main chain and a method for manufacturing the silicate polymer (α'), but also, by coating a substrate with a composition in which the silicate polymer (α') is dissolved in an organic solvent and then heating and curing it, a cured film with Si-H groups as crosslinking points and excellent heat resistance can be obtained. Furthermore, the silicate polymer (α') can introduce functional groups into the Si-H groups, thus it is also useful as an intermediate for manufacturing silicate polymers with highly controllable heat resistance or mechanical properties.

[0198] 4-1-b. Method for manufacturing intermediate (α) Many examples of methods for manufacturing intermediate (α) are known, such as by equilibrium polymerization of the following compounds , , and <C> in the presence of an acid catalyst. Compound can be obtained by hydrolyzing the following compounds <D> with compounds <E> or <F> (see, for example, paragraph 0032 of Japanese Patent Application Publication No. 2006-022207). However, the specific structure of intermediate (α) or siloxane polymer (α') is not known.

[0199]

[0200]

[0201]

[0202]

[0203] 4-2. Method for manufacturing intermediate (αOH) Regarding the method for manufacturing intermediate (αOH), for example, it can be manufactured by converting intermediate (α) into silanol group in the presence of transition metal catalyst.

[0204]

[0205] 4-3. Method for manufacturing compound (β) The method for manufacturing compound (β) will also be described. Compound (β) can be manufactured by reacting compound (β-0) with allyltrichlorosilane.

[0206]

[0207] The compound (βOH) can be produced by hydrolyzing the compound (β-O).

[0208]

[0209] Compound (βCl) can be produced by reacting compound (β-O) with tetrachlorosilane.

[0210]

[0211] Compound (βH) can be produced by reacting compound (β-O) with trichlorosilane.

[0212]

[0213] Many examples of methods for manufacturing compound (β-0) are known, such as manufacturing it by hydrolysis and condensation of trifluoropropyltrimethoxysilane in the presence of alkali metal hydroxide.

[0214]

[0215] Regarding these manufacturing methods, for example, they are described in paragraph 32 of Japanese Patent Application Publication No. 2005-15738.

[0216] 5. Solvent The silicate polymer of the present invention can be used as a silicate polymer composition containing a solvent. Preferably, such a solvent is one capable of dissolving the silicate polymer and does not condense with crosslinked silica compounds or crosslinked compounds. Examples of such solvents include hydrocarbon solvents such as hexane or heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF), and dioxane, halogenated hydrocarbon solvents such as dichloromethane and carbon tetrachloride, and ester solvents such as ethyl acetate. The solvent may be a single solvent or two or more solvents. For example, from the viewpoint of coatability, the content of the solvent is preferably 20% to 80% by mass of the silicate polymer, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass.

[0217] 6. Calcined Material and Film By calcining a silicone polymer composition containing the silicone polymer or solvent of the present invention, a calcined material with high transparency and low coefficient of thermal expansion with flexibility can be obtained. The calcination temperature is preferably 150°C to 250°C. The calcined material can be used as a film. Specifically, calcination is performed by applying the silicone polymer composition to a substrate and then heating it using an oven or the like. There are no particular limitations on the calcination temperature and time if the silicone polymer can be made into a film (self-supporting film). After cooling, the calcined silicone polymer can be peeled off from the substrate as a film. There are no particular limitations on the substrate if it is capable of withstanding the firing temperature and the film formed on it can be peeled off from the substrate and removed as a self-supporting film. Examples include glass substrates such as quartz, barium borosilicate glass, and aluminum borosilicate glass; calcium fluoride substrates; metal oxide substrates such as indium tin oxide (ITO); ceramic substrates; polycarbonate (PC) films, silicone-based films, polyethylene terephthalate (PET) films, polyethylene naphthalate (PEN) films, cycloolefin polymer (COP) films, polypropylene films, polyethylene films, acrylic polymer films, polyvinyl alcohol films, triacetyl cellulose films, and polyimide (PI) films; and polytetrafluoroethylene (PTFE) and perfluoroalkoxy alkanes. Fluoropolymer substrates such as Alkane (PFA); laminated substrates made of glass or the like coated with fluoropolymer resin; metal substrates such as SUS and copper, etc. [Examples]

[0218] Hereinafter, the present invention will be described in more detail with reference to embodiments, but the scope of the present invention is not limited by these descriptions.

[0219] The measurements in the examples were performed in the following manner.

[0220] ·GPC (Gel Permeation Chromatography) <Determination Conditions> Column: Shodex KF-804L 300 mm × 8.0 mm (Showa Denko Co., Ltd.) Shodex KF-805L 300 mm × 8.0 mm (Showa Denko Co., Ltd.) 2 tandem mobile phases: THF Flow rate: 1.0 ml / min Temperature: 40℃ Detector: RI Molecular weight standard: Polymethyl methacrylate (PMMA) resin with known molecular weight

[0221] ·DMA (Dynamic Mechanical Analysis) Dynamic Viscoelasticity Measurement <Measurement Conditions> Hitachi High-Tech Science DMS6100 5℃ / min, Sample area 10 mm × 1 mm, Load 10 mN, Measurement frequency 10 Hz

[0222] ·TMA (Thermal Mechanical Analysis) <Measurement Conditions> Hitachi High-Tech Science SS / TMA6100, tensile mode, 10℃ / min, length 20 mm, cross-sectional area 0.3 mm2, load 9.8 mN

[0223] ·TG-DTA (Thermogravimetric Differential Thermal Analysis) <Determination Conditions> Measurement Apparatus: Seiko Instruments EXSTAR 6000TG / DTA6300 Pot: Pt Standard Sample: Alumina (10 mg) Sample Mass: Approximately 10 mg Temperature Program: 25℃~800℃ Heating Rate: 10℃ / min

[0224] ·Total light transmittance: Total light transmittance was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) based on Japanese Industrial Standards (JIS) K 7361-1.

[0225] ·HAZE: HAZE (darkness, haze) was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) based on JIS K7136.

[0226] ·Glass transfer temperature: The temperature at which the loss elastic coefficient (E'') peaks in the dynamic viscoelasticity determination using DMA.

[0227] · Crosslinking density: The crosslinking density is calculated according to the formula (1). n=E' / 3RT···(1) In formula (1), n: crosslinking density (mol / m3), E': storage elasticity coefficient (Pa), R: gas constant ((Pa·m3) / K·mol)), T: temperature (K)

[0228] ·Coefficient of Thermal Expansion (CTE): Measured by TMA. The coefficient of thermal expansion is calculated based on the results of the first scan (first heating, heating rate: 10℃ / min) of the temperature range of 40℃ to 250℃.

[0229] ·Thermal decomposition temperature (Td5): Measured by TG-DTA. The temperature at which the weight decreases by 5%.

[0230] · Elastic modulus: Determined using a Tensilon RTF-1310 universal testing machine (manufactured by A&D Corporation) by tensile testing at a tensile speed of 5 mm / min and at room temperature. The test piece was prepared using an 8-gauge dumbbell, and the tangent of the maximum slope of the stress / strain curve before the membrane undergoes plastic deformation was used.

[0231] ·Maximum stress: Determined using a Tensilon RTF-1310 universal testing machine (manufactured by A&D Corporation) by tensile testing at a tensile speed of 5 mm / min and at room temperature. The test piece was made using a No. 8 dumbbell, and the maximum stress was measured before the test piece broke.

[0232] ·Volume resistivity: The volume resistivity was calculated based on the resistance value when an applied voltage of 250 V was applied, using a Femto Picoammeter B2981A, controller GP-32, controller GP-HV, and test fixture N1259A (manufactured by Keysight Technologies, Inc.). For the test pieces, a silicone polymer film was formed on a Cr-plated substrate using a spin coater and then calcined, followed by Al-plated substrate.

[0233] Silicon oxyalkane polymers were manufactured according to the reaction formulas shown below (Examples 1 to 3), and their physical properties were evaluated. The obtained silicon oxyalkane polymers were prepared into solutions according to the compositions shown in Table 3, coated onto a substrate coated with fluororesin, heated at a temperature of 180°C or higher for more than 3 hours, cooled, and then peeled off from the substrate to obtain a self-supporting film.

[0234]

[0235] The relationships of x, y and z in the intermediate (α), compound (β-1) and product in Examples 1 to 3 are shown in Table 1.

[0236] [Table 1] Example (α) (β-1) Products 1 x = average 3.2, y + z = average 0.8 The y+z ratio relative to the intermediate (α) is 0.5 mol. (x=3.2, y: 0.41, z: 0.39) z: 7.6% of all units 2 Same as above The y+z ratio relative to the intermediate (α) is 0.7 mol. (x=3.2, y: 0.24, z: 0.56) z: 11.2% of all units 3 x = average 2.1, y + z = average 2.0 The y+z ratio relative to the intermediate (α) is 0.6 mol. (x=2.1, y: 0.79, z: 1.21) z: 23.7% of all units

[0237] [Example 1] 5 g of compound (α), 1.5 g of compound (β-1), and 15.0 g of ethyl acetate were added to a 100 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 2.1 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 70°C, and the mixture was stirred at reflux temperature for 5 hours. After cooling to room temperature, 2.8 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered to separate the solids, and the filtrate was concentrated at 50°C. Propylene glycol monomethyl ether acetate (PGMEA) was added to the concentrate, and ethyl acetate was removed by vacuum concentration, thereby obtaining 10.9 g of a (A) solution with a solid content of 60%. The molecular weight of (A) was determined using GPC. The weight-average molecular weight (Mw) is 47,000, and the polydispersity (Mw / Mn) is 4.0. The average values ​​of (x, y, z) were calculated by 1H nuclear magnetic resonance (NMR) and 29Si NMR, with an average x of 3.2, an average y of 0.41, and an average z of 0.39.

[0238] (1H-NMR determination results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.17~7.66 (Ph), 4.65~4.74 (Si-H), 2.34 (CF3CH2), 1.51~1.60 (CH2), 1.02 (CF3CH2CH2), 0.65~0.87 (CH2), 0.27~0.41 (O3SiMe), -0.04~0.13 (O2SiMe2). (29Si-NMR Measurement Results) 29Si-NMR (99 MHz, CO(CD3)2) δ: 9.9, -21.9~-18.3, -37.6.9~-34.8, -65.0~-64.0, -67.2~-66.8, -67.6~-67.2, -70.1, -79.6~-78.6

[0239] [Example 2] 5 g of compound (α), 2.2 g of compound (β-1), and 16.0 g of ethyl acetate were added to a 100 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 2.1 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 70°C, and the mixture was stirred at reflux temperature for 5 hours. After cooling to room temperature, 5.0 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered, and the filtrate was concentrated at 50°C. PGMEA was added to the concentrate, and ethyl acetate was removed by vacuum concentration, thereby obtaining 11.6 g of a (B) solution with a solid content of 60%. The molecular weight of (B) was determined by GPC. The weight-average molecular weight Mw was 128,000, and the polydispersity Mw / Mn = 4.0. The average values ​​of (x, y, z) were calculated by 1H-NMR and 29Si-NMR measurements. The average value of x was 3.2, the average value of y was 0.24, and the average value of z was 0.56.

[0240] (1H-NMR determination results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.17~7.65 (Ph), 4.64~4.82 (Si-H), 2.33 (CF3CH2), 1.49~1.58 (CH2), 1.01 (CF3CH2CH2), 0.61~0.89 (CH2), 0.26~0.39 (O3SiMe), -0.06~0.12 (O2SiMe2). (29Si-NMR Measurement Results) 29Si-NMR (99 MHz, CO(CD3)2) δ: 9.9, -21.9~-18.5, -37.6.9~-34.8, -65.0~-64.0, -66.4~-66.1, -67.7~-67.2, -70.1, -79.6~-78.6

[0241] [Example 3] 5 g of compound (α), 4.4 g of compound (β-1), and 22.0 g of ethyl acetate were added to a 100 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 6.0 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 70°C, and the mixture was stirred at reflux temperature for 5 hours. After cooling to room temperature, 8.0 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered, and the filtrate was concentrated at 50°C. PGMEA was added to the concentrate, and ethyl acetate was removed by vacuum concentration, thereby obtaining 15.5 g of a (C) solution with a solid content of 60%. The molecular weight of (C) was determined by GPC. The weight-average molecular weight Mw was 163,000, and the polydispersity Mw / Mn = 4.8. The average values ​​of (x, y, z) were calculated by 1H-NMR and 29Si-NMR measurements. The average value of x was 2.1, the average value of y was 0.79, and the average value of z was 1.21.

[0242] (1H-NMR determination results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.23~7.69 (Ph), 4.67~4.86 (Si-H), 2.36 (CF3CH2), 1.52~1.62 (CH2), 1.04 (CF3CH2CH2), 0.64~0.89 (CH2), 0.29~0.43 (O3SiMe), 0.00~0.17 (O2SiMe2). (29Si-NMR Measurement Results) 29Si-NMR (99 MHz, CO(CD3)2) δ: 9.9, -21.9~-18.3, -36.3~-34.7, -65.0~-64.0, -66.1~-66.3, -67.9~-67.2, -70.1, -79.4~-78.9

[0243] [Example 4] (β-5) was used as compound (β).

[0244]

[0245] The following siloxane polymer can be obtained by the same manufacturing method as in Example 1.

[0246] Silicon oxane polymers were manufactured according to the reaction formulas shown below (Examples 4 to 9), and their physical properties were evaluated. The obtained silicon oxane polymers were prepared into solutions according to the compositions shown in Tables 3 and 4, coated onto a substrate coated with fluororesin, heated at a temperature of 180°C or higher for more than 3 hours, cooled, and then peeled off from the substrate to obtain a self-supporting film.

[0247]

[0248] The relationships of x, y and z in the intermediate (α), compound (β-2) and products in Examples 4 to 9 are shown in Table 2.

[0249] [Table 2] Example (α) (β-1) Products 4 x = average 3.6, y + z = average 0.8 The y-value relative to the intermediate (α) is 0.4 mol. (x=3.6, y: 0.48, z: 0.32) z: 6.0% of all units 5 x = average 3.3, y + z = average 1.1 The y-value relative to the intermediate (α) is 0.4 mol. (x=3.3, y: 0.68, z: 0.42) z: 7.7% of all units 6 x = average 2.8, y + z = average 1.6 The y-value relative to the intermediate (α) is 0.3 times the mol value. (x=2.8, y: 1.12, z: 0.48) z: 8.9% of all units 7 Same as above The y-value relative to the intermediate (α) is 0.2 mol. (x=2.8, y: 1.33, z: 0.27) z: 5.1% of all units 8 Same as above The y-value relative to the intermediate (α) is 0.4 mol. (x=2.8, y: 0.91, z: 0.69) z: 12.7% of all units 9 x = average 3.8, y + z = average 1.2 The y-value relative to the intermediate (α) is 0.4 mol. (x=3.8, y: 0.78, z: 0.42) z: 7.0% of all units

[0250] [Example 4] 5 g of compound (α), 1.3 g of compound (β-2), and 14.7 g of THF were added to a 50 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 2.1 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 60°C, and the mixture was stirred at reflux temperature for 3 hours. Then, 2.1 μL of Pt-VTSC×3.0 was added, and the mixture was stirred at reflux temperature for another 3 hours. After cooling to room temperature, 1.8 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered, and the filtrate was concentrated at 50°C. The concentrated solution was added dropwise to 200 mL of heptane to obtain 4.2 g of a white polymer precipitate. The molecular weight of the polymer was determined using GPC, and the weight-average molecular weight (Mw) was 115,000, with a polydispersity (Mw / Mn) of 2.1. The average values ​​of (x, y, z) were calculated using 1H-NMR, with an average x of 3.6, an average y of 0.48, and an average z of 0.32. (1H-NMR results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.17–7.66 (Ph), 4.65–4.74 (Si-H), 1.51–1.60 (CH2), 0.65–0.87 (CH2), 0.27–0.41 (O3SiMe), -0.04–0.13 (O2SiMe2).

[0251] [Example 5] 5.25 g of compound (α), 1.33 g of compound (β-2), and 15.8 g of THF were added to a 50 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 3.0 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 60°C, and the mixture was stirred at reflux temperature for 3 hours. Then, 3.0 μL of Pt-VTSC×3.0 was added, and the mixture was stirred at reflux temperature for another 4 hours. After cooling to room temperature, 2.5 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered, and the filtrate was concentrated at 50°C. The concentrated solution was added dropwise to 200 mL of heptane to obtain 4.7 g of a white polymer precipitate. The molecular weight of the polymer was determined using GPC, and the weight-average molecular weight (Mw) was 88,000, with a polydispersity (Mw / Mn) of 2.4. The average values ​​of (x, y, z) were calculated using 1H-NMR, with an average x of 3.3, an average y of 0.68, and an average z of 0.42. (1H-NMR results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.17–7.66 (Ph), 4.65–4.74 (Si-H), 1.51–1.60 (CH2), 0.65–0.87 (CH2), 0.27–0.41 (O3SiMe), -0.04–0.13 (O2SiMe2).

[0252] [Example 6] 30 g of compound (α), 7.6 g of compound (β-2), and 87.8 g of THF were added to a 200 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 14 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 60°C, and the mixture was stirred at reflux temperature for 3.5 hours. Then, 14 μL of Pt-VTSC×3.0 was added, and the mixture was stirred at reflux temperature for another 3 hours. After cooling to room temperature, 7.5 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered, and the filtrate was concentrated at 50°C. The concentrated solution was added dropwise to 1.5 L of heptane to obtain 33.7 g of a white polymer precipitate. The molecular weight of the polymer was determined using GPC, and the weight-average molecular weight (Mw) was 100,000, with a polydispersity (Mw / Mn) of 2.9. The average values ​​of (x, y, z) were calculated using 1H-NMR, with an average x of 2.8, an average y of 1.12, and an average z of 0.48. (1H-NMR results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.17–7.66 (Ph), 4.65–4.74 (Si-H), 1.51–1.60 (CH2), 0.65–0.87 (CH2), 0.27–0.41 (O3SiMe), -0.04–0.13 (O2SiMe2).

[0253] [Example 7] 6 g of compound (α), 0.9 g of compound (β-2), and 16.1 g of THF were added to a 50 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 2.5 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 60°C, and the mixture was stirred at reflux temperature for 1.5 hours. After cooling to room temperature, 2.5 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered, and the filtrate was concentrated at 50°C. The concentrated solution was added dropwise to 300 mL of heptane to obtain 6.1 g of a white polymer precipitate. The molecular weight of the polymer was determined by GPC, and the weight-average molecular weight Mw was 112,000, and the polydispersity Mw / Mn = 2.6. The average values ​​(x, y, z) were calculated using 1H-NMR. The average x value was 2.8, the average y value was 1.33, and the average z value was 0.27. (1H-NMR measurement results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.17~7.66 (Ph), 4.65~4.74 (Si-H), 1.51~1.60 (CH2), 0.65~0.87 (CH2), 0.27~0.41 (O3SiMe), -0.04~0.13 (O2SiMe2).

[0254] [Example 8] 6 g of compound (α), 2.0 g of compound (β-2), and 19.5 g of THF were added to a 50 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 3.3 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 60°C, and the mixture was stirred at reflux temperature for 3 hours. Then, 3.3 μL of Pt-VTSC×3.0 was added, and the mixture was stirred at reflux temperature for another 2 hours. After cooling to room temperature, 2.5 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered, and the filtrate was concentrated at 50°C. The concentrated solution was added dropwise to 300 mL of heptane to obtain 7.4 g of a white polymer precipitate. The molecular weight of the polymer was determined using GPC, and the weight-average molecular weight (Mw) was 92,000, with a polydispersity (Mw / Mn) of 2.9. The average values ​​of (x, y, z) were calculated using 1H-NMR, with an average x of 2.8, an average y of 0.91, and an average z of 0.269. (1H-NMR results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.17–7.66 (Ph), 4.65–4.74 (Si-H), 1.51–1.60 (CH2), 0.65–0.87 (CH2), 0.27–0.41 (O3SiMe), -0.04–0.13 (O2SiMe2).

[0255] [Example 9] 6 g of compound (α), 1.4 g of compound (β-2), and 17.9 g of THF were added to a 50 mL four-necked round-bottom flask. A thermometer, reflux tube, stirrer, and oil bath were set up, and the mixture was stirred while nitrogen was introduced. 2.7 μL of Pt-VTSC×3.0 (manufactured by Umicore Japna, Ltd.) was added at 60°C, and the mixture was stirred at reflux temperature for 7 hours. After cooling to room temperature, 2.5 g of activated carbon was added, and the mixture was stirred overnight. The activated carbon was filtered, and the filtrate was concentrated at 50°C. The concentrated solution was added dropwise to 200 mL of heptane to obtain 5.4 g of a white polymer precipitate. The molecular weight of the polymer was determined by GPC, and the weight-average molecular weight Mw was 116,000, and the polydispersity Mw / Mn = 2.8. The average values ​​(x, y, z) were calculated using 1H-NMR. The average x value was 3.8, the average y value was 0.78, and the average z value was 0.42. (1H-NMR measurement results) 1H-NMR (400 MHz, CO(CD3)2) δ: 7.17~7.66 (Ph), 4.65~4.74 (Si-H), 1.51~1.60 (CH2), 0.65~0.87 (CH2), 0.27~0.41 (O3SiMe), -0.04~0.13 (O2SiMe2).

[0256] [Comparative Example 1] A polymer solution containing the formulas (1), (2), and (3) described in items [1] and [2] (excluding formula (4)) was coated onto a substrate coated with fluororesin. After heating at a temperature of 180°C or higher for more than 3 hours, the film was peeled off from the substrate after cooling to obtain a self-supporting film.

[0257] [Comparative Example 2] MKC (registered trademark) silicone ester MS51 (Mitsubishi Chemical Co., Ltd., trade name) and dibutyltin dilaurate (DBTL) were added to a polymer solution, coated onto an Afrex (AGC Co., Ltd., trade name) substrate, calcined at 70°C for 10 minutes, calcined at 90°C for 1 hour, calcined at 110°C for 40 minutes, and calcined at 220°C for 2 hours. After cooling, the film was peeled off from the substrate to obtain a self-supporting film.

[0258] [Comparative Example 3] After mixing and stirring the compound (β-5) in a polymer solution containing the formulas (1), (2), and (3) described in items [1] and [2] (excluding formula (4)), the compound was coated onto a substrate coated with fluororesin and calcined at 70°C for 10 minutes, at 90°C for 1 hour, at 110°C for 40 minutes, and at 220°C for 2 hours. However, the mixture became cloudy, had low self-retention properties, and could not obtain a transparent film.

[0259] The results of Examples 1 to 9 and Comparative Examples 1 to 3 are summarized in Tables 3 to 4.

[0260] [Table 3] project unit Example 1 2 3 4 5 6 Siloxane polymers Mw g / mol 47,000 128,000 163,000 115,000 88,000 100,000 Mw / Mn - 4 4 4.8 2.1 2.4 2.9 x unit 3.2 3.2 2.1 3.2 3.2 2.8 y unit 0.4 0.2 0.8 0.5 0.7 1.0 z unit 0.4 0.6 1.2 0.3 0.4 0.6 Content of compound (β-1) % 8 11 twenty four - - - Content of compound (β-2) % - - - 6 8 9 Silicon oxyalkane polymer composition Siloxane polymers g 0.6 0.6 0.6 0.5 0.5 0.5 Compound (β-1) g - - - - - - Crosslinking agent MS51 μl - - - - - - catalyst DBTL ppm - - - - - - solvent PGMEA g 0.4 0.4 0.4 0.5 0.5 0.5 Optical properties Total light transmittance % 93.2 92.5 93.7 92.3 92.8 92.5 Haze % 0.4 0.9 0.7 0.5 0.4 0.3 DMA Glass transition temperature ℃ 69.6 69.5 83.7 111.6 97.7 103.9 Crosslinking density_200℃ mmol / cc 0.09 0.11 0.21 0.12 2.77 11.7 Crosslinking density - 250℃ mmol / cc 0.08 0.08 0.13 0.09 0.77 5.6 TMA CTE 40℃-250℃ ppm / K 142 194 181 161 155 171 40℃-100℃ - - - - - - TG-DTA T d5 ℃ 417 381 372 432 425 421 Mechanical properties Elasticity coefficient GPa 0.69 0.86 0.80 0.91 0.98 1.12 Maximum stress MPa 16 16 twenty three 25 28 33

[0261] [Table 4] project unit Example Comparative example 7 8 9 1 2 3 Siloxane polymers Mw g / mol 112,000 92,000 116,000 29,000 39,000 26,000 Mw / Mn - 2.6 2.9 2.8 1.9 1.9 1.7 x unit 2.8 2.8 3.8 3.2 4.3 2.5 y unit 1.3 0.9 0.8 0.8 0 0.6 z unit 0.3 0.7 0.4 - - - Content of compound (β-1) % - - - - - 7 Content of compound (β-2) % 5 13 7 - - - Silicon oxyalkane polymer composition Siloxane polymers g 0.5 0.5 0.5 0.6 2.6 0.6 Compound (β-1) g - - - - - 0.15 Crosslinking agent MS51 μl - - - - 270 - catalyst DBTL ppm - - - - 2500 - solvent PGMEA g 0.5 0.5 0.5 0.4 1.8 0.4 Optical properties Total light transmittance % 92.5 92.4 92.5 91.4 91 Unable to determine Haze % 0.8 0.4 0.3 2.5 11.8 Unable to determine DMA Glass transition temperature ℃ 104.8 115.7 91.7 49.7 61.4 Unable to determine Crosslinking density_200℃ mmol / cc 8.8 5.2 0.6 0.07 0.10 Unable to determine Crosslinking density - 250℃ mmol / cc 4.5 1.1 0.4 0.07 0.09 Unable to determine TMA CTE 40℃-250℃ ppm / K 164 155 139 - 238 Unable to determine 40℃-100℃ - - - 4018 - Unable to determine TG-DTA T d5 ℃ 420 421 436 484 479 - Mechanical properties Elasticity coefficient GPa 1.17 1.21 1.07 0.31 0.68 - Maximum stress MPa 32 32 28 8 16 -

[0262] The volume resistivity (Ω·cm) of Example 6 and Comparative Examples 1 to 2 was measured. The results are shown in Table 5.

[0263] [Table 5] project unit Example Comparative example 6 1 2 Siloxane polymers Mw g / mol 100,000 29,000 39,000 Mw / Mn - 2.9 1.9 1.9 x unit 2.8 3.2 4.3 y unit 1.0 0.8 0 z unit 0.6 - - Content of compound (β-1) % - - - Content of compound (β-2) % 9 - - Silicon oxyalkane polymer composition Siloxane polymers g 0.5 0.6 2.6 Compound (β-1) g - - - Crosslinking agent MS51 μl - - 270 catalyst DBTL ppm - - 2500 solvent PGMEA g 0.5 0.4 1.8 Electrical properties Volume resistivity_DC250V Ω·cm 2.3×10 16 1.8×10 16 1.0×10 16

[0264] [Example 10] (β-3) was used as compound (β).

[0265]

[0266] The following siloxane polymer can be obtained by the same manufacturing method as in Example 1.

[0267]

[0268] The following examples relate to siloxane polymers (α'). The siloxane polymers were manufactured according to the reaction formulas shown below (Examples 1' to 7').

[0269]

[0270] The synthesis conditions of Examples 1' to 7' are shown in Table 6, and the weight average molecular weight, polydispersity, and x and y relationship of the generated compound (α') are shown in Table 7.

[0271] [Table 6] Example compound Compound XQ1115[g] Compound D4[g] Compound <C> D'4[g] End sealing material catalyst monomer concentration Reaction conditions Temperature [°C] / Time [h] type Quantity [g] type Quantity [g] 1' a'-1 100.0 0.0 30.4 MM 1.20 MSA 6.08 50% 75 / 2 2' a'-2 50.0 15.0 3.0 MM 0.47 MSA 10.13 50% 80 / 3 3' a'-3 50.0 9.4 7.6 MM 0.47 MSA 10.13 50% 80 / 2 4' a'-4 30.0 10.8 2.2 MM 0.03 MSA 2.04 50% 80 / 10 5' a'-5 45.0 14.8 4.0 MM 0.20 MSA 2.21 60% 80 / 8 6' a'-6 150.0 59.1 16.0 MM 0.01 Sulfuric acid 5.77 50% 80 / 3 → 60 / 2 7' a'-7 45.0 15.2 4.1 MM 0.05 Sulfuric acid 2.09 50% 75 / 9

[0272] [Table 7] Example compound Mw PDI Acquisition volume [g] Products 1' a'-1 24,700 2.0 88 x=0, y=average 3.7 2' a'-2 31,800 1.7 27.5 x = average 3.2, y = average 0.8 3' a'-3 28,100 1.7 29 x = average 2.1, y = average 2.0 4' a'-4 74,000 2.0 19 x = average 3.6, y = average 0.8 5' a'-5 59,400 2.0 41 x = average 3.2, y = average 1.1 6' a'-6 68,000 2.1 121 x = average 2.8, y = average 1.6 7' a'-7 91,000 2.4 36 x = average 3.8, y = average 1.2

[0273] [Example 1'] 100 g of compound , 0 g of compound , 30.4 g of compound <C>, and 1.20 g of hexamethyldisiloxane (MM) as an end sealant were added to a 300 mL four-necked round-bottom flask. The mixture was diluted with a 4:1 mixture of toluene and 4-methyltetrahydroxypyran to achieve a monomer concentration of 50% by weight. A thermometer, reflux tube, and oil bath were set up, and nitrogen gas was introduced while stirring with a stirring blade. 6.08 g of methanesulfonic acid was added as an acid catalyst, and the reaction was carried out at 75°C for 2 hours. After cooling to below 50°C, the acid in the system was removed by washing with water. Then, the acid was completely removed by using Kyoward 500SN adsorbent manufactured by Kyowa Chemical Industry Co., Ltd., and the solid was precipitated using heptane as a poor solvent. The precipitated solid was dried under reduced pressure at 80°C for 5 hours to obtain 88 g of white compound (α'-1). The molecular weight of (α'-1) was determined by GPC, and the weight-average molecular weight Mw was 24,700, with a polydispersity Mw / Mn = 2.0. The average values ​​of (x, y) were calculated by 1H-NMR and 29Si-NMR, with x averaging 0 and y averaging 3.7.

[0274] [Examples 2' to 7'] Except for the reaction conditions shown in Table 6, compound (α'-7) was obtained from compound (α'-2) according to Example 1'. The weight-average molecular weight, polydispersity, x, and y of each compound were determined using the method of Example 1, and the results are shown in Table 7.

[0275] For the obtained silicate polymer, a self-supporting film was prepared using the method shown below, and the physical properties were evaluated (Examples 8' to 10').

[0276] [Example 8'] For the silicone polymer, a solution was prepared according to the composition shown in Table 8, coated on a substrate coated with fluororesin, heated at a temperature above 180°C for more than 3 hours, cooled and then peeled off from the substrate to obtain a self-supporting film.

[0277] [Examples 9' to 10'] Except for the composition shown in Table 8, a self-supporting membrane was obtained according to Example 8'.

[0278] [Comparative Example 1', Comparative Example 2'] For the silicate polymer, MKC (registered trademark) silicate MS51 (Mitsubishi Chemical Co., Ltd., trade name) and dibutyltin dilaurate (DBTL) were added according to the composition shown in Table 8, coated on an Afrex (AGC Co., Ltd., trade name) substrate, calcined at 70°C for 10 minutes, calcined at 90°C for 1 hour, calcined at 110°C for 40 minutes, and calcined at 220°C for 2 hours. After cooling, the film was peeled off from the substrate to obtain a self-supporting film. "Comparative Example 1'" is the same as "Comparative Example 2" and is disclosed again for comparison with Examples 8' to 10'.

[0279] The results of Examples 8' to 10' and Comparative Examples 1' and 2' above are summarized in Table 8.

[0280] [Table 8] project unit Example Comparative example 8' 9' 10' 1' 2' Siloxane polymers Mw g / mol 59,400 68,000 91,000 39,000 117,000 Mw / Mn - 2.0 2.1 2.4 1.9 2.5 x unit 3.2 2.8 3.8 4.3 4 y unit 1.1 1.6 1.2 0 0 z unit - - - - - Content of compound (β-1) % - - - - - Content of compound (β-2) % - - - - - Silicon oxyalkane polymer composition Siloxane polymers g 0.5 0.5 0.5 2.6 0.8 Compound (β-1) g - - - - - Crosslinking agent MS51 μl - - - 270 twenty two catalyst Pt-VTSC×3.0 ppm 1 1 1 - - DBTL ppm - - - 2500 2500 solvent PGMEA g 0.5 0.5 0.5 1.8 0.6 Optical properties Total light transmittance % 92.9 92.9 93.2 91.0 91.8 Haze % 0.8 0.5 0.5 11.8 0.6 DMA Glass transition temperature ℃ 77.6 95.5 85.7 61.4 62.5 Crosslinking density_200℃ mmol / cc 6.3 9.4 9.0 0.10 0.06 Crosslinking density - 250℃ mmol / cc 3.4 6.9 6.7 0.09 0.05 TMA CTE 40℃-250℃ ppm / K 162 156 147 238 250 40℃-100℃ - - - - - TG-DTA T d5 ℃ 415 419 415 479 476 Mechanical properties Elasticity coefficient GPa 0.90 0.99 0.90 0.68 0.8 Maximum stress MPa twenty one 25 twenty four 16 19

[0281] The volume resistivity (Ω·cm) of Example 9' and Comparative Example 1' was measured. The results are shown in Table 9 ("Comparative Example 1'" is the same as "Comparative Example 2" and is disclosed again for comparison with the volume resistivity of Example 9').

[0282] [Table 9] project unit Example Comparative example 9' 1' Siloxane polymers Mw g / mol 68,000 39,000 Mw / Mn - 2.1 1.9 x unit 2.8 4.3 y unit 1.6 0 z unit - - Content of compound (β-1) % - - Content of compound (β-2) % - - Silicon oxyalkane polymer composition Siloxane polymers g 0.5 2.6 Compound (β-1) g - - Crosslinking agent MS51 μl - 270 catalyst DBTL ppm - 2500 solvent PGMEA g 0.5 1.8 Electrical properties Volume resistivity_DC250V Ω·cm 1.7×10 16 1.0×10 16 [Industry availability]

[0283] The film obtained by calcining the silicate polymer of the present invention is a material that combines heat resistance, transparency, and a low coefficient of thermal expansion, and is particularly suitable for use as an electronic component. Furthermore, the silicate polymer (α') of the present invention is useful as an intermediate for manufacturing the silicate polymer, and the hardened film of the silicate polymer (α') itself also exhibits excellent heat resistance, thus making it particularly suitable for use as an electronic component. [Simplified Explanation of the Diagram]

[0026] None

Claims

1. A siloxane polymer (α') having repeating units represented by formulas (1), (2) and (4H), with terminal groups represented by formulas (5L) and (5R) at the left and right ends; (formula (5L) represents the terminal group bonded to the left side of the formula, and formula (5R) represents the terminal group bonded to the right side; R0 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 and the cycloalkyl group having 5 to 6 carbon atoms may be independently substituted by a fluorine atom or an alkyl group having 1 to 20 carbon atoms); R1 independently represents a hydrogen atom, 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 group having 6 to 20 carbon atoms, the cycloalkyl group having 5 to 6 carbon atoms, and the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom may be independently substituted 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 may be substituted by a fluorine atom. Any -CH2- may be independently substituted by -O-, -CH=CH-, or an alkyl group having 5 to 20 carbon atoms. In the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently substituted by a fluorine atom. Any -CH2- may be independently substituted by -O- or an alkyl group having 5 to 20 carbon atoms. R2 independently represents hydroxyl, aryl (6-20 carbons), cycloalkyl (5-6 carbons), arylalkyl (7-40 carbons), or alkyl (1-40 carbons). In the aryl group of the 6-20 carbons, the cycloalkyl (5-6 carbons), and the arylalkyl (7-40 carbons), any hydrogen atom may be independently substituted by a fluorine atom or an alkyl group of 1-20 carbons. In the alkyl group of the 7-40 carbons, any hydrogen atom may be substituted by a fluorine atom. Any -CH2- may be independently substituted by -O-, -CH=CH-, or an alkyl group of 5-20 carbons. In the alkyl group of 1-40 carbons, any hydrogen atom may be independently substituted by a fluorine atom. Any -CH2- may be independently substituted by -O- or an alkyl group of 5-20 carbons. R5 independently represents a hydroxyl group, 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. In the aryl groups of the 6 to 20 carbon atoms, the cycloalkyl groups of the 5 to 6 carbon atoms, and the arylalkyl groups of the 7 to 40 carbon atoms, any hydrogen atom may be independently substituted with a fluorine atom or an alkyl group with 1 to 20 carbon atoms. In the alkyl groups of the 7 to 40 carbon atoms, any hydrogen atom may be substituted with a fluorine atom. Any -CH2- group may be independently substituted with -O-, -CH=CH-, or an alkyl group with 5 to 20 carbon atoms. In the alkyl groups of 1 to 40 carbon atoms, any hydrogen atom may be independently substituted with a fluorine atom. Any -CH2- group may be independently substituted with -O- or an alkyl group with 5 to 20 carbon atoms. p represents a real number greater than 1, x is 0.5 to 10, and z is 0.1-8; * indicates the bond position.

2. The siloxane polymer (α') as claimed in claim 1, having repeating units represented by formula (2+4H) and / or formula (4H+2); (R2 represents the same R2 as R2 in formula (4H) of claim 1; x is 0.5 to 10, z is 0.1 to 8).

3. The siloxane polymer (α') as described in claim 1 or claim 2, wherein R2 is independently methyl or phenyl.

4. The siloxane polymer (α') as claimed in claim 1 or claim 2, wherein the weight average molecular weight is 2,000 to 10,000,000.

5. The siloxane polymer (α') as claimed in claim 3, wherein the weight average molecular weight is 2,000 to 10,000,000.

6. A silicate polymer composition comprising the silicate polymer (α') as described in any one of claims 1 to 5 and a solvent.

7. A molded article formed by curing a silicone polymer (α') as described in any one of claims 1 to 5 or a silicone polymer composition as described in claim 6.

8. The molded body as described in claim 7 has electrical insulation properties.

9. A molded article, comprising: A hardened material formed by curing a silicone polymer (α') as described in any one of claims 1 to 5 or a silicone polymer composition as described in claim 6, and a substrate covered by said hardened material.

10. The molded body as described in claim 9 has electrical insulation properties.

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