Siloxane polymer, siloxane polymer composition and molded article

Abstract

A crosslinkable siloxane polymer (α') including a silsesquioxane unit, a linear siloxane unit, and an Si-H group in the main chain is provided, and a cured film having excellent heat resistance in which Si-H groups serve as crosslinking points is provided by applying a composition including the siloxane polymer (α') to a base material and heating and curing.　A siloxane polymer (α') having repeating units represented by formulas (1), (2), and (4H) in which both the left and right ends are end groups represented by formulas (5L) and (5R).

Description

[Technical Field]

[0001] The present invention relates to a novel siloxane polymer in which a cage-type silsesquioxane is introduced into the side chain of a siloxane polymer composed of a double-decker cage-type silsesquioxane (a type of cage-type silsesquioxane) and a linear siloxane, a siloxane polymer composition containing the same, and a molded article. The present invention also relates to a siloxane polymer compound that serves as an intermediate for producing the siloxane polymer. [Background technology]

[0002] Cage silsesquioxanes and double-decker silsesquioxanes, obtained by hydrolysis and condensation of trialkoxysilanes and trichlorosilanes, have a rigid inorganic skeleton similar to the basic structural unit of silica, consisting of Si-O bonds, and have a structure in which an organic group is bonded to each silicon atom. Furthermore, the organic groups (reactive or non-reactive) bonded to the silicon atoms can be selected according to the purpose, such as improving the affinity with various polymer materials or modifying resins through reactions, making them ideal research subjects in the field of organic-inorganic hybrids.

[0003] Polymers containing a cage-type silsesquioxane skeleton in the main chain can significantly improve heat resistance, transparency, hydrophobicity, and other properties that could not be achieved with organic polymers alone, and known examples include polyimide-based polymers (see Non-Patent Documents 1 and 2), polyazomethine-based polymers (see Non-Patent Document 3), and polysiloxane-based polymers (see Non-Patent Document 4).

[0004] Many polymers containing a double-decker silsesquioxane skeleton, a type of cage silsesquioxane, in the main chain are known (see Non-Patent Documents 5 and 6), polysiloxane (see Patent Documents 1 to 5 and Non-Patent Documents 7 to 10), polybenzoxazine (see Non-Patent Document 11), and polyurethane (see Non-Patent Document 12) (see Non-Patent Documents 13 and 14). In particular, for the polysiloxanes, molded articles with excellent transparency and heat resistance have been developed by introducing crosslinkable functional groups into the molecular structure and performing chemical crosslinking with a crosslinking agent (see Patent Documents 3 to 5). [Prior art documents] [Patent documents]

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

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

[0007] Flexible electronic devices using heat-resistant transparent plastic films as substrates not only increase the degree of freedom in shape and broaden the scope of device design, but also have heat resistance during the device manufacturing process, so they are increasingly being incorporated into next-generation devices that require thinness and lightness, such as smartphones, tablets, and organic light-emitting diode (OLED) displays.Intense development is underway not only of transparent polyimides, polyamides, and polyether ether ketones, but also of polymers containing a cage-type silsesquioxane skeleton in the main chain, but many challenges remain, such as improving transparency, heat resistance, linear expansion coefficient, and smoothness.

[0008] For example, in Non-Patent Documents 1 and 2, they have succeeded in synthesizing polyimides containing a cage-type silsesquioxane skeleton in the main chain, and have reported excellent heat resistance (T d5 It has been reported that it exhibits low linear expansion (81.3 ppm / K, room temperature to 350°C), but the transmittance at 360 nm is only at the 80% level, and a slight yellow coloration is observed. In Non-Patent Document 6, a polyimide containing a double-decker silsesquioxane skeleton, which is one of the cage silsesquioxanes, in the main chain was successfully synthesized, and it was reported to have excellent heat resistance (T d5 It has been reported that the polymer also has a low dielectric constant (1 MHz: 2.63, 100 kHz: 2.65) and low water absorption (40-80°C: <1%), but a yellow coloration is observed, suggesting the presence of a charge transfer complex. In Patent Documents 3-5, the synthesis of a siloxane polymer containing a double-decker silsesquioxane skeleton in the main chain was successful, and by introducing a crosslinkable functional group into the molecular structure and using an intermolecular chemical crosslink or a crosslinking agent in combination, it was possible to obtain a polymer that is colorless, transparent, and heat-resistant (T d5 Although molded products with excellent thermal resistance (temperatures ranging from 467 to 540°C) have been developed, many technical challenges remain, such as the time required for intermolecular chemical crosslinking or reaction with crosslinking agents, the high transparency required for flexible electronic devices (haze <1%, total light transmittance >90%), and low linear expansion (<200 ppm). [Means for solving the problem]

[0009] The present inventors have conducted extensive research into methods for creating a siloxane polymer containing a double-decker silsesquioxane skeleton in the main chain, which does not require chemical crosslinking and has high transparency and low linear expansion. As a result, they have discovered that by introducing a cage silsesquioxane skeleton into the side chain of the siloxane polymer, molecular mobility can be suppressed and intermolecular cohesion can be strengthened. Arrival That is, the above-mentioned problems are solved by the present invention.

[0010] The embodiments of the present invention include the following configurations.

[0011] [1] A siloxane polymer having repeating units represented by formulas (1) and (4), and having terminal groups represented by formulas (5L) and (5R) at both the left and right ends. TIFF0007810112000001.tif36112 TIFF0007810112000002.tif2549 (Formula (5L) represents the terminal group attached to the left side of the formula, and formula (5R) represents the terminal group attached to the right side; A represents the following structure: TIFF0007810112000003.tif4154R 0 each independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and any hydrogen atom in the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms; R 1each independently represent a hydrogen atom, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, wherein any hydrogen atom of the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms, wherein any hydrogen atom of the alkylene in the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and wherein any hydrogen atom of the alkylene in the alkyl having 1 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or cycloalkylene having 5 to 20 carbon atoms; R 2 each independently represent a hydroxyl group, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, wherein any hydrogen atom of the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms, wherein any hydrogen atom of the alkylene in the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and wherein any hydrogen atom of the alkylene in the alkyl having 1 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or cycloalkylene having 5 to 20 carbon atoms; R 3 each independently represents an alkylene having 1 to 40 carbon atoms, and in the alkylene having 1 to 40 carbon atoms, any -CH2- may be independently replaced by -O- or a cycloalkylene having 5 to 20 carbon atoms; R 4each independently represent an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, wherein any hydrogen atom of the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms, wherein any hydrogen atom of the alkylene in the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and wherein any hydrogen atom of the alkylene in the alkyl having 1 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or cycloalkylene having 5 to 20 carbon atoms; R 5 each independently represent a hydroxyl group, hydrogen, a crosslinkable functional group which is alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, alkoxyl having 1 to 15 carbon atoms, oxime having 1 to 15 carbon atoms, amino which may have a substituent, amide having 1 to 15 carbon atoms which may have a substituent, aminoxy which may have a substituent, or a vinyl alcohol residue having 2 to 15 carbon atoms which may have a substituent, wherein in the amino and aminoxy which have a substituent, the substituent has 1 to 15 carbon atoms; p represents a real number greater than or equal to 1, z represents a positive real number; * indicates the bond position.)

[0012] [2] The siloxane polymer according to the above item [1], further comprising repeating units represented by formula (2) and / or (3). TIFF0007810112000004.tif3047 (R 2 is R in equation (4) in [1] 2 represents the same thing as; x and y are each independently positive real numbers.)

[0013] [3] The siloxane polymer according to the above item [1], having repeating units represented by the formula (2+4) and / or (4+2). TIFF0007810112000005.tif3078(R 2 is R in equation (4) in [1] 2 represents the same thing as; x and z are each independently positive real numbers.)

[0014] [4] The siloxane polymer according to item [1] or [3] above, having at least one repeating unit selected from the group consisting of repeating units represented by the formulas (4+2+3), (2+4+3), (2+3+4), (4+3+2), (3+4+2), and (3+2+4). TIFF0007810112000006.tif108134(R 2 is R in equation (4) in [1] 2 represents the same thing as; x, y, and z each independently represent a positive real number.)

[0015] [5] R 2 are each independently methyl or phenyl, R 4 are each independently phenyl, isobutyl, cyclopentyl, cyclohexyl, trifluoropropyl, nonafluorohexyl, or pentafluorophenyl.

[0016] [6] The siloxane polymer according to any one of the above items [1] to [5], which has a weight-average molecular weight of 2,000 to 10,000,000.

[0017] [7] A siloxane polymer composition containing the siloxane polymer according to any one of the above items [1] to [6] and a solvent.

[0018] [8] A molded article obtained by curing the siloxane polymer according to any one of the above items [1] to [6] or the siloxane polymer composition according to the above item [7].

[0019] [9] The molded article according to the above item [8], which has a haze value of 1% or less, a thermal decomposition temperature in the range of 350 to 450°C, and a linear expansion coefficient of 200 ppm or less.

[0020]

[10] The molded article according to the above item [8], which has electrical insulation properties.

[0021]

[11] A molded article comprising a cured product obtained by curing the siloxane polymer according to any one of items [1] to [6] above or the siloxane polymer composition according to item [7] above, and a substrate covered with the cured product.

[0022]

[12] The molded article according to the above item

[11] , wherein the difference in haze value between the molded article and the substrate is 1% or less, and the linear expansion coefficient is 200 ppm or less.

[0023]

[13] The molded article according to the above item

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

[0024] The present invention provides a siloxane polymer containing silsesquioxane units and linear siloxane units in its main chain and having cage silsesquioxane structures in its side chains, as well as a method for producing the siloxane polymer. Furthermore, by dissolving the siloxane polymer in an organic solvent, a composition can be applied to a substrate, baked, and then peeled off from the substrate, thereby obtaining a highly transparent, flexible film with a low coefficient of linear thermal expansion that utilizes the cohesive force (physical crosslinking) of the cage silsesquioxanes in the side chains. DETAILED DESCRIPTION OF THE INVENTION

[0025] Hereinafter, the embodiments of the present invention will be described in detail, but the following description is an example (typical example) of the embodiment of the present invention, and the present invention is not limited to these details. Furthermore, the embodiments of the present invention can be combined as appropriate.

[0026] The terms used in this specification are defined as follows. Alkyl and alkylene may be straight-chain or branched. This also applies 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, or the like. The term "any" used in this specification indicates that not only the position but also the number is optional. When there are multiple -CH2-, each may be replaced with a different group. For example, when two -CH2- in an alkyl group are replaced with -O- and -CH=CH-, this represents an alkoxyalkenyl or alkenyloxyalkyl. In this case, the alkoxy, alkenylene, alkenyl, and alkylene groups may be straight-chain or branched. However, when describing that any -CH2- is replaced with -O-, this does not mean that multiple consecutive -CH2- are replaced with -O-. That is, for example, -CH2-CH2- is not replaced with -OO-.

[0027] A siloxane polymer according to one embodiment of the present invention has repeating units represented by formulas (1) and (4), and both the left and right terminals are terminal groups represented by formulas (5L) and (5R). Note that the "both left and right terminals" refers to the structural formula of the siloxane polymer of the present invention. TIFF0007810112000007.tif36112 TIFF0007810112000008.tif2549

[0028] Formula (5L) represents a terminal group attached to the left side of the formula, formula (5R) represents a terminal group attached to the right side, and A represents the following structure: TIFF0007810112000009.tif4154

[0029] The siloxane polymer of the present invention may further have repeating units represented by formula (2) and / or (3). TIFF0007810112000010.tif3047

[0030] The symbols in the formula are as described in the above sections [1] and [2], but will be described in detail later.

[0031] The siloxane polymer of the present invention has repeating units represented by formulas (1) and (4), and this structure constitutes the "main chain." This main chain may further contain repeating units represented by formulas (2) and / or (3). Terminal groups represented by formulas (5L) and (5R) are attached to both ends of the main chain. Formula (5L) represents the terminal group attached to the left side of the formula, and formula (5R) represents the terminal group attached to the right side. Of these, A is attached to formula (4) as a "side chain."

[0032] The side chain represented by A has the following structure: TIFF0007810112000011.tif4154

[0033] 1. Siloxane polymer "main chain" The following examples are given focusing on the "main chain" structure of the siloxane polymer of the present invention. The siloxane polymer of the present invention includes siloxane polymers having main chain structures represented by the following formulae (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 formulae, m represents a real number of 1 or greater, x', y', and z' each independently have the same meaning as x, y, and z, and the meanings of the other symbols are as described in sections [1] and [2] above.

[0034] TIFF0007810112000012.tif39109

[0035] TIFF0007810112000013.tif37126

[0036] TIFF0007810112000014.tif37122

[0037] TIFF0007810112000015.tif37127

[0038] TIFF0007810112000016.tif37126

[0039] TIFF0007810112000017.tif37126

[0040] TIFF0007810112000018.tif37122

[0041] TIFF0007810112000019.tif37127

[0042] TIFF0007810112000020.tif37126

[0043] TIFF0007810112000021.tif37140

[0044] TIFF0007810112000022.tif37136

[0045] TIFF0007810112000023.tif37140

[0046] TIFF0007810112000024.tif37140

[0047] TIFF0007810112000025.tif37140

[0048] TIFF0007810112000026.tif37136

[0049] TIFF0007810112000027.tif37140

[0050] TIFF0007810112000028.tif37140

[0051] TIFF0007810112000029.tif37140

[0052] TIFF0007810112000030.tif37136

[0053] TIFF0007810112000031.tif37140

[0054] TIFF0007810112000032.tif37140

[0055] TIFF0007810112000033.tif39157

[0056] TIFF0007810112000034.tif37155

[0057] TIFF0007810112000035.tif37155

[0058] TIFF0007810112000036.tif37155

[0059] TIFF0007810112000037.tif37155

[0060] TIFF0007810112000038.tif37157

[0061] TIFF0007810112000039.tif37157

[0062] TIFF0007810112000040.tif37157

[0063] TIFF0007810112000041.tif37156

[0064] TIFF0007810112000042.tif37157

[0065] TIFF0007810112000043.tif37157

[0066] TIFF0007810112000044.tif37157

[0067] TIFF0007810112000045.tif37155

[0068] TIFF0007810112000046.tif39151

[0069] TIFF0007810112000047.tif37153

[0070] TIFF0007810112000048.tif39153

[0071] TIFF0007810112000049.tif39153

[0072] TIFF0007810112000050.tif37151

[0073] TIFF0007810112000051.tif37153

[0074] TIFF0007810112000052.tif39151

[0075] TIFF0007810112000053.tif37153

[0076] TIFF0007810112000054.tif39155

[0077] TIFF0007810112000055.tif37153

[0078] TIFF0007810112000056.tif39155

[0079] TIFF0007810112000057.tif39157

[0080] TIFF0007810112000058.tif37155

[0081] TIFF0007810112000059.tif37155

[0082] TIFF0007810112000060.tif37155

[0083] TIFF0007810112000061.tif37155

[0084] TIFF0007810112000062.tif37157

[0085] TIFF0007810112000063.tif37157

[0086] TIFF0007810112000064.tif37157

[0087] TIFF0007810112000065.tif37156

[0088] TIFF0007810112000066.tif37157

[0089] TIFF0007810112000067.tif37157

[0090] TIFF0007810112000068.tif37157

[0091] TIFF0007810112000069.tif37155

[0092] TIFF0007810112000070.tif39151

[0093] TIFF0007810112000071.tif37153

[0094] TIFF0007810112000072.tif39153

[0095] TIFF0007810112000073.tif39153

[0096] TIFF0007810112000074.tif37151

[0097] TIFF0007810112000075.tif37153

[0098] TIFF0007810112000076.tif39151

[0099] TIFF0007810112000077.tif37153

[0100] TIFF0007810112000078.tif39155

[0101] TIFF0007810112000079.tif37153

[0102] TIFF0007810112000080.tif39155

[0103] TIFF0007810112000081.tif36168

[0104] TIFF0007810112000082.tif36168

[0105] TIFF0007810112000083.tif36168

[0106] TIFF0007810112000084.tif36168

[0107] TIFF0007810112000085.tif36168

[0108] TIFF0007810112000086.tif36168

[0109] TIFF0007810112000087.tif36168

[0110] TIFF0007810112000088.tif37167

[0111] TIFF0007810112000089.tif36167

[0112] TIFF0007810112000090.tif36167

[0113] TIFF0007810112000091.tif36167

[0114] TIFF0007810112000092.tif36167

[0115] TIFF0007810112000093.tif36168

[0116] TIFF0007810112000094.tif36168

[0117] TIFF0007810112000095.tif36168

[0118] TIFF0007810112000096.tif36168

[0119] TIFF0007810112000097.tif36168

[0120] TIFF0007810112000098.tif36168

[0121] TIFF0007810112000099.tif36167

[0122] TIFF0007810112000100.tif36167

[0123] TIFF0007810112000101.tif36167

[0124] TIFF0007810112000102.tif36167

[0125] TIFF0007810112000103.tif36167

[0126] TIFF0007810112000104.tif36168

[0127] TIFF0007810112000105.tif36168

[0128] TIFF0007810112000106.tif36168

[0129] TIFF0007810112000107.tif36168

[0130] TIFF0007810112000108.tif36167

[0131] TIFF0007810112000109.tif36168

[0132] TIFF0007810112000110.tif36168

[0133] TIFF0007810112000111.tif36168

[0134] TIFF0007810112000112.tif36168

[0135] TIFF0007810112000113.tif36168

[0136] TIFF0007810112000114.tif36168

[0137] TIFF0007810112000115.tif36168

[0138] TIFF0007810112000116.tif36168

[0139] 2. Siloxane polymer "side chain" In the present invention, the partial structure represented by A is called a "side chain." R in the side chain A 4 and R 3 This is as stated in section [1] above. TIFF0007810112000117.tif4154

[0140] The side chain represented by A specifically includes the structures (A-1) to (A-8) exemplified below.

[0141] In A, R 3 is -CH2CH2CH2-, R 4 Structure (A-1) where is -CH2CH2CF3. TIFF0007810112000118.tif6193

[0142] In A, R 3 is -CH2CH2CH2-, R 4 is phenyl (A-2). TIFF0007810112000119.tif5676

[0143] In A, R 3 is -CH2CH2CH2-, R 4 is cyclohexyl (A-3). TIFF0007810112000120.tif6098

[0144] In A, R 3 is -CH2CH2CH2-, R 4 isobutyl. TIFF0007810112000121.tif67100

[0145] In A, R 3 is -CH2CH2-, R 4 Structure (A-5) where is -CH2CH2CF3. TIFF0007810112000122.tif6193

[0146] In A, R 3 is -CH2CH2-, R 4 The structure (A-6) is -phenyl. TIFF0007810112000123.tif5676

[0147] In A, R 3 is -CH2CH2-, R 4 is cyclohexyl (A-7). TIFF0007810112000124.tif6098

[0148] In A, R 3 is -CH2CH2-, R 4 isobutyl (A-8). TIFF0007810112000125.tif67100

[0149] In the above, R 3 Although examples where R is -CH2CH2- or -CH2CH2CH2- have been given, 3 The structure of R is not limited to these. 3 Other preferred examples include: -CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2- -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2- Examples include:

[0150] In addition to the above (A-1) to (A-8), R 4 is nonafluorohexyl, pentafluorophenyl, or R 4 Among them, a structure having a fluorinated polyether structure can be mentioned.

[0151] 3. Partial structure of siloxane polymer 3-1.(R 0 ) R 0 each independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms. Examples of aryl having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, etc. Among these, phenyl, naphthyl, anthryl, and phenanthryl are preferred, and phenyl, naphthyl, and anthryl are more preferred. Examples of the cycloalkyl having 5 to 6 carbon atoms include cyclopentyl and cyclohexyl. In the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms. R 0 is preferably phenyl or cyclohexyl.

[0152] 3-2.(R 1 ) R 1 are independently a hydrogen atom, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms. An aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms is represented by R 0Examples include those similar to those described above. Examples of the arylalkyl 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 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 of the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the aryl of the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom or an alkyl of 1 to 20 carbon atoms; in the alkylene of the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, or any -CH2- may be independently replaced by -O-, -CH=CH-, or cycloalkylene of 5 to 20 carbon atoms; and in the alkyl of 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, or any -CH2- may be independently replaced by -O- or cycloalkylene of 5 to 20 carbon atoms. R 1 is preferably selected from a hydrogen atom, phenyl, cyclohexyl, and alkyl having 1 to 5 carbon atoms, and more preferably selected from alkyl having 1 to 5 carbon atoms.

[0153] 3-3.(R 2 , R 5 ) R 2 , R 5 independently represent a hydroxyl group, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms. Aryl having 6 to 20 carbon atoms and cycloalkyl having 5 to 6 carbon atoms are R 0Examples include those similar to those described above. The arylalkyl having 7 to 40 carbon atoms includes R 1 Examples include those similar to those described above. As the alkyl having 1 to 40 carbon atoms, R 1 Examples include those similar to those described above. In the aryl of the aryl having 6 to 20 carbon atoms, the cycloalkyl of 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms; in the alkylene of the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, or any —CH— may be independently replaced by —O—, —CH═CH—, or cycloalkylene having 5 to 20 carbon atoms; and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, or any —CH— may be independently replaced by —O— or cycloalkylene having 5 to 20 carbon atoms. R 2 , R 5 is preferably selected from phenyl, cyclohexyl, and alkyl having 1 to 40 carbon atoms, and more preferably selected from alkyl having 1 to 5 carbon atoms.

[0154] 3-4.(p) p represents a real number of 1 or more. From the viewpoint of production, it is preferably 1 or more and 3,000 or less, and more preferably 1 or more and 300 or less.

[0155] 3-5.(x, y) x is a value that depends on the amount of repeating units having the structure of formula (2) contained in the main chain of the siloxane polymer, and is 0 if the structure of formula (2) is not contained. The content of the repeating units of formula (2) varies depending on the amount of moieties corresponding to the same structure added as raw materials for the siloxane polymer, and the physical properties of the siloxane polymer can be controlled by adjusting this amount. The preferred range of x is 0.5 to 10.

[0156] y is a repeating unit (structure represented by formula (3)) contained in a certain proportion in the intermediate in the stage of producing the siloxane polymer of the present invention, and the structure of side chain A is introduced into this -Si-H moiety by an addition reaction (the method for producing the siloxane polymer of the present invention will be described in detail later). Therefore, the value of y depends on the proportion of the structure of side chain A introduced. The value of y is 0 when the structure of side chain A is introduced into all of the -Si-H moieties of the intermediate. The preferred range of y is 0.1 to 8.

[0157] 3-6.(z) The value of z is determined by how much of the structure A has been introduced into the side chain of the siloxane polymer. The preferred range of z is 0.2 to 5.

[0158] 4. Method for producing siloxane polymers The method for producing the siloxane polymer of the present invention will now be described. First, a siloxane polymer having a structure in which the moiety A of the siloxane polymer of the present invention is replaced with a hydrogen atom is prepared. This siloxane polymer is referred to herein as "intermediate (α)." Compound (β) corresponding to the structure of A is introduced into the -Si-H moiety of intermediate (α) by an addition reaction, elimination reaction, or substitution reaction.

[0159] For example, as shown in the following reaction scheme, it can be produced by introducing a compound represented by formula (β) into a siloxane polymer intermediate represented by formula (α) through an addition reaction.

[0160] TIFF0007810112000126.tif114161

[0161] The compound (β) above corresponds to the side chain A, and in this example, the terminal double bond undergoes an addition reaction with the silicon atom of the siloxane polymer intermediate (α). In this example, R 3 The structure of 'R' 3 The structure has two fewer carbon atoms (the two carbon atoms become -CH=CH2 and participate in the addition reaction).

[0162] The compounds (β) corresponding to the above-mentioned side chains A (A-1) to (A-8) are the following (β-1) to (β-8), respectively.

[0163] TIFF0007810112000127.tif6191

[0164] TIFF0007810112000128.tif5675

[0165] TIFF0007810112000129.tif5897 TIFF0007810112000130.tif67101

[0166] TIFF0007810112000131.tif5185

[0167] TIFF0007810112000132.tif4671

[0168] TIFF0007810112000133.tif4997

[0169] TIFF0007810112000134.tif5796

[0170] In the above example, R 3 The structures of the parts corresponding to R are -CH=CH2 and -CH2CH=CH2. 3 When it is desired to introduce an alkylene having 4 to 12 carbon atoms as the alkylene group, the following groups are suitable. -CH2CH2CH=CH2, -CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2 -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2.

[0171] The siloxane polymer of the present invention can be produced by subjecting these compounds (β) to an addition reaction with the siloxane polymer intermediate (α). A preferred example of the addition reaction is known to be the hydrosilylation reaction using a Karstedt catalyst.

[0172] Also, R 3 When a side chain having -CH2- is introduced, the following compounds can be selected as starting materials for (β).

[0173] TIFF0007810112000135.tif4183

[0174] Also, R 3 When a side chain in which is -O- is introduced, it can be produced by introducing a compound represented by compound (β) into siloxane polymer intermediate (α) by dehydrogenation reaction, as shown in the following reaction formula.

[0175] TIFF0007810112000136.tif102167

[0176] The above compound (β OH ) corresponds to side chain A, and in this example, the terminal silanol group undergoes a dehydrogenation reaction with the hydrosilyl group of the siloxane polymer intermediate (α) in the presence of a boron compound catalyst.

[0177] Also, R 2 Siloxane polymer intermediate (α OH The siloxane polymer of the present invention can be produced by an elimination reaction or substitution reaction between the compound (β) and the compound (β).

[0178] TIFF0007810112000137.tif103166

[0179] The above compound (β H ) corresponds to the side chain A, and in this example, the terminal hydrosilyl group is a siloxane polymer intermediate (α OH ) undergoes a dehydrogenation reaction with the silanol groups in the presence of a boron compound catalyst.

[0180] TIFF0007810112000138.tif106165

[0181] The above compound (β OH ) corresponds to the side chain A, and in this example, the terminal silanol group is a siloxane polymer intermediate (α OH ) undergoes dehydration condensation with the silanol groups under acidic conditions.

[0182] TIFF0007810112000139.tif106166

[0183] The above compound (β Cl ) corresponds to the side chain A, and in this example, the terminal chlorosilane is a siloxane polymer intermediate (α OH This reaction can be easily accelerated by adding a compound with an amino group, such as triethylamine (TEA), or a basic organic compound.

[0184] 4-1-a. Siloxane polymer intermediate (α) The siloxane polymer intermediate (α) (hereinafter simply referred to as "intermediate (α)") is useful as a raw material for producing the siloxane polymer of the present invention. In addition, as will be described later, the intermediate (α) can be converted into the intermediate (α) by converting the hydrogen atom of Si-H to a silanol group in the presence of a transition metal catalyst. OH ) can also be used as a raw material for manufacturing the intermediate (α). Furthermore, the intermediate (α) itself is not just an "intermediate" but can also be used as a material after hardening. Therefore, the intermediate (α) can also be considered a useful invention.

[0185] Here, when the intermediate (α) is regarded as an invention, it is redefined as a siloxane polymer (α') as follows.

[0186] [1'] Equations (1), (2) and (4 H and a siloxane polymer (α') having a repeating unit represented by the formula (5L) and a terminal group represented by the formula (5R) at both the left and right ends. TIFF0007810112000140.tif39135 TIFF0007810112000141.tif2549 (Formula (5L) represents the terminal group attached to the left side of the formula, and formula (5R) represents the terminal group attached to the right side; R 0 each independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and any hydrogen atom in the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms; R 1 each independently represent a hydrogen atom, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, wherein any hydrogen atom of the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms, wherein any hydrogen atom of the alkylene in the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and wherein any hydrogen atom of the alkylene in the alkyl having 1 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or cycloalkylene having 5 to 20 carbon atoms; R 2each independently represent a hydroxyl group, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, wherein any hydrogen atom of the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms, wherein any hydrogen atom of the alkylene in the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and wherein any hydrogen atom of the alkylene in the alkyl having 1 to 40 carbon atoms may be independently replaced by a fluorine atom, and any -CH2- may be independently replaced by -O- or cycloalkylene having 5 to 20 carbon atoms; R 5 each independently represent a hydroxyl group, hydrogen, a crosslinkable functional group which is alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, alkoxyl having 1 to 15 carbon atoms, oxime having 1 to 15 carbon atoms, amino which may have a substituent, amide having 1 to 15 carbon atoms which may have a substituent, aminoxy which may have a substituent, or a vinyl alcohol residue having 2 to 15 carbon atoms which may have a substituent, wherein in the amino and aminoxy which have a substituent, the substituent has 1 to 15 carbon atoms; p represents a real number greater than or equal to 1, and x and z each independently represent a positive real number; * indicates the bond position.)

[0187] [2'] Expression(2+4 H ) and / or (4 H The siloxane polymer (α') according to item [1'], having a repeating unit represented by the formula: TIFF0007810112000142.tif3895 (R 2 teeth, [ 1 '] term In equation (4 H ) in R 2 represents the same thing as; Each x is independently 0 or a positive real number, and each z is independently a positive real number.)

[0188] [3'] R 2 are each independently methyl or phenyl.

[0189] [4'] The siloxane polymer (α') according to any one of items [1'] to [3'], which has a weight-average molecular weight of 2,000 to 10,000,000.

[0190] [5'] A siloxane polymer composition containing the siloxane polymer (α') according to any one of items [1'] to [4'] and a solvent.

[0191] [6'] The siloxane polymer (α') according to any one of items [1'] to [4'], or [ 5 '] term 2. A molded article obtained by curing the siloxane polymer composition according to claim 1.

[0192] [7'] The molded article according to item [6'], which has electrical insulation properties.

[0193] [8'] The siloxane polymer (α') according to any one of items [1'] to [4'], or [5'] term 1. A molded article comprising a cured product obtained by curing the siloxane polymer composition according to claim 1, and a substrate covered with the cured product.

[0194] [9'] A molded article according to claim [8'], having electrical insulation properties.

[0195] The effects of the siloxane polymer (α') as an invention are not only that it provides a siloxane polymer (α') containing silsesquioxane units and linear siloxane units in its main chain and a method for producing the siloxane polymer (α'), but also that by dissolving the siloxane polymer (α') in an organic solvent and applying the resulting composition to a substrate and curing it by heating, the Si-H groups become crosslinking points, thereby producing a cured coating with excellent heat resistance. Furthermore, because functional groups can be introduced into the Si-H groups of the siloxane polymer (α'), it is also useful as an intermediate for producing a siloxane polymer whose heat resistance and mechanical properties can be highly controlled.

[0196] 4-1-b. Method for producing intermediate (α) Many examples of methods for producing the intermediate (α) are known, including the following compounds: and compounds and compounds <c> The compound is obtained by equilibrium polymerization of the compound in the presence of an acid catalyst.< / c> is the following compound <d>and the compound <e>or compounds <f>and then hydrolyzing the reactant (see, for example, paragraph 0032 of JP-A-2006-022207). However, the specific structure of the intermediate (α) or the siloxane polymer (α') is not known.

[0197] TIFF0007810112000143.tif4376

[0198] TIFF0007810112000144.tif40101

[0199] TIFF0007810112000145.tif4381

[0200] TIFF0007810112000146.tif2684

[0201] 4-2. Intermediate (α OH ) manufacturing method Intermediate (α OH The compound (A) can be produced, for example, by converting the intermediate (α) into a silanol group in the presence of a transition metal catalyst.

[0202] TIFF0007810112000147.tif110145

[0203] 4-3. Method for producing compound (β) A method for producing compound (β) will also be explained. The compound (β) can be produced by reacting the compound (β-0) with allyltrichlorosilane.

[0204] TIFF0007810112000148.tif46150

[0205] Compound (β OH ) can be produced by hydrolyzing compound (β-0).

[0206] TIFF0007810112000149.tif51100

[0207] Compound (β Cl ) can be produced by reacting compound (β-0) with tetrachlorosilane.

[0208] TIFF0007810112000150.tif50119

[0209] Compound (β H ) can be produced by reacting compound (β-0) with trichlorosilane.

[0210] TIFF0007810112000151.tif53120

[0211] Many examples of methods for producing the compound (β-0) are known. For example, it can be produced by hydrolyzing trifluoropropyltrimethoxysilane in the presence of an alkali metal hydroxide and then polycondensing it.

[0212] TIFF0007810112000152.tif47114

[0213] These manufacturing methods are described, for example, in paragraph 32 of Japanese Patent Application Laid-Open No. 2005-15738.

[0214] 5. Solvent The siloxane polymer of the present invention can be used as a siloxane polymer composition further containing a solvent. Such a solvent is preferably one that can dissolve the siloxane polymer but does not condense with the crosslinkable silicon compound or crosslinkable compound. Examples of such solvents include hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF), and dioxane, halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, and ester solvents such as ethyl acetate. The solvent may be a single solvent or a mixture of two or more solvents. From the standpoint of coatability, the content of the solvent is preferably an amount that results in a siloxane polymer content of 20 to 80% by mass, more preferably an amount that results in a siloxane polymer content of 30 to 70% by mass, and even more preferably an amount that results in a siloxane polymer content of 40 to 60% by mass.

[0215] 6. Baked products and films By baking the siloxane polymer of the present invention or a siloxane polymer composition containing a solvent, a highly transparent, flexible baked product with a low coefficient of linear thermal expansion can be obtained. The baking temperature is preferably 150 to 250°C. This baked product can be used as a film. Specifically, the baking may be carried out by applying the siloxane polymer composition to a substrate and then heating the composition in an oven or the like. The baking temperature and time are not particularly limited as long as the siloxane polymer can be made into a film (self-supporting film). After the baked siloxane polymer is allowed to cool, it can be peeled off from the substrate as a film. The substrate is not particularly limited as long as it can withstand the baking temperature and the film formed on the substrate can be peeled off from the substrate and removed as a free-standing film. Examples of suitable substrates include glass substrates such as quartz, barium borosilicate glass, and aluminoborosilicate glass; calcium fluoride substrates; metal oxide substrates such as indium tin oxide (ITO); ceramic substrates; plastic films such as polycarbonate (PC) film, silicone film, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, cycloolefin polymer (COP) film, polypropylene film, polyethylene film, acrylic polymer film, polyvinyl alcohol film, triacetyl cellulose film, and polyimide (PI) film; fluororesin substrates such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA); laminate substrates such as glass coated with a fluororesin; and metal substrates such as stainless steel and copper. [Example]

[0216] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited by these descriptions.

[0217] The measurements in the examples were carried out as follows.

[0218] GPC Gel Permeation Chromatography <Measurement conditions> Column: Showa Denko Shodex KF-804L 300 x 8.0 mm Showa Denko Shodex KF-805L 300 x 8.0 mm, 2 pieces 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

[0219] ·DMA Dynamic Viscoelasticity Measurement <Measurement conditions> Hitachi High-Tech Science DMS6100 5℃ / min, sample area 10mm x 1mm Load 10mN, measurement frequency 10 Hz

[0220] ·TMA thermomechanical analysis <Measurement conditions> Hitachi High-Tech Science SS / TMA6100 Tensile mode, 10℃ / min, length 20mm, cross-sectional area 0.3mm 2 Load 9.8 mN

[0221] ·TG-DTA thermogravimetric differential thermal analysis <Measurement conditions> Measurement equipment: Seiko Instruments EXSTAR6000 TG / DTA6300 Bread: Pt Standard sample: aluminum oxide (10 mg) Sample mass: approx. 10 mg Temperature program: 25 to 800°C Heating rate: 10℃ / min

[0222] Total light transmittance: The total light transmittance was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JISK 7361-1.

[0223] Haze: Haze (cloudiness, haze) was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7136.

[0224] Glass transition temperature: The temperature at the top of the loss modulus (E") peak in dynamic viscoelasticity measurements by DMA.

[0225] Crosslink density: The crosslink density was calculated using the formula (1). n=E' / 3RT (1) In equation (1), n: crosslink density (mol / m3), E': storage modulus (Pa), R: gas constant ((Pa·m3) / K·mol), T: temperature (K)

[0226] Coefficient of linear expansion (CTE): Measured by TMA. The coefficient of linear expansion was calculated from the TMA results of the first scan (first heating, heating rate: 10°C / min) in the temperature range of 40°C to 250°C.

[0227] ·Thermal decomposition temperature (T d5 ): Measured by TG-DTA. Temperature at which 5% weight loss occurs.

[0228] Elastic modulus: Measured using a Tensilon universal testing machine RTF-1310 (manufactured by A&D Co., Ltd.) at a tensile speed of 5 mm / min at room temperature. No. 8 dumbbells were used to prepare test specimens, and the tangent to the maximum slope of the stress / strain curve before the film underwent plastic deformation was measured.

[0229] Maximum stress: Measured using a Tensilon universal testing machine RTF-1310 (manufactured by A&D Co., Ltd.) at a tensile speed of 5 mm / min at room temperature. No. 8 dumbbells were used to prepare the test specimens, and the maximum stress measured until the specimen broke was the maximum value.

[0230] Volume resistivity: Using a femto-picoammeter B2981A, controller GP-32, controller GP-HV, and test fixture N1259A (manufactured by Keysight Technologies, Inc.), the volume resistivity was calculated from the resistance value at an applied voltage of 250 V. The test specimen was a Cr-plated substrate on which a siloxane polymer film was formed using a spin coater, baked, and then Al was vapor-deposited.

[0231] Siloxane polymers were produced according to the reaction formula shown below (Examples 1 to 3), and their physical properties were evaluated. Solutions of the obtained siloxane polymers were prepared with the compositions shown in Table 3, which were then applied to a substrate coated with a fluororesin and heated at a temperature of 180°C or higher for 3 hours or more. After allowing to cool, the film was peeled off from the substrate to obtain a free-standing film.

[0232] TIFF0007810112000153.tif98166

[0233] Table 1 shows the relationships between x, y, and z in the intermediate (α), compound (β-1), and product in Examples 1 to 3.

[0234] [Table 1]

[0235] [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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. 2.1 μL of Pt-VTSC×3.0 (Umicore Japan) was added at 70 °C, and the mixture was stirred at reflux 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 off, and the filtrate was concentrated at 50 °C. PGMEA was added to the concentrated solution, and the ethyl acetate was removed by vacuum concentration, yielding 10.9 g of (A) solution with a solids concentration of 60%. The molecular weight of (A) was measured by GPC. The weight average molecular weight Mw was 47,000, and the polydispersity Mw / Mn was 4.0. The average values ​​of (x, y, z) were 1 H-NMR, 29 Calculations from Si-NMR measurements showed that x was 3.2 on average, y was 0.41 on average, and z was 0.39 on average.

[0236] ( 1 H-NMR measurement results) 1 H-NMR (400MHz, CO(CD3)2)δ:7.17~7.66(Ph), 4.65~4.74(Si-H), 2.34(CF3C H 2), 1.51~1.60(CH2), 1.02(CF3CH2C H 2), 0.65~0.87(CH2), 0.27~0.41(O3SiMe), -0.04~0.13(O2SiMe2). ( 29 Si-NMR measurement results) 29 Si-NMR(99MHz, 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

[0237] [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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. 2.1 μL of Pt-VTSC×3.0 (Umicore Japan) was added at 70 °C, and the mixture was stirred at reflux 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 off, and the filtrate was concentrated at 50 °C. PGMEA was added to the concentrated solution, and the ethyl acetate was removed by vacuum concentration, yielding 11.6 g of (B) solution with a solids concentration of 60%. The molecular weight of (B) was measured by GPC. The weight average molecular weight Mw was 128,000, and the polydispersity Mw / Mn was 4.0. The average value of (x, y, z) 1 H-NMR, 29 Calculations from Si-NMR measurements showed that x was 3.2 on average, y was 0.24 on average, and z was 0.56 on average.

[0238] ( 1 H-NMR measurement results) 1 H-NMR (400MHz, CO(CD3)2)δ:7.17~7.65(Ph), 4.64~4.82(Si-H), 2.33(CF3C H 2), 1.49~1.58(CH2), 1.01(CF3CH2C H 2), 0.61~0.89(CH2), 0.26~0.39(O3SiMe), -0.06~0.12(O2SiMe2). ( 29 Si-NMR measurement results) 29 Si-NMR(99MHz, 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

[0239] [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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. 6.0 μL of Pt-VTSC×3.0 (Umicore Japan) was added at 70 °C, and the mixture was stirred at reflux 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 off, and the filtrate was concentrated at 50 °C. PGMEA was added to the concentrated solution, and the ethyl acetate was removed by vacuum concentration, yielding 15.5 g of (C) solution with a solids concentration of 60%. The molecular weight of (C) was measured by GPC. The weight average molecular weight Mw was 163,000, and the polydispersity Mw / Mn was 4.8. The average values ​​of (x, y, z) 1 H-NMR, 29 Calculations from Si-NMR measurements showed that x was 2.1 on average, y was 0.79 on average, and z was 1.21 on average.

[0240] ( 1 H-NMR measurement results) 1 H-NMR (400MHz, CO(CD3)2)δ:7.23~7.69(Ph), 4.67~4.86(Si-H), 2.36(CF3C H 2), 1.52~1.62(CH2), 1.04(CF3CH2C H 2), 0.64~0.89(CH2), 0.29~0.43(O3SiMe), 0.00~0.17(O2SiMe2). ( 29 Si-NMR measurement results) 29 Si-NMR(99MHz, 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

[0241] [Example 4] (β-5) is used as compound (β).

[0242] TIFF0007810112000155.tif5185

[0243] A siloxane polymer of the following formula can be obtained by the same production method as in Example 1. TIFF0007810112000156.tif45162

[0244] Siloxane polymers were produced according to the reaction formula shown below (Examples 4 to 9), and their physical properties were evaluated. Solutions of the obtained siloxane polymers were prepared with the compositions shown in Tables 3 and 4, which were then applied to a substrate coated with a fluororesin and heated at a temperature of 180°C or higher for 3 hours or more. After allowing to cool, the film was peeled off from the substrate to obtain a free-standing film.

[0245] TIFF0007810112000157.tif86143

[0246] Table 2 shows the relationships between x, y, and z in the intermediate (α), compound (β-2), and product in Examples 4 to 9.

[0247] [Table 2]

[0248] [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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. At 60 °C, 2.1 μL of Pt-VTSC×3.0 (Umicore Japan) was added, and the mixture was stirred at reflux for 3 hours. An additional 2.1 μL of Pt-VTSC×3.0 was added, and the mixture was stirred at reflux for 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 off, and the filtrate was concentrated at 50 °C. The concentrated mixture was added dropwise to 200 mL of heptane, yielding 4.2 g of a white polymer precipitate. The molecular weight of the polymer was measured by GPC, and the weight average molecular weight Mw was 115,000, and the polydispersity Mw / Mn was 2.1. 1 Calculations from H-NMR showed that x was 3.6 on average, y was 0.48 on average, and z was 0.32 on average. ( 1 H-NMR measurement results) 1 H-NMR (400MHz, 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).

[0249] [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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. At 60 °C, 3.0 μL of Pt-VTSC×3.0 (Umicore Japan) was added, and the mixture was stirred at reflux for 3 hours. An additional 3.0 μL of Pt-VTSC×3.0 was added, and the mixture was stirred at reflux for 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 off, and the filtrate was concentrated at 50 °C. The concentrated mixture was added dropwise to 200 mL of heptane, yielding 4.7 g of a white polymer precipitate. The molecular weight of the polymer was measured by GPC, and the weight average molecular weight Mw was 88,000, and the polydispersity Mw / Mn was 2.4. 1 Calculations from H-NMR showed that x was 3.3 on average, y was 0.68 on average, and z was 0.42 on average. ( 1 H-NMR measurement results) 1 H-NMR (400MHz, 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).

[0250] [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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. At 60 °C, 14 μL of Pt-VTSC×3.0 (Umicore Japan) was added, and the mixture was stirred at reflux for 3.5 hours. Another 14 μL of Pt-VTSC×3.0 was added, and the mixture was stirred at reflux for 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 off, and the filtrate was concentrated at 50 °C. This concentrated solution was added dropwise to 1.5 L of heptane, yielding 33.7 g of a white polymer precipitate. The molecular weight of the polymer was measured by GPC, and the weight average molecular weight Mw was 100,000 and the polydispersity Mw / Mn was 2.9. 1 Calculations from H-NMR showed that x was 2.8 on average, y was 1.12 on average, and z was 0.48 on average. ( 1 H-NMR measurement results) 1 H-NMR (400MHz, 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 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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. 2.5 μL of Pt-VTSC×3.0 (Umicore Japan) was added at 60 °C, and the mixture was stirred at reflux 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 off, and the filtrate was concentrated at 50 °C. This concentrated solution was added dropwise to 300 mL of heptane, yielding 6.1 g of a white polymer precipitate. The molecular weight of the polymer was measured by GPC, and the weight average molecular weight Mw was 112,000, and the polydispersity Mw / Mn was 2.6. 1 Calculations from H-NMR showed that x was 2.8 on average, y was 1.33 on average, and z was 0.27 on average. ( 1 H-NMR measurement results) 1 H-NMR (400MHz, 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 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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. At 60 °C, 3.3 μL of Pt-VTSC×3.0 (Umicore Japan) was added, and the mixture was stirred at reflux for 3 hours. An additional 3.3 μL of Pt-VTSC×3.0 was added, and the mixture was stirred at reflux for 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 off, and the filtrate was concentrated at 50 °C. The concentrated mixture was added dropwise to 300 mL of heptane, yielding 7.4 g of a white polymer precipitate. The molecular weight of the polymer was measured by GPC, and the weight average molecular weight Mw was 92,000, and the polydispersity Mw / Mn was 2.9. 1 Calculations from H-NMR showed that x was 2.8 on average, y was 0.91 on average, and z was 0.69 on average. ( 1 H-NMR measurement results) 1 H-NMR (400MHz, 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 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-neck round-bottom flask. A thermometer, reflux condenser, stirrer, and oil bath were attached, and the mixture was stirred under nitrogen flow. 2.7 μL of Pt-VTSC×3.0 (Umicore Japan) was added at 60 °C, and the mixture was stirred at reflux 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 off, and the filtrate was concentrated at 50 °C. This concentrated solution was added dropwise to 200 mL of heptane, yielding 5.4 g of a white polymer precipitate. The molecular weight of the polymer was measured by GPC, and the weight average molecular weight Mw was 116,000, and the polydispersity Mw / Mn was 2.8. 1 Calculations from H-NMR showed that x was 3.8 on average, y was 0.78 on average, and z was 0.42 on average. ( 1 H-NMR measurement results) 1 H-NMR (400MHz, 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] [Comparative Example 1] A polymer solution composed of the formulas (1), (2), and (3) (excluding formula (4)) described in the above items [1] and [2] was applied to a substrate coated with a fluororesin, heated at a temperature of 180°C or higher for 3 hours or more, and then allowed to cool. The film was then peeled off from the substrate to obtain a free-standing film.

[0255] Comparative Example 2 MKC (registered trademark) Silicate MS51 (trade name, Mitsubishi Chemical Corporation) and dibutyltin dilaurate (DBTL) were added to the polymer solution, which was then applied to an Aflex (trade name, AGC Corporation) substrate. The resulting film was baked 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. After allowing it to cool, the film was peeled off from the substrate to obtain a free-standing film.

[0256] Comparative Example 3 Compound (β-5) was mixed and stirred with a polymer solution composed of formulas (1), (2), and (3) (not including formula (4)) described in items [1] and [2] above, and then applied to a substrate coated with a fluororesin. The solution was then baked at 70°C for 10 minutes, 90°C for 1 hour, 110°C for 40 minutes, and 220°C for 2 hours, but the resulting film became cloudy and had poor self-sustaining properties, making it impossible to obtain a transparent film.

[0257] The results of Examples 1 to 9 and Comparative Examples 1 to 3 are summarized in Tables 3 and 4.

[0258] [Table 3]

[0259] [Table 4]

[0260] The volume resistivity (Ω·cm) was measured for Example 6 and Comparative Examples 1 and 2. The results are shown in Table 5.

[0261] [Table 5]

[0262] [Example 10] (β-3) is used as the compound (β).

[0263] TIFF0007810112000162.tif5897

[0264] A siloxane polymer of the following formula can be obtained by the same production method as in Example 1.

[0265] TIFF0007810112000163.tif48167

[0266] The following examples relate to siloxane polymer (α'). Siloxane polymers were produced according to the reaction formula shown below (Examples 1' to 7').

[0267] TIFF0007810112000164.tif72141

[0268] Table 6 shows the synthesis conditions in Examples 1' to 7', and Table 7 shows the weight average molecular weight, polydispersity, and relationship between x and y of the compound (α') produced.

[0269] [Table 6]

[0270] [Table 7]

[0271] [Example 1'] compound< / f> < / e> < / d> 100g, compound 0g, compound <c>30.4 g of α-methyldisiloxane and 1.20 g of hexamethyldisiloxane (MM) as an end-capping agent were added to a 300 mL four-neck round-bottom flask and diluted with a 4:1 mixture of toluene and 4-methyltetrahydroxypyran to a monomer concentration of 50 wt%. A thermometer, reflux tube, and oil bath were attached, and nitrogen was passed through the mixture 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. The acid was then completely removed using Kyowa Chemical Industry Co., Ltd.'s Kyoward 500SN adsorbent, and a solid was precipitated using heptane as a poor solvent. The precipitated solid was dried under reduced pressure at 80 °C for 5 hours, yielding 88 g of a white compound (α'-1). The molecular weight of (α'-1) was measured by GPC, and the weight average molecular weight Mw was 24,700, and the polydispersity Mw / Mn was 2.0. 1 H-NMR, 29 Calculations based on Si-NMR measurements revealed that x was 0 on average and y was 3.7 on average.

[0272] [Examples 2' to 7'] Compound (α'-7) was obtained from compound (α'-2) in accordance with Example 1', except that the reaction was carried out under the conditions shown in Table 6. The weight average molecular weight, polydispersity index, x, and y of each compound were measured by the method of Example 1, and the results are shown in Table 7.

[0273] The obtained siloxane polymer was prepared into a free-standing film by the method described below, and the physical properties were evaluated (Examples 8' to 10').

[0274] [Example 8'] A solution of siloxane polymer was prepared with the composition shown in Table 8. Made The film was then applied to a substrate coated with a fluororesin, heated at a temperature of 180°C or higher for 3 hours or more, allowed to cool, and then peeled off from the substrate to obtain a free-standing film.

[0275] [Examples 9'-10'] A self-supporting membrane was obtained in the same manner as in Example 8' except for the composition shown in Table 8.

[0276] [Comparative Examples 1' and 2'] Siloxane polymer was used in the composition shown in Table 8. MKC (registered trademark) Silicate MS51 (trade name, Mitsubishi Chemical Corporation) and dibutyltin dilaurate (DBTL) were added, and the mixture was applied to an Aflex (trade name, AGC Corporation) substrate. The mixture was baked 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. After allowing to cool, the film was peeled off from the substrate to obtain a free-standing film. "Comparative Example 1'" is the same as the above-mentioned "Comparative Example 2", but is listed again for comparison with Examples 8' to 10'.

[0277] The results of Examples 8' to 10' and Comparative Examples 1' and 2' are summarized in Table 8.

[0278] [Table 8]

[0279] The volume resistivity (Ω·cm) was measured for Example 9' and Comparative Example 1'. The results are shown in Table 9. ("Comparative Example 1'" is the same as "Comparative Example 2" above. It is listed again for comparison of volume resistivity with Example 9'.)

[0280] [Table 9] [Industrial Applicability]

[0281] The film obtained by baking the siloxane polymer of the present invention is a material that combines heat resistance, transparency, and a low linear thermal expansion coefficient, and is particularly suitable for use as an electronics component. The siloxane polymer (α') of the present invention is useful as an intermediate for producing the siloxane polymer, and a cured film of the siloxane polymer (α') itself also exhibits excellent heat resistance, making it particularly suitable for use as an electronics component.< / c>

Claims

1. Formulas (1), (2) and (4) H and a siloxane polymer (α′) having a repeating unit represented by the formula (5L) and a terminal group represented by the formula (5R) at both the left and right ends. (Formula (5L) represents a terminal group attached to the left side of the formula, and formula (5R) represents a terminal group attached to the right side of the formula; R ０ each independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and any hydrogen atom in the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms; R １ each independently represents a hydrogen atom, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, and any hydrogen atom of the aryl in the aryl having 6 to 20 carbon atoms and the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom or an alkylene having 1 to 20 carbon atoms, any hydrogen atom of the alkylene in the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom, and any —CH ２ - may be independently replaced by -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH ２ - may be independently replaced by -O- or cycloalkylene having 5 to 20 carbon atoms; R ２ each independently represents a hydroxyl group, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, and any hydrogen atom of the aryl in the aryl having 6 to 20 carbon atoms and the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms, any hydrogen atom of the alkylene in the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom, and any —CH ２ - may be independently replaced by -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced by a fluorine atom, and any -CH ２ - may be independently replaced by -O- or cycloalkylene having 5 to 20 carbon atoms; R ５ each independently represent a hydroxyl group, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, wherein any hydrogen atom of the aryl in the aryl having 6 to 20 carbon atoms and the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom or an alkyl having 1 to 20 carbon atoms, any hydrogen atom of the alkylene in the arylalkyl having 7 to 40 carbon atoms may be independently replaced by a fluorine atom, or any —CH 2 — may be independently replaced by —O—, —CH═CH—, or a cycloalkylene having 5 to 20 carbon atoms, and any hydrogen atom of the alkylene in the alkyl having 1 to 40 carbon atoms may be independently replaced by a fluorine atom, or any —CH 2 — may be independently replaced by —O— or a cycloalkylene having 5 to 20 carbon atoms; p represents a real number greater than or equal to 1, and x and z each independently represent a positive real number; * indicates the bond position.)

2. Formula (2+4 Ｈ ) and / or (4 Ｈ The siloxane polymer (α') according to claim 1, having a repeating unit represented by the formula: (R ２ is the formula (4) in claim 1 Ｈ ) in R ２ represents the same thing as x independently represents 0 or a positive real number, and z independently represents a positive real number.

3. R ２ The siloxane polymer (α') according to claim 1 or 2, wherein each independently represents methyl or phenyl.

4. The siloxane polymer (α') according to any one of claims 1 to 3, having a weight average molecular weight of 2,000 to 10,000,000.

5. A siloxane polymer composition comprising the siloxane polymer (α') according to any one of claims 1 to 4 and a solvent.

6. A molded article obtained by curing the siloxane polymer (α') according to any one of claims 1 to 4 or the siloxane polymer composition according to claim 5.

7. The molded article according to claim 6, which has electrical insulation properties.

8. A molded article comprising a cured product obtained by curing the siloxane polymer (α') according to any one of claims 1 to 4 or the siloxane polymer composition according to claim 5, and a substrate covered with the cured product.

9. The molded article according to claim 8, which has electrical insulation properties.

Images