Fluorene skeleton-containing polymer

Abstract

To provide a novel fluorene skeleton-containing polymer that provides a coating film more excellent in heat resistance than that obtained from a conventional fluorene skeleton-containing polymer containing a siloxane structure.SOLUTION: Provided is a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in a main chain, and containing a polyhydric alcohol structure in a side chain.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fluorene skeleton-containing polymer. [Background technology]

[0002] Fluorene skeleton-containing polymers are known to have excellent heat resistance and electrical properties. An example is the functional epoxy resin represented by the following formula (X) disclosed in Patent Document 1. However, this epoxy resin does not have a flexible site in the main chain, so it is expected to crack when cured. [ka]

[0003] In response to this, fluorene skeleton-containing resins have been proposed in which divalent hydrocarbon groups or polysiloxane structures have been introduced as flexible moieties (Patent Documents 2 and 3), and are known to exhibit good flexibility. Furthermore, fluorene skeleton-containing resins in which polysiloxane structures and silphenylene structures have been introduced have also been proposed (Patent Document 4), and are known to be excellent not only in flexibility but also in film properties and chemical resistance.

[0004] However, in recent years, there has been a demand for even higher heat resistance in materials for semiconductors used in automobiles, and new resins containing fluorene skeletons have been in demand. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 4873223 [Patent Document 2] JP 2014-47207 A [Patent Document 3] JP 2014-62055 A [Patent Document 4] JP 2008-184571 A Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel fluorene skeleton-containing polymer that gives a film having better heat resistance than a conventional fluorene skeleton-containing polymer containing a siloxane structure.

Means for Solving the Problems

[0007] As a result of repeated studies to achieve the above object, the present inventors have found that a polymer having a silylphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and containing a polyhydric alcohol structure in the side chain gives a film having better heat resistance than a conventional fluorene skeleton-containing polymer, and completed the present invention.

[0008] That is, the present invention provides the following fluorene skeleton-containing polymer. 1. A polymer having a silylphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and containing a polyhydric alcohol structure in the side chain. 2. A polymer according to 1, which contains a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), and may further contain a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4).

Chemical formula

Advantages of the Invention

[0009] The polymer of the present invention can provide a film with better heat resistance than a conventional fluorene skeleton-containing polymer containing a siloxane structure.

Modes for Carrying Out the Invention

[0010] [Fluorene Skeleton-Containing Polymer] The fluorene skeleton-containing polymer of the present invention is a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and containing a polyhydric alcohol structure in the side chain.

[0011] Such a polymer preferably contains a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), and may further contain a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4).

Chemical Formula

[0012] In formulas (A1) to (A4), a, b, c, and d are numbers satisfying 0 < a < 1, 0 < b < 1, 0 ≤ c < 1, 0 ≤ d < 1, and a + b + c + d = 1, but preferably satisfy 0.1 < a < 0.8, 0.1 < b < 0.8, 0 ≤ c < 0.15, 0 ≤ d < 0.15, and a + b + c + d = 1.

[0013] In formulas (A2) and (A4), R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. m is each independently an integer of 1 to 600, preferably an integer of 8 to 100. When m is an integer of 2 or more, each R 3 may be the same as or different from each other, and each R 4 may be the same as or different from each other.

[0014] In formulas (A2) and (A4), when there are two or more siloxane units (i.e., when m is an integer of 2 or more), the siloxane units may all be the same, or may contain two or more different types of siloxane units. When two or more different types of siloxane units are contained, the siloxane units may be bonded randomly or alternately, or may contain multiple blocks of the same type of siloxane units.

[0015] In formulas (A1) and (A2), X 1 is a divalent group represented by the following formula (X1): The divalent group represented by the following formula (X1) is a group having a fluorene skeleton. [ka] (In the formula, the dashed lines represent bonds.)

[0016] In formula (X1), n 1 and n 2 are each independently an integer of 1 to 7, and preferably 1.

[0017] In formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group, R 11 and R 12 and R are preferably both hydrogen atoms.

[0018] In formula (X1), L 1 ~L 4 are each independently a saturated hydrocarbylene group having 1 to 15 carbon atoms, and the -CH 2 - is part of -O-, -S-, -SO 2 The saturated hydrocarbylene group may be substituted with -, -CO- or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. 2 - may be located at the end.

[0019] The saturated hydrocarbylene group may be linear, branched, or cyclic. Specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,1 alkanediyl groups having 1 to 15 carbon atoms, such as an 0-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, or a pentadecane-1,15-diyl group; and cyclic saturated hydrocarbylene groups having 3 to 15 carbon atoms, such as a cyclopentanediyl group, a cyclohexanediyl group, a norbornanediyl group, or an adamantanediyl group.

[0020] L 1 and L 3 Preferably, each of L 2 and L 4 However, it is more preferable that both of them have 1 carbon atom.

[0021] In formulas (A3) and (A4), X 2 is a divalent group represented by the following formula (X2). [ka] (In the formula, the dashed lines represent bonds.)

[0022] In formula (X2), R 21 and R 22 are each independently a hydrogen atom or a methyl group, and preferably a hydrogen atom.

[0023] In formula (X2), R 23 and R 24 are each independently a hydrocarbyl group having 1 to 8 carbon atoms.

[0024] In formula (X2), k 1 and k 2are each independently an integer of 0 to 7, and are preferably 0.

[0025] In formula (X2), p is an integer of 0 to 600, preferably an integer of 0 to 100, and more preferably an integer of 0 to 30. When p is an integer of 2 or more, each R 23 may be the same or different, and each R 24 may be the same or different from each other.

[0026] The fluorene skeleton-containing polymer of the present invention preferably has a weight average molecular weight (Mw) of 2000 to 500000, more preferably 8000 to 100000. If the Mw is within the above range, the polymer can be obtained as a solid, and film-forming properties can be ensured. In the present invention, the Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0027] The fluorene skeleton-containing polymer of the present invention may be a polymer in which a repeating unit represented by formula (A1), a repeating unit represented by formula (A2), a repeating unit represented by formula (A3), and a repeating unit represented by formula (A4) are randomly or alternately bonded, or may contain a plurality of blocks of each unit.

[0028] [Method of producing fluorene skeleton-containing polymer] The method for producing the fluorene skeleton-containing polymer is not particularly limited, but for example, the fluorene skeleton-containing polymer can be produced by addition polymerization of a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), and, if necessary, a compound represented by the following formula (4) in the presence of a metal catalyst. [ka] (In the formula, R 1 ~R 4 and m are the same as above.)

[0029] [ka] (In the formula, R 11 and R 12 , n 1 , n 2 , L 1 ~L 4 is the same as above.)

[0030] [ka] (In the formula, R 21 ~R 24 , k 1 , k 2 and p is the same as above.

[0031] The metal catalyst includes platinum group metals such as platinum (including platinum black), rhodium, and palladium; 2 PtCl 4 xH 2 O, H 2 PtCl 6 xH 2 O, NaHPtCl 6 xH 2 O, KHPtCl 6 xH 2 O, Na 2 PtCl 6 xH 2 OK 2 PtCl 4 xH 2 O, PtCl 4 xH 2 O, PtCl 2 , Na 2 HPtCl 4 xH 20 (wherein x is preferably an integer of 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, as described in U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, as described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on carriers such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinic acid salts with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes); and the like can be used.

[0032] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1 mass% as platinum group metal relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent may be used as necessary. For example, a hydrocarbon solvent such as toluene or xylene is preferable. As the polymerization conditions, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time, the polymerization temperature is preferably, for example, 40 to 150°C, and particularly preferably 60 to 120°C. The polymerization time depends on the type and amount of the polymer, but is preferably about 0.5 to 100 hours, and particularly preferably 0.5 to 30 hours, in order to prevent moisture from entering the polymerization system. After the polymerization reaction is completed, if a solvent is used, the polymer can be obtained by distilling it off.

[0033] The reaction method is not particularly limited, but it is preferable to first mix and heat the compound represented by formula (2), the compound represented by formula (3) and, if necessary, the compound represented by formula (4), add a metal catalyst to the mixed solution, and then dropwise add the compound represented by formula (1) over a period of 0.1 to 5 hours.

[0034] The raw material compounds are preferably blended so that the molar ratio of the total of the hydrosilyl groups in the compound represented by formula (1) and the compound represented by formula (2) to the total of the alkenyl groups in the compound represented by formula (3) and the compound represented by formula (4) is 0.67 to 1.67, more preferably 0.83 to 1.25. The Mw of the polymer of the present invention can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight regulator.

[0035] In the polymerization reaction, a polymerization inhibitor may be used optionally. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the compound represented by formula (3).

[0036] After the reaction is completed, a solvent is optionally added, the mixture is washed with water, and the organic layer is heated under reduced pressure to remove the solvent, thereby obtaining the fluorene skeleton-containing polymer of the present invention. When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, a metal carbonate such as sodium carbonate, sodium hydrogen carbonate or potassium carbonate, or a metal hydrogen carbonate may be used.

[0037] Another method for producing the fluorene skeleton-containing polymer of the present invention includes a reaction between a polymer (hereinafter also referred to as polymer B) containing a repeating unit represented by the following formula (B1) and a repeating unit represented by the following formula (B2), and optionally containing a repeating unit represented by the following formula (B3) and a repeating unit represented by the following formula (B4), and a compound represented by the following formula (5). [ka] (In the formula, R 1 ~R 4 , m, a, b, c, d and X2 is the same as above.) [ka]

[0038] In formulas (B1) and (B2), X 3 is a divalent group represented by the following formula (X3): The divalent group represented by the following formula (X3) is a group having a fluorene skeleton. [ka] (In the formula, R 11 , R 12 , n 1 and n 2 is the same as above. The dashed lines indicate bonds.)

[0039] In formula (5), L 5 is a saturated hydrocarbylene group having 1 to 14 carbon atoms, and the -CH 2 - is part of -O-, -S-, -SO 2 A part or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted by a hydroxy group. 5 The saturated hydrocarbylene group represented by the following formula (1) may be linear, branched, or cyclic, but preferably has 1 to 7 carbon atoms.

[0040] In formula (5), L 6 is a saturated hydrocarbylene group having 1 to 14 carbon atoms, and the -CH 2 - is part of -O-, -S-, -SO 2 A part or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted by a hydroxy group. 5 The saturated hydrocarbylene group represented by the following formula (1) may be linear, branched, or cyclic, but preferably has 1 to 7 carbon atoms.

[0041] Specific examples of the compound represented by formula (5) include, but are not limited to, glycidol (Epiol OH (registered trademark) manufactured by NOF Corporation).

[0042] The reaction conditions are not particularly limited, but usually, the polymer B and the compound represented by formula (5) are mixed in a solvent and heated. As the solvent, from the viewpoint of promoting the reaction, it is preferable to use a polar solvent, and it is particularly preferable to use an alcohol solvent such as propylene glycol monomethyl ether. From the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time, the reaction temperature is preferably, for example, 35 to 130°C, and particularly preferably 45 to 100°C. The reaction time, which depends on the type and amount of the reaction substrate, is preferably about 0.5 to 50 hours, and particularly preferably 0.5 to 24 hours.

[0043] In the above reaction, each raw material compound is X in polymer B. 3 The compound represented by formula (5) is preferably blended in such an amount that the molar ratio of the compound represented by formula (5) is 1.0 to 8.0, and more preferably 4.0 to 6.0. The compound represented by formula (5) may be used alone or in combination of two or more kinds.

[0044] In the reaction, a catalyst may be used optionally. Examples of the catalyst include amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl)ether, and N-methylmorpholine; phosphines such as triphenylphosphine and tri(o-tolyl)phosphine; quaternary ammonium salts such as tetrabutylammonium chloride, benzyltriethylammonium chloride, and tetraethylhydroxylammonium; imidazoles such as imidazole and 2-ethyl-4-methylimidazole; pyridines such as pyridine, N,N-dimethyl-4-aminopyridine, and 2,6-lutidine; tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, and dimethyltin. organic tin compounds such as dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dibutyltin(IV) dilaurate), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride; organic lead compounds such as lead octoate and lead naphthenate; organic nickel compounds such as nickel naphthenate; organic cobalt compounds such as cobalt naphthenate; organic copper compounds such as copper octoate; organic bismuth compounds such as bismuth octoate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

[0045] The amount of the catalyst used is usually a catalytic amount, and X in the polymer B 3 The amount of the catalyst is preferably 0.1 to 20 mol % based on the total amount of the catalyst. The catalyst may be used alone or in combination of two or more kinds.

[0046] In the reaction, a polymerization inhibitor may be used optionally. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the compound represented by formula (3).

[0047] After the reaction is completed, a solvent is optionally added, the mixture is washed with water, and the organic layer is heated under reduced pressure to remove the solvent, thereby obtaining the fluorene skeleton-containing polymer of the present invention. When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, a metal carbonate such as sodium carbonate, sodium hydrogen carbonate or potassium carbonate, or a metal hydrogen carbonate may be used.

[0048] The polymer of the present invention can be made into a composition containing the polymer and a curing agent, and then coated on a substrate and heated to give a cured film having excellent heat resistance.

[0049] As the curing agent, an isocyanate curing agent can be used, which includes aliphatic isocyanates such as methyl isocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aromatic isocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and metaphenylene diisocyanate, and modified versions of these.

[0050] The content of the curing agent in the composition is preferably 5 to 50 parts by mass, more preferably 5 to 45 parts by mass, based on 100 parts by mass of the polymer of the present invention. The curing agent may be used alone or in combination of two or more kinds.

[0051] The composition may contain a solvent as necessary. Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. These may be used alone or in combination of two or more. The content of the solvent in the composition is preferably 50 to 2000 parts by mass, more preferably 50 to 1000 parts by mass, and even more preferably 50 to 100 parts by mass, based on 100 parts by mass of the polymer of the present invention. The solvent may be used alone or in combination of two or more kinds.

[0052] The composition can be applied to the substrate by a known method. For example, a dipping method, a spin coating method, a roll coating method, etc. can be used. The amount of coating can be appropriately selected depending on the purpose, but an amount that results in a film thickness of 0.1 to 100 μm is preferable.

[0053] The applied composition can be heated and cured to obtain a coating having excellent heat resistance. The heating conditions are appropriately selected depending on the type of fluorene skeleton-containing polymer and curing agent used, but it is usually preferable to perform the heating at 50 to 250°C for about 10 minutes to 6 hours. EXAMPLES

[0054] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, Mw was measured by GPC using a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column under analysis conditions of a flow rate of 0.6 mL / min, an elution solvent of THF, and a column temperature of 40° C., with monodisperse polystyrene as the standard.

[0055] The compounds used in the synthesis of the polymer are shown below. [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [Example 1] Synthesis of polymer 1 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 245.4g (0.235 mol) of the compound represented by formula (S-2a) and 430.5g (1.00 mol) of the compound represented by formula (S-4a) were added, followed by adding 1500g of toluene and heating to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 142.9g (0.735 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.97: 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 90°C and aged for 11 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a polymer. After confirming that 2000 g of propylene glycol monomethyl ether was added to this polymer and dissolved, 444.5 g (6.00 mol) of the compound represented by formula (S-5a) and 10.1 g (0.10 mol) of triethylamine were added and heated at 80° C. for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to obtain polymer 1. The Mw of polymer 1 was 8000. The Mw was measured by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent, using a polystyrene-equivalent value. In addition, polymer 1 is 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2).

[0061] [Example 2] Synthesis of polymer 2 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 530.5g (0.18 mol) of the compound represented by formula (S-2b), 387.5g (0.90 mol) of the compound represented by formula (S-4a) and 18.64g (0.10 mol) of the compound represented by formula (S-3) were added, followed by adding 1500g of toluene and heating to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 153.6g (0.79 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.97: 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 90°C and aged for 11 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a polymer. 2000 g of propylene glycol monomethyl ether was added to this polymer, and after confirming that it was dissolved, 400.0 g (5.40 mol) of the compound represented by formula (S-5a) and 9.11 g (0.09 mol) of triethylamine were added and heated at 80° C. for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to obtain polymer 2. The Mw of polymer 2 was 80,000. Note that polymer 2 was 1 H-NMR (Bruker) confirmed that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2), repeating units represented by formula (A3) and repeating units represented by formula (A4).

[0062] [Example 3] Synthesis of polymer 3 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 245.4g (0.235 mol) of the compound represented by formula (S-2a) and 430.5g (1.00 mol) of the compound represented by formula (S-4a) were added, followed by adding 1500g of toluene and heating to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 142.9g (0.735 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.97: 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 90°C and aged for 11 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a polymer. 2000 g of propylene glycol monomethyl ether was added to this polymer, and after confirming that it was dissolved, 528.6 g (6.00 mol) of the compound represented by formula (S-5b) and 10.1 g (0.10 mol) of triethylamine were added and heated at 80° C. for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to obtain polymer 3. The Mw of polymer 3 was 8500. Note that polymer 3 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2).

[0063] [Example 4] Synthesis of polymer 4 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 245.4g (0.235 mol) of the compound represented by formula (S-2a) and 430.5g (1.00 mol) of the compound represented by formula (S-4a) were added, followed by adding 1500g of toluene and heating to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 142.9g (0.735 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.97: 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 90°C and aged for 11 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a polymer. 2000 g of propylene glycol monomethyl ether was added to this polymer, and after confirming that it was dissolved, 696.7 g (6.00 mol) of the compound represented by formula (S-5c) and 10.1 g (0.10 mol) of triethylamine were added and heated at 80° C. for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to obtain polymer 4. Mw of polymer 4 was 9000. Polymer 1 was obtained by the following procedure: 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2).

[0064] [Comparative Example 1] Synthesis of Comparative Polymer 1 A 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser was charged with 401g (0.50 mol) of the compound represented by formula (S-2a), 488g (0.90 mol) of the compound represented by formula (S-4b) and 18.6g (0.10 mol) of the compound represented by formula (S-3), then 1100g of toluene was added and heated to 80°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 95.3g (0.49 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain comparative polymer 1. The Mw of comparative polymer 1 was 12000.

[0065] [Comparative Example 2] Synthesis of Comparative Polymer 2 A 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser was charged with 362g (0.45 mol) of the compound represented by formula (S-2b), 215g (0.50 mol) of the compound represented by formula (S-4a) and 271g (0.50 mol) of the compound represented by formula (S-4b), and then 2100g of toluene was added and heated to 70°C. Then, 2.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 105g (0.54 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 12 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain comparative polymer 2. The Mw of comparative polymer 2 was 14000.

[0066] [Heat resistance test] 20 parts by mass of Duranate TMA-100 (manufactured by Asahi Kasei Corporation) was added as an isocyanate curing agent to 100 parts by mass of polymers 1 to 4 and comparative polymers 1 to 2, and 55 parts by mass of cyclopentanone was added to dissolve the mixture until it was uniform. Each solution was applied to a silicon wafer by spin coating, prebaked at 120°C for 2 minutes, and then thermally cured at 180°C for 4 hours to form a film (thickness 20 μm) on the silicon wafer. The weight loss rate of this sample was measured when it was heated at 150°C for 300 hours, and the heat resistance was evaluated. The heat resistance was judged as ◯ if the weight loss rate was less than 1%, and × if it was 1% or more. The results are shown in Table 1.

[0067] [Table 1]

[0068] From the above results, it was found that the coating obtained from the polymer of the present invention has excellent heat resistance.

Claims

1. A polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and containing a polyhydric alcohol structure in the side chain.

2. The polymer according to claim 1, which comprises a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), and may further comprise a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4). 【Chemistry 1】 (In the formula, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer of 1 to 600. When m is an integer of 2 or more, each R 3 may be the same or different, and each R 4 may be the same or different. a, b, c, and d are numbers that satisfy 0<a<1, 0<b<1, 0≦c<1, 0≦d<1, and a+b+c+d=1. X 1 is a divalent group represented by the following formula (X1): 2 is a divalent group represented by the following formula (X2): 【Chemistry 2】 (In the formula, n 1 and n 2 are each independently an integer from 1 to 7. 11 and R 12 Each of L is independently a hydrogen atom or a methyl group. 1 ~L 4 are each independently a saturated hydrocarbylene group having 1 to 15 carbon atoms, and the —CH 2 Part of - is -O-, -S-, -SO 2 The saturated hydrocarbylene group may be substituted with --, --CO-- or --CONH--, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. The dashed lines represent bonds. 【Chemistry 3】 (In the formula, R 21 and R 22 R is each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. 1 and k 2 are each independently an integer of 0 to 7. p is an integer of 0 to 600. The dashed lines represent bonds.

3. L 1 and L 3 The polymer according to claim 2, wherein each of the carbon numbers of

4. L 2 and L 4 The polymer according to claim 2 or 3, wherein each of the carbon numbers of

5. n 1 and n 2 The polymer according to claim 2 or 3, wherein both of

6. R 11 and R 12 The polymer according to claim 2 or 3, wherein both of are hydrogen atoms.

7. R 21 and R 22 The polymer according to claim 2 or 3, wherein both of are hydrogen atoms.

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