Fluorene skeleton-containing polymer

Abstract

Provided is a polymer having in its main chain a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton, and having in its side chain a urethane bond, a carboxy group, and an acryloyl group, or a methacryloyl group.

Description

Fluorene-containing polymers

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

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

[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, and are known to exhibit good flexibility (Patent Documents 2 and 3). 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 have excellent not only flexibility but also film properties and chemical resistance.

[0004] However, while the introduction of a polysiloxane structure into a fluorene skeleton-containing resin is effective in improving flexibility and film properties, it also has the problem of reducing scratch resistance. Therefore, there has been a demand for a new fluorene skeleton-containing resin that can maintain scratch resistance even after the introduction of a polysiloxane structure.

[0005] Japanese Patent No. 4873223 Japanese Patent No. 5890284 Japanese Patent No. 5890288 Japanese Patent Laid-Open No. 2008-184571

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a new fluorene skeleton-containing polymer that provides a coating having superior scratch resistance compared to conventional fluorene skeleton-containing polymers containing a siloxane structure.

[0007] As a result of extensive investigations to achieve the above object, the present inventors have found that a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain, and having a urethane bond, a carboxy group, and an acryloyl group or a methacryloyl group in its side chain, can provide a coating that is more excellent in abrasion resistance than conventional fluorene skeleton-containing polymers, and have completed the present invention.

[0008] That is, the present invention provides the following fluorene skeleton-containing polymer: 1. A polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain, and having a urethane bond, a carboxy group, and an acryloyl group or a methacryloyl group in its side chain. 2. The polymer of 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). [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 from each other. a, b, c, and d are numbers that satisfy the following conditions: 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). (In the formula, n 1 and n 2 are each independently an integer of 1 to 7. 11 and R 12 are each independently a hydrogen atom or a methyl group. 1 ~L 4 are each independently a saturated hydrocarbylene group having 1 to 8 carbon atoms, and a portion of the -CH2- in the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-. The -CH2- in the saturated hydrocarbylene group may be located at its terminal. 13 ~R 16 are each independently a hydrogen atom, a monovalent group represented by the following formula (Y) or a monovalent group represented by the following formula (Z), but all R 13 ~R 16 Among these, at least 10 mol % of R 13 ~R 16is a group represented by the following formula (Y), and at least 10 mol % of R 13 ~R 16 is a group represented by the following formula (Z): The dashed lines represent bonds. (In the formula, L 5 is a hydrocarbylene group having 2 to 14 carbon atoms, and a portion of the -CH2- in the hydrocarbylene group may be substituted with -O-, -S-, -SO2- or -CO-. The -CH2- in the hydrocarbylene group may be located at its terminal. 17 is a hydrogen atom or a methyl group. 6 is a saturated or unsaturated hydrocarbylene group having 2 to 14 carbon atoms, and some of the -CH2- in the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- in the hydrocarbylene group may be located at its terminal. The dashed line represents a bond. (In the formula, R 21 and R 22 are 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 line represents a bond. 3. All R 13 ~R 16 Among these, at least 20 mol % of R 13 ~R 16 is a group represented by formula (Y), and at least 20 mol % of R 13 ~R 16 4. The polymer of 2, wherein L is a group represented by formula (Z). 6 5. A polymer of 2 or 3 having 2 to 10 carbon atoms. 1 ~L 4 6. A polymer of any one of 2 to 4, in which the number of carbon atoms in each of the above is 1. 1 and n 2 Any of the polymers 2 to 5, wherein R 11 and R 12 and R are both hydrogen atoms.21 and R 22 and a polymer of any one of 2 to 7, wherein both are hydrogen atoms.

[0009] The polymer of the present invention exhibits higher scratch resistance than conventional fluorene skeleton-containing polymers containing a polysiloxane structure and a silphenylene structure.

[0010] 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 a urethane bond, a carboxy group, and an acryloyl group or a methacryloyl group in the side chain.

[0011] Such a polymer is preferably a polymer that 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).

[0012] In formulas (A1) to (A4), 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, but preferably are numbers that 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. Each m is 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 or different, and each R 4 may be the same 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 two or more different types of siloxane units may be included. When two or more different types of siloxane units are included, the siloxane units may be randomly bonded or alternately bonded, or may include 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. (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, preferably 1.

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

[0018] In formula (X1), L 1 ~L 4 are each independently a saturated hydrocarbylene group having 1 to 8 carbon atoms, and a portion of the -CH2- in the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO2- or -CO-. The -CH2- in the saturated hydrocarbylene group may be located at its terminal.

[0019] The saturated hydrocarbylene group may be linear, branched, or cyclic, and specific examples thereof include alkanediyl groups having 1 to 8 carbon atoms, such as methanediyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group; and cyclic saturated hydrocarbylene groups having 3 to 8 carbon atoms, such as cyclopentanediyl group, cyclohexanediyl group, and norbornanediyl group.

[0020] L 1 ~L 4 Preferably, each of these groups has one carbon atom (i.e., a methanediyl group).

[0021] In formula (X1), R 13 ~R 16 are each independently a hydrogen atom, a group represented by the following formula (Y) or a group represented by the following formula (Z). (In the formula, the dashed lines represent bonds.)

[0022] In formula (Y), L 5 is a hydrocarbylene group having 2 to 14 carbon atoms, and a portion of the -CH2- in the hydrocarbylene group may be substituted with -O-, -S-, -SO2- or -CO-. The -CH2- in the hydrocarbylene group may be located at its terminal.

[0023] The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,2-diyl group, a pentane-1,2-diyl group, a hexane-1,2-diyl group, a heptane-1,2-diyl group, and an octane-1,2-diyl group. Alkanediyl groups having 2 to 14 carbon atoms, such as nonane-1,2-diyl, decane-1,2-diyl, undecane-1,2-diyl, dodecane-1,2-diyl, tridecane-1,2-diyl, and tetradecane-1,2-diyl; cyclic saturated hydrocarbylene groups having 3 to 14 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; ethene-1,1 -diyl group, ethene-1,2-diyl group, propene-1,2-diyl group, 1-butene-1,2-diyl group, 1-pentene-1,2-diyl group, 1-hexene-1,2-diyl group, 1-heptene-1,2-diyl group, 1-octene-1,2-diyl group, 3-octene-1,2-diyl group, 1-nonene-1,2-diyl group, 1-decene-1,2-diyl group, 4-decene-1,2-diyl group, 1-undecene-1,2-diyl group, alkenediyl groups having 2 to 14 carbon atoms, such as 1-decene-1,2-diyl, 1-dodecene-1,2-diyl, 1-tridecene-1,2-diyl, and 1-tetradecene-1,2-diyl; cyclic unsaturated carbylene groups having 3 to 14 carbon atoms, such as cyclohexenediyl and norbornenediyl; and aromatic hydrocarbylene groups having 6 to 14 carbon atoms, such as phenylene, methylphenylene, and naphthalenediyl.

[0024] In formula (Y), R 17 is a hydrogen atom or a methyl group.

[0025] In formula (Z), L 6 is a hydrocarbylene group having 2 to 14 carbon atoms, and a portion of the -CH2- in the hydrocarbylene group may be substituted with -O-, -S-, -SO2- or -CO-. The -CH2- in the hydrocarbylene group may be located at its terminal.

[0026] The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, pentane-1,2-diyl, hexane-1,2-diyl, heptane-1,2-diyl, octane-1,2-diyl, nonane-1,2-diyl, decane-1,2-diyl, and undecane-1,2-diyl. alkanediyl groups having 2 to 14 carbon atoms, such as 1,2-diyl, dodecane-1,2-diyl, tridecane-1,2-diyl, and tetradecane-1,2-diyl groups; cyclic saturated hydrocarbylene groups having 3 to 14 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl groups; ethene-1,1-diyl, ethene-1,2-diyl, and propene-1,1-diyl groups; 1-butene-1,2-diyl group, 1-pentene-1,2-diyl group, 1-hexene-1,2-diyl group, 1-heptene-1,2-diyl group, 1-octene-1,2-diyl group, 3-octene-1,2-diyl group, 1-nonene-1,2-diyl group, 1-decene-1,2-diyl group, 4-decene-1,2-diyl group, 1-undecene-1,2-diyl group alkenediyl groups having 2 to 14 carbon atoms such as 1-dodecene-1,2-diyl, 1-tridecene-1,2-diyl, and 1-tetradecene-1,2-diyl; cyclic unsaturated carbylene groups having 3 to 14 carbon atoms such as cyclohexenediyl and norbornenediyl; and aromatic hydrocarbylene groups having 6 to 14 carbon atoms such as phenylene, methylphenylene, and naphthalenediyl.

[0027] L 6 is preferably a hydrocarbylene group having 2 to 10 carbon atoms.

[0028] All R in the polymer 13 ~R 16 Among these, at least 10 mol % of R 13 ~R 16 is a group represented by formula (Y), and 20 mol % or more of R 13 ~R 16 is preferably a group represented by formula (Y), and 25 mol % or more of R 13 ~R16 is more preferably a group represented by formula (Y).

[0029] In addition, all R 13 ~R 16 Among these, at least 10 mol % of R 13 ~R 16 is a group represented by formula (Z), and 20 mol % or more of R 13 ~R 16 is preferably a group represented by formula (Z), and 25 mol % or more of R 13 ~R 16 is more preferably a group represented by formula (Z).

[0030] In formulas (A3) and (A4), X 2 is a divalent group represented by the following formula (X2). (The dashed lines represent bonds.)

[0031] In formula (X2), R 21 and R 22 are each independently a hydrogen atom or a methyl group, and preferably a hydrogen atom.

[0032] In formula (X2), R 23 and R 24 are each independently a hydrocarbyl group having 1 to 8 carbon atoms.

[0033] In formula (X2), k 1 and k 2 are each independently an integer of 0 to 7, preferably 0.

[0034] 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.

[0035] The fluorene skeleton-containing polymer of the present invention preferably has a weight average molecular weight (Mw) of 2,000 to 500,000, more preferably 4,000 to 100,000. When the Mw is within the above range, the polymer can be obtained in a solid form, and film-forming properties can also be ensured. In the present invention, the Mw is a polystyrene-equivalent measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0036] The fluorene skeleton-containing polymer of the present invention may be a polymer in which the repeating unit represented by formula (A1), the repeating unit represented by formula (A2), the repeating unit represented by formula (A3), and the repeating unit represented by formula (A4) are randomly or alternately bonded, or may contain a plurality of blocks of each unit.

[0037] [Method for Producing Fluorene Skeleton-Containing Polymer] The method for producing the fluorene skeleton-containing polymer is not particularly limited, but the fluorene skeleton-containing polymer can be produced, for example, by reacting a polymer containing a repeating unit represented by the following formula (B1) and a repeating unit represented by the following formula (B2), and optionally further containing a repeating unit represented by the following formula (B3) and a repeating unit represented by the following formula (B4) (hereinafter also referred to as polymer B), with a compound represented by the following formula (1), and then reacting the obtained reaction intermediate with a compound represented by the following formula (2). (In the formula, R 1 ~R 4 , m, a, b, c, d and X 2 is the same as above.) (In the formula, L 5 , L 6 and R 17 is the same as above.)

[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. (In the formula, R 11 and R 12 , L 1 ~L 4 , n 1 and n2 is the same as above. The dashed lines represent bonds.)

[0039] In formula (1), R 18 is an isocyanate group or a blocked isocyanate group.

[0040] Specific examples of the compound represented by formula (1) include, but are not limited to, 2-isocyanatoethyl acrylate (Karenz AOI manufactured by Resonac Co., Ltd.), 2-isocyanatoethyl methacrylate (Karenz MOI manufactured by Resonac Co., Ltd.), 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (Karenz MOI-EG manufactured by Resonac Co., Ltd.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP manufactured by Resonac Co., Ltd.), 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate (Karenz MOI-BM manufactured by Resonac Co., Ltd.), and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Karenz BEI manufactured by Resonac Co., Ltd.).

[0041] Specific examples of the compound represented by formula (2) include succinic anhydride (Rikacid SA, manufactured by New Japan Chemical Co., Ltd.), maleic anhydride, hexahydrophthalic anhydride (Rikacid HH, manufactured by New Japan Chemical Co., Ltd.), 1,2,3,6-tetrahydrophthalic anhydride (Rikacid TH, manufactured by New Japan Chemical Co., Ltd.), 4-methylhexahydrophthalic anhydride (Rikacid MH-700, manufactured by New Japan Chemical Co., Ltd.), and the like, but are not limited to these.

[0042] The reaction conditions are not particularly limited. First, polymer B and the compound represented by formula (1) are mixed in a solvent, and the mixture is heated if necessary. As the solvent, from the viewpoint of promoting the reaction while suppressing side reactions, it is preferable to use an aprotic polar solvent. It is particularly preferable to use ketones such as cyclopentanone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; or esters such as ethyl acetate and propylene glycol monomethyl ether acetate. 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, 30 to 100°C, and particularly preferably 30 to 60°C. The reaction time, which varies depending on the type and amount of the reaction substrate, is preferably approximately 0.5 to 50 hours, and particularly preferably 3 to 24 hours.

[0043] In the reaction, the compounding ratio of the polymer B and the compound represented by formula (1) is 3 The compound represented by formula (1) is preferably blended in such a manner that the molar ratio of the compound represented by formula (1) to the total amount of the cellulose acetate solution is 0.40 to 4.00, and more preferably 0.80 to 3.20. Only one type of compound represented by formula (1) may be used, or two or more types of compounds may be used in combination.

[0044] In the reaction, a catalyst may be optionally used. 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; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

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

[0046] In the reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor that can be used 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, relative to the compound represented by formula (3).

[0047] After the reaction is completed, a solvent is optionally added, the mixture is washed with water, and then the organic layer is heated under reduced pressure to distill off the solvent, thereby obtaining a reaction intermediate.

[0048] Next, the reaction intermediate and the compound represented by formula (2) are mixed in a solvent and heated. As the solvent, an aprotic polar solvent is preferably used from the viewpoint of promoting the reaction while suppressing side reactions, and it is particularly preferable to use ketones such as cyclopentanone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; or esters such as ethyl acetate and propylene glycol monomethyl ether acetate. The reaction temperature is preferably, for example, 35 to 130°C, particularly 60 to 110°C, from the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time. The reaction time, which varies depending on the type and amount of the reaction substrate, is preferably about 0.5 to 50 hours, particularly 3 to 24 hours.

[0049] In the reaction, the compounding ratio of the reaction intermediate and the compound represented by formula (2) is 3 The compound represented by formula (2) is preferably blended in such a manner that the molar ratio of the compound represented by formula (2) to the total amount of the cellulose acetate solution is 0.80 to 8.00, and more preferably 1.60 to 6.40. Only one type of compound represented by formula (2) may be used, or two or more types of compounds may be used in combination.

[0050] In the reaction, a catalyst may be optionally used. 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; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

[0051] The amount of catalyst used is usually a catalytic amount, and X in polymer B 3 The amount of the catalyst is preferably 0.1 to 20 mol % relative to the total amount of the catalyst. The catalyst may be used alone or in combination of two or more.

[0052] In the reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor that can be used 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 amount of (meth)acrylic groups in the reaction intermediate.

[0053] After the reaction is completed, optionally, a solvent is added, the mixture is washed with water, and then the organic layer is heated under reduced pressure to remove the solvent, thereby obtaining the fluorene skeleton-containing polymer of the present invention. In addition, when washing with water, an acidic aqueous solution such as hydrochloric acid may be used optionally.

[0054] The method for producing polymer B is not particularly limited, but it can be produced, for example, by addition polymerization of a compound represented by the following formula (3), a compound represented by the following formula (4), a compound represented by the following formula (5), and, if necessary, a compound represented by the following formula (6), in the presence of a metal catalyst. (In the formula, R 1 ~R 4 and m are the same as above.)

[0055] (In the formula, R 11 and R 12 , n 1 , n 2 , L 1 ~L 4 is the same as above.)

[0056] (In the formula, R 21 ~R 24 , k 1 , k 2 and p are the same as above.

[0057] Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chlorides, chloroplatinic acids, and chloroplatinic salts such as HPtCl.xH0, HPtCl.xH0, NaHPtCl.xH0, KHPtCl.xH0, NaPtCl.xH0, KPtCl.xH0, PtCl.xH0, PtCl, and NaHPtCl.xH0 (where 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, those 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 a support such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes), and the like can be used.

[0058] The amount of catalyst used is a catalytic amount, and typically, it is preferably 0.001 to 0.1 mass% of the platinum group metal relative to the total amount of the reaction polymer. A solvent may be used in the polymerization reaction, if necessary. Examples of suitable solvents include hydrocarbon solvents such as toluene and xylene. Regarding the polymerization conditions, the polymerization temperature is preferably 40 to 150°C, particularly 60 to 120°C, from the viewpoint of preventing catalyst deactivation and enabling polymerization to be completed in a short time. The polymerization time varies depending on the type and amount of polymer, but is preferably approximately 0.5 to 100 hours, particularly 0.5 to 30 hours, in order to prevent moisture from entering the polymerization system. After the polymerization reaction is complete, if a solvent was used, it can be distilled off to obtain the polymer.

[0059] The reaction method is not particularly limited, but it is preferable to first mix and heat the compound represented by formula (4), the compound represented by formula (5), and, if necessary, the compound represented by formula (6), and then add a metal catalyst to the mixed solution, and then dropwise add the compound represented by formula (3) over 0.1 to 5 hours.

[0060] The raw material compounds are preferably blended so that the molar ratio of the total hydrosilyl groups in the compound represented by formula (3) and the compound represented by formula (4) to the total alkenyl groups in the compound represented by formula (5) and the compound represented by formula (6) is 0.67 to 1.67, and 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 modifier.

[0061] In the polymerization reaction, a polymerization inhibitor may be optionally used. 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, relative to the compound represented by formula (5).

[0062] After the reaction is completed, optionally a solvent is added, the organic layer is washed with water, and then 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, or a metal carbonate or metal hydrogencarbonate such as sodium carbonate, sodium hydrogencarbonate or potassium carbonate may be used.

[0063] Another example of a method for producing polymer B is a reaction between a polymer (hereinafter also referred to as polymer C) containing a repeating unit represented by formula (C1) below and a repeating unit represented by formula (C2) below, and optionally containing a repeating unit represented by formula (C3) below and a repeating unit represented by formula (C4) below, and a compound represented by formula (7) below. (In the formula, R 1 ~R 4 , m, a, b, c, d and X 2 is the same as above.)

[0064] In formulas (C1) and (C2), X 4 is a divalent group represented by the following formula (X4): The divalent group represented by the following formula (X4) is a group having a fluorene skeleton. (In the formula, R 11 , R 12 , n 1 and n 2 is the same as above. The dashed lines represent bonds.)

[0065] In formula (7), L 7 is a saturated hydrocarbylene group having 1 to 14 carbon atoms, in which some of the -CH2- groups may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. 7 The saturated hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic, but preferably has 1 to 7 carbon atoms.

[0066] In formula (7), L 8is a saturated hydrocarbylene group having 1 to 14 carbon atoms, in which some of the -CH2- groups may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. 8 The saturated hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic, but preferably has 1 to 7 carbon atoms.

[0067] Specific examples of the compound represented by formula (7) include, but are not limited to, glycidol (Epiol OH (registered trademark) manufactured by NOF Corporation).

[0068] The reaction conditions are not particularly limited, but typically involve mixing polymer C and the compound represented by formula (7) in a solvent and heating the mixture. From the viewpoint of accelerating the reaction, it is preferable to use a polar solvent as the 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 varies depending on the type and amount of the reactant, but is preferably about 0.5 to 50 hours, and particularly preferably 0.5 to 24 hours.

[0069] In the reaction, each raw material compound is X in polymer C. 4 The compound represented by formula (7) is preferably blended in such a way that the molar ratio of the compound represented by formula (7) to the total amount of the cellulose acetate solution is 1.0 to 8.0, and more preferably 4.0 to 6.0. Only one type of compound represented by formula (7) may be used, or two or more types of compounds may be used in combination.

[0070] In the reaction, a catalyst may be optionally used. 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 octoate, tin oleate, tin laurate, dibutyltin diacetate, and dimethyltin. organic copper compounds such as copper octenate; organic bismuth compounds such as bismuth octoate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octenate.

[0071] The amount of catalyst used is usually a catalytic amount, and X in polymer C 4 The amount of the catalyst is preferably 0.1 to 20 mol % relative to the total amount of the catalyst. The catalyst may be used alone or in combination of two or more.

[0072] In the reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor that can be used 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, relative to the compound represented by formula (7).

[0073] After the reaction is completed, optionally a solvent is added, the organic layer is washed with water, and then 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, or a metal carbonate or metal hydrogencarbonate such as sodium carbonate, sodium hydrogencarbonate or potassium carbonate may be used.

[0074] The method for producing polymer C is not particularly limited, but it can be produced, for example, by addition polymerization of a compound represented by the following formula (3), a compound represented by the following formula (4), a compound represented by the following formula (5′), and, if necessary, a compound represented by the following formula (6) in the presence of a metal catalyst. (In the formula, R 1 ~R 4 and m are the same as above.)

[0075] (In the formula, R 11 and R 12 , n 1 , n 2 , L 1 ~L 4 is the same as above.)

[0076] (In the formula, R 21 ~R 24 , k 1 , k 2 and p are the same as above.

[0077] Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chlorides, chloroplatinic acids, and chloroplatinic salts such as HPtCl.xH0, HPtCl.xH0, NaHPtCl.xH0, KHPtCl.xH0, NaPtCl.xH0, KPtCl.xH0, PtCl.xH0, PtCl, and NaHPtCl.xH0 (where 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, those 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 a support such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes), and the like can be used.

[0078] The amount of catalyst used is a catalytic amount, and typically, it is preferably 0.001 to 0.1 mass% of the platinum group metal relative to the total amount of the reaction polymer. A solvent may be used in the polymerization reaction, if necessary. Examples of suitable solvents include hydrocarbon solvents such as toluene and xylene. Regarding the polymerization conditions, the polymerization temperature is preferably 40 to 150°C, particularly 60 to 120°C, from the viewpoint of preventing catalyst deactivation and enabling polymerization to be completed in a short time. The polymerization time varies depending on the type and amount of polymer, but is preferably approximately 0.5 to 100 hours, particularly 0.5 to 30 hours, in order to prevent moisture from entering the polymerization system. After the polymerization reaction is complete, if a solvent was used, it can be distilled off to obtain the polymer.

[0079] The reaction method is not particularly limited, but it is preferable to first mix and heat the compound represented by formula (4), the compound represented by formula (5'), and, if necessary, the compound represented by formula (6), and then add a metal catalyst to the mixed solution, and then dropwise add the compound represented by formula (3) over 0.1 to 5 hours.

[0080] The raw material compounds are preferably blended so that the molar ratio of the total hydrosilyl groups in the compound represented by formula (3) and the compound represented by formula (4) to the total alkenyl groups in the compound represented by formula (5') and the compound represented by formula (6) is 0.67 to 1.67, and 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 modifier.

[0081] In the polymerization reaction, a polymerization inhibitor may be optionally used. 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, relative to the compound represented by formula (5').

[0082] After the reaction is completed, optionally a solvent is added, the organic layer is washed with water, and then 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, or a metal carbonate or metal hydrogencarbonate such as sodium carbonate, sodium hydrogencarbonate or potassium carbonate may be used.

[0083] The polymer of the present invention can be made into a composition containing the polymer and a curing agent, and by applying the composition to a substrate and then heating the composition, a cured film having excellent scratch resistance can be obtained.

[0084] The curing agent may be an isocyanate curing agent, such as an aliphatic isocyanate such as methyl isocyanate, tetramethylene diisocyanate, or hexamethylene diisocyanate, an alicyclic isocyanate such as isophorone diisocyanate, an aromatic isocyanate such as toluene diisocyanate, diphenylmethane diisocyanate, or metaphenylene diisocyanate, or a modified version of any of these.

[0085] 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 agents may be used alone or in combination of two or more.

[0086] The composition may contain a solvent, if 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; and 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 solvents 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, relative to 100 parts by mass of the polymer of the present invention. The solvent may be used alone or in combination of two or more.

[0087] The composition can be applied to the substrate by a known method, such as dipping, spin coating, or roll coating. 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 preferred.

[0088] The applied composition can be heated and cured to obtain a coating with excellent scratch 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.

[0089] The present invention will be described in detail 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 analytical 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.

[0090] The compounds used in the synthesis of the polymer are shown below.

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097] [Synthesis Example 1] Synthesis of Polymer b1 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser, 245.4 g (0.235 mol) of the compound represented by formula (S-2a) and 430.5 g (1.00 mol) of the compound represented by formula (S-3a) were added, followed by 1500 g of toluene, and the mixture was heated to 70 ° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 142.9 g (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 completion of the dropwise addition, the mixture was heated to 90 ° C. and aged for 11 hours, after which the 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 had dissolved, 444.5 g (6.00 mol) of the compound represented by formula (S-5) and 10.1 g (0.10 mol) of triethylamine were added, and the mixture was heated at 80°C for 12 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, dissolved in cyclopentanone, and washed with pure water. The organic layer was then distilled off under reduced pressure to obtain polymer b1. The Mw of polymer b1 was 8000. The Mw was measured by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent, using a polystyrene equivalent value. Polymer b1 was 1 It was confirmed by H-NMR (manufactured by Bruker) that the polymer contained repeating units represented by formula (B1) and repeating units represented by formula (B2).

[0098] [Synthesis Example 2] Synthesis of Polymer b2 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser, 530.5 g (0.18 mol) of the compound represented by formula (S-2b), 387.5 g (0.90 mol) of the compound represented by formula (S-3a), and 18.64 g (0.10 mol) of the compound represented by formula (S-4) were added, followed by 1500 g of toluene, and the mixture was heated to 70 ° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 153.6 g (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 completion of the dropwise addition, the mixture was heated to 90 ° C. and aged for 11 hours, after which the 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 had dissolved, 400.0 g (5.40 mol) of the compound represented by formula (S-5) and 9.11 g (0.09 mol) of triethylamine were added, and the mixture was heated at 80°C for 12 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, dissolved in cyclopentanone, and washed with pure water. The organic layer was then distilled off under reduced pressure to obtain polymer b2. The Mw of polymer b2 was 80,000. The Mw was measured using gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent, using a polystyrene equivalent value. Polymer b2 was also 1 H-NMR (manufactured by Bruker) confirmed that the polymer contained a repeating unit represented by formula (B1), a repeating unit represented by formula (B2), a repeating unit represented by formula (B3), and a repeating unit represented by formula (B4).

[0099] Example 1 Synthesis of Polymer 1: 800 g of polymer b1 was added to a 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, and dissolved in 2200 g of cyclopentanone. 231.4 g (1.64 mol) of the compound represented by formula (S-6a) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After completion of the reaction, the reaction solution was washed with pure water, and the organic layer was evaporated under reduced pressure to obtain a reaction intermediate. The reaction intermediate was then dissolved in 2200 g of propylene glycol monomethyl ether acetate. 328.2 g (3.28 mol) of the compound represented by formula (S-7a) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After completion of the reaction, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was evaporated under reduced pressure to obtain polymer 1. The Mw of polymer 1 was 9000. 1 H-NMR (manufactured by Bruker) confirmed that the polymer contained repeating units represented by formula (A1) and repeating units represented by formula (A2). 13 ~R 16 Of these, 50 mol % of R 13 ~R 16 is a group represented by formula (Y), and 50 mol % of R 13 ~R 16 was a group represented by formula (Z).

[0100] Example 2: Synthesis of Polymer 2: 800 g of polymer b1 was added to a 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, and dissolved in 2200 g of cyclopentanone. 115.7 g (0.82 mol) of the compound represented by formula (S-6a) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After completion of the reaction, the reaction solution was washed with pure water, and the organic layer was evaporated under reduced pressure to obtain a reaction intermediate. The reaction intermediate was then dissolved in 2200 g of propylene glycol monomethyl ether acetate. 492.3 g (4.92 mol) of the compound represented by formula (S-7a) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After completion of the reaction, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was evaporated under reduced pressure to obtain polymer 2. The Mw of polymer 2 was 9000. 1 H-NMR (manufactured by Bruker) confirmed that the polymer contained repeating units represented by formula (A1) and repeating units represented by formula (A2). 13 ~R 16 Of these, 25 mol% of R 13 ~R 16 is a group represented by formula (Y), and 75 mol % of R 13 ~R 16 was a group represented by formula (Z).

[0101] Example 3: Synthesis of Polymer 3: 800 g of polymer b1 was added to a 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, and dissolved in 2200 g of cyclopentanone. 347.1 g (2.46 mol) of the compound represented by formula (S-6a) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After completion of the reaction, the reaction solution was washed with pure water, and the organic layer was evaporated under reduced pressure to obtain a reaction intermediate. The reaction intermediate was then dissolved in 2200 g of propylene glycol monomethyl ether acetate. 164.1 g (1.64 mol) of the compound represented by formula (S-7a) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After completion of the reaction, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was evaporated under reduced pressure to obtain polymer 3. The Mw of polymer 3 was 9000. 1 H-NMR (manufactured by Bruker) confirmed that the polymer contained repeating units represented by formula (A1) and repeating units represented by formula (A2). 13 ~R 16 Of these, 75 mol% of R 13 ~R 16 is a group represented by formula (Y), and 25 mol % of R 13 ~R 16 was a group represented by formula (Z).

[0102] Example 4: Synthesis of Polymer 4: 800 g of polymer b1 was added to a 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, and dissolved in 2200 g of cyclopentanone. 254.4 g (1.64 mol) of the compound represented by formula (S-6b) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After completion of the reaction, the reaction solution was washed with pure water, and the organic layer was evaporated under reduced pressure to obtain a reaction intermediate. The reaction intermediate was then dissolved in 2200 g of propylene glycol monomethyl ether acetate. 505.6 g (3.28 mol) of the compound represented by formula (S-7b) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After completion of the reaction, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was evaporated under reduced pressure to obtain polymer 4. The Mw of polymer 4 was 10,000. 1 H-NMR (manufactured by Bruker) confirmed that the polymer contained repeating units represented by formula (A1) and repeating units represented by formula (A2). 13 ~R 16 Of these, 50 mol % of R 13 ~R 16 is a group represented by formula (Y), and 50 mol % of R 13 ~R 16 was a group represented by formula (Z).

[0103] Example 5 Synthesis of Polymer 5: 800 g of polymer b1 was added to a 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, and dissolved in 2200 g of cyclopentanone. 254.4 g (1.64 mol) of the compound represented by formula (S-6b) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After completion of the reaction, the reaction solution was washed with pure water, and the organic layer was evaporated under reduced pressure to obtain a reaction intermediate. The reaction intermediate was then dissolved in 2200 g of propylene glycol monomethyl ether acetate. 485.8 g (3.28 mol) of the compound represented by formula (S-7c) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After completion of the reaction, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was evaporated under reduced pressure to obtain polymer 5. The Mw of polymer 5 was 10,000. 1 H-NMR (manufactured by Bruker) confirmed that the polymer contained repeating units represented by formula (A1) and repeating units represented by formula (A2). 13 ~R 16 Of these, 50 mol % of R 13 ~R 16 is a group represented by formula (Y), and 50 mol % of R 13 ~R 16 was a group represented by formula (Z).

[0104] Example 6 Synthesis of Polymer 6: 800 g of polymer b2 was added to a 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, and dissolved in 2200 g of cyclopentanone. 166.5 g (1.18 mol) of the compound represented by formula (S-6a) and 14.7 g (0.12 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After completion of the reaction, the reaction solution was washed with pure water, and the organic layer was evaporated under reduced pressure to obtain a reaction intermediate. The reaction intermediate was then dissolved in 2200 g of propylene glycol monomethyl ether acetate. 236.2 g (2.36 mol) of the compound represented by formula (S-7a) and 12.1 g (0.12 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After completion of the reaction, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was evaporated under reduced pressure to obtain polymer 6. The Mw of polymer 6 was 82,000. 1 It was confirmed by H-NMR (manufactured by Bruker) that the polymer contained 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). 13 ~R 16 Of these, 50 mol % of R 13 ~R 16 is a group represented by formula (Y), and 50 mol % of R 13 ~R 16 was a group represented by formula (Z).

[0105] Example 7 Synthesis of Polymer 7: 800 g of polymer b2 was added to a 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, and dissolved in 2200 g of cyclopentanone. 183.1 g (1.18 mol) of the compound represented by formula (S-6b) and 14.7 g (0.12 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After completion of the reaction, the reaction solution was washed with pure water, and the organic layer was evaporated under reduced pressure to obtain a reaction intermediate. The reaction intermediate was then dissolved in 2200 g of propylene glycol monomethyl ether acetate. 363.8 g (2.36 mol) of the compound represented by formula (S-7b) and 12.1 g (0.12 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After completion of the reaction, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was evaporated under reduced pressure to obtain polymer 7. The Mw of polymer 7 was 82,000. 1 It was confirmed by H-NMR (manufactured by Bruker) that the polymer contained 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). 13 ~R 16 Of these, 50 mol % of R 13 ~R 16 is a group represented by formula (Y), and 50 mol % of R 13 ~R 16 was a group represented by formula (Z).

[0106] Example 8 Synthesis of Polymer 8: 800 g of polymer b2 was added to a 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, and dissolved in 2200 g of cyclopentanone. 183.1 g (1.18 mol) of the compound represented by formula (S-6b) and 14.7 g (0.12 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After completion of the reaction, the reaction solution was washed with pure water, and the organic layer was evaporated under reduced pressure to obtain a reaction intermediate. The reaction intermediate was then dissolved in 2200 g of propylene glycol monomethyl ether acetate. 349.5 g (2.36 mol) of the compound represented by formula (S-7c) and 12.1 g (0.12 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After completion of the reaction, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was evaporated under reduced pressure to obtain polymer 8. The Mw of polymer 8 was 82,000. 1 It was confirmed by H-NMR (manufactured by Bruker) that the polymer contained 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). 13 ~R 16 Of these, 50 mol % of R 13 ~R 16 is a group represented by formula (Y), and 50 mol % of R 13 ~R 16 was a group represented by formula (Z).

[0107] [Comparative Example 1] Synthesis of Comparative Polymer 1: 401 g (0.50 mol) of the compound represented by formula (S-2a), 488 g (0.90 mol) of the compound represented by formula (S-3b), and 18.6 g (0.10 mol) of the compound represented by formula (S-4) were added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser. Then, 1,100 g of toluene was added and the mixture was heated to 80 ° C. Subsequently, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 95.3 g (0.49 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups: total alkenyl groups = 0.99:1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 6 hours. The toluene was then removed from the reaction solution by distillation under reduced pressure to obtain Comparative Polymer 1. The Mw of Comparative Polymer 1 was 12,000.

[0108] [Comparative Example 2] Synthesis of Comparative Polymer 2: 1,362 g (0.45 mol) of the compound represented by formula (S-2b) and 430 g (1.00 mol) of the compound represented by formula (S-3a) were added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser, followed by the addition of 2,100 g of toluene, and the mixture was heated to 70 ° C. Subsequently, 2.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 105 g (0.54 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 100 ° C. and aged for 12 hours. The toluene was then removed from the reaction solution by distillation under reduced pressure to obtain Comparative Polymer 2. The Mw of Comparative Polymer 2 was 14,000.

[0109] [Scratch Resistance Evaluation] 20 parts by weight of Duranate TMA-100 (manufactured by Asahi Kasei Corporation) was added as an isocyanate curing agent to 100 parts by weight of each of Polymers 1-6 and Comparative Polymers 1-2, and 55 parts by weight of cyclopentanone was added to dissolve the mixture until uniform. Each solution was applied to a polyethylene terephthalate film and thermally cured at 190°C for 4 hours to produce a film (20 μm thick). The scratch resistance of these samples was evaluated by a pencil hardness test. The test was conducted in accordance with JIS K 5600-5-4, in which pencils of various hardnesses (5B to 5H) were applied to the surface of the sample at a 45° angle and a load was applied. The hardness of the hardest pencil that did not scratch the sample was recorded as the pencil hardness. The measurement results for each composition are shown in Table 1.

[0110] [Flexibility Evaluation] 20 parts by weight of Duranate TMA-100 (manufactured by Asahi Kasei Corporation) was added as an isocyanate curing agent to 100 parts by weight of each of Polymers 1 to 6 and Comparative Polymers 1 to 2, and 55 parts by weight of cyclopentanone was added to dissolve the mixture until uniform. Each solution was applied to a polyethylene terephthalate film and thermally cured at 190°C for 4 hours to produce a film (20 μm thick). Flexibility was evaluated for these samples. Testing was performed using a cylindrical mandrel with a diameter of 32 mm in accordance with JIS K5600-5-1. After bending, the samples were observed for cracks. Those without cracks were marked with a ◎, those with several small cracks were marked with a ○, and those in which the film itself was fractured were marked with an ×. The measurement results for each composition are shown in Table 1.

[0111] [Chemical Resistance Evaluation] 20 parts by weight of Duranate TMA-100 (manufactured by Asahi Kasei Corporation) was added as an isocyanate curing agent to 100 parts by weight of each of Polymers 1-6 and Comparative Polymers 1-2, and 55 parts by weight of cyclopentanone was added to dissolve the mixture until uniform. Each solution was applied to a polyethylene terephthalate film and thermally cured at 190°C for 4 hours to produce a film (20 μm thick). The chemical resistance of this sample was evaluated. After immersion in NMP at 60°C for 30 minutes, the solvent on the film surface was removed by air blowing, and the film thickness was measured. A film thickness change of less than 1% was evaluated as ◎, a film thickness change of 1% to less than 5% was evaluated as ◯, and a film thickness change of 5% or more was evaluated as ×. The measurement results for each composition are shown in Table 1.

[0112] [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 each of Polymers 1-6 and Comparative Polymers 1-2, and 55 parts by mass of cyclopentanone was added to dissolve the mixture until homogeneous. Each solution was applied to a polyethylene terephthalate film and thermally cured at 190°C for 4 hours to produce a film (20 μm thick). The weight loss rate of this sample was measured after heating at 150°C for 300 hours, and heat resistance was evaluated. A weight loss rate of less than 1% was evaluated as ◯, and a weight loss rate of 1% or more was evaluated as ×. The measurement results for each composition are shown in Table 1.

[0113]

[0114] From the above results, the polymer of the present invention was found to have excellent scratch resistance while maintaining flexibility, compared to conventional polymers containing a fluorene skeleton including a siloxane structure.

Claims

A polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain, and having a urethane bond, a carboxy group, and an acryloyl group or a methacryloyl group in the side chain. 　 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): [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 from each other. a, b, c, and d are numbers that satisfy the following conditions: 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). (In the formula, n 1 and n 2 are each independently an integer of 1 to 7. 11 and R 12 are each independently a hydrogen atom or a methyl group. 1 ~L 4 are each independently a saturated hydrocarbylene group having 1 to 8 carbon atoms, and a portion of the -CH2- in the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-. The -CH2- in the saturated hydrocarbylene group may be located at its terminal. 13 ~R 16 are each independently a hydrogen atom, a monovalent group represented by the following formula (Y) or a monovalent group represented by the following formula (Z), but all R 13 ~R 16 Among these, at least 10 mol % of R 13 ~R 16 is a group represented by the following formula (Y), and at least 10 mol % of R 13 ~R 16 is a group represented by the following formula (Z): The dashed lines represent bonds. (In the formula, L 5 is a hydrocarbylene group having 2 to 14 carbon atoms, and a portion of the -CH2- in the hydrocarbylene group may be substituted with -O-, -S-, -SO2- or -CO-. The -CH2- in the hydrocarbylene group may be located at its terminal. 17 is a hydrogen atom or a methyl group. 6 is a saturated or unsaturated hydrocarbylene group having 2 to 14 carbon atoms, and some of the -CH2- in the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- in the hydrocarbylene group may be located at its terminal. The dashed line represents a bond. (In the formula, R 21 and R 22 are 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 line represents a bond. All R in the polymer 13 ~R 16 Among these, at least 20 mol % of R 13 ~R 16 is a group represented by formula (Y), and at least 20 mol % of R 13 ~R 16 The polymer according to claim 2, wherein is a group represented by formula (Z): L 6 4. The polymer according to claim 2, wherein the number of carbon atoms is 2 to 10. L 1 ~L 4 4. The polymer according to claim 2, wherein each of the carbon atoms of n 1 and n 2 and both are 1. The polymer according to claim 2 or 3. R 11 and R 12 The polymer according to claim 2 or 3, wherein both of are hydrogen atoms. R 21 and R 22 The polymer according to claim 2 or 3, wherein both of are hydrogen atoms.

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