WO2026048832A1 - Fluorene skeleton-containing polymer - Google Patents

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

The present invention relates to a polymer containing a fluorene skeleton.

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.

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

However, while the introduction of polysiloxane structures into fluorene skeleton-containing resins is effective in improving flexibility and film properties, it also comes with the problem of reduced scratch resistance. Therefore, there has been a demand for new fluorene skeleton-containing resins that can maintain scratch resistance even after the introduction of polysiloxane structures.

Patent No. 4873223 Patent No. 5890284 Patent No. 5890288 Japanese Patent Application Laid-Open No. 2008-184571

The present invention has been developed in consideration of the above circumstances, and aims to provide a new fluorene skeleton-containing polymer that provides a coating with superior scratch resistance compared to conventional fluorene skeleton-containing polymers that contain siloxane structures.

As a result of extensive research into achieving the above-mentioned objectives, the inventors discovered that 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, produces a coating that is more scratch-resistant than conventional polymers containing a fluorene skeleton, and thus completed the present invention.

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 the main chain, and a urethane bond, a carboxy group, and an acryloyl group or a methacryloyl group 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).
[In the formula, R ¹ to R ⁴ each independently represent a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. Each m independently represents an integer of 1 to 600. When m is an integer of 2 or greater, each R ³ may be the same or different from each other, and each R ⁴ may be the same or different from each other. a, b, c, and d are numbers which 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). X ² is a divalent group represented by the following formula (X2).
(In the formula, ⁿ¹ and ⁿ² each independently represent an integer of 1 to 7. ^R11 and ^R12 each independently represent a hydrogen atom or a methyl group. ^L1 to ^L4 each independently represent a saturated hydrocarbylene group having 1 to 8 carbon atoms, and some of the _-CH2- groups in the saturated hydrocarbylene group may be substituted with -O-, -S-, _-SO2- , -CO-, or -CONH-. The _-CH2- groups in the saturated hydrocarbylene group may be located at the terminals thereof. ^R13 to ^{R16 each independently represent a hydrogen atom, a monovalent group represented by the following formula (Y) or a monovalent group represented by the following formula (Z), and of all R13 to R16 in the polymer, at least 10 mol% of R13 to R16 are groups} represented by the following formula (Y), and at least 10 mol% of ^{R13 to R16} are groups represented by the following formula (Z). ¹⁶ is a group represented by the following formula (Z): The dashed lines represent bonds.
(In the formula, ^L5 is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the _--CH2-- groups of the hydrocarbylene group may be substituted with --O--, --S--, _--SO2-- , or --CO--. The _--CH2-- groups of the hydrocarbylene group may be located at the terminal. ^R17 is a hydrogen atom or a methyl group. ^L6 is a saturated or unsaturated hydrocarbylene group having 2 to 14 carbon atoms, and some of the _--CH2-- groups of the hydrocarbylene group may be substituted with --O--, --S--, _--SO2-- , or --CO--. The _--CH2-- groups of the hydrocarbylene group may be located at the terminal. The dashed lines represent bonds.)
(In the formula, R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group. R ²³ and R ²⁴ each independently represent a hydrocarbyl group having 1 to 8 carbon atoms. ^{k 1} and k ² each independently represent an integer of 0 to 7. p represents an integer of 0 to 600. The dashed lines represent bonds.)
3. The polymer of 2, wherein, of all R ¹³ to R ¹⁶ in the polymer, at least 20 mol % of R ¹³ to R ¹⁶ are groups represented by formula (Y) and at least 20 mol % of R ¹³ to R ¹⁶ are groups represented by formula (Z).
4. The polymer of 2 or 3, wherein L ⁶ has 2 to 10 carbon atoms.
5. A polymer of any of 2 to 4 in which the number of carbon atoms in L ¹ to L ⁴ is 1.
6. The polymer of any one of 2 to 5, wherein n ¹ and n ² are both 1.
7. The polymer of any one of 2 to 6, wherein R ¹¹ and R ¹² are both hydrogen atoms.
8. The polymer of any one of 2 to 7, wherein R ²¹ and R ²² are both hydrogen atoms.

The polymers of the present invention exhibit higher scratch resistance than conventional fluorene skeleton-containing polymers containing polysiloxane structures and silphenylene structures.

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.

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).

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.

In formulas (A2) and (A4), R ¹ to R ⁴ each independently represent a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. Each m independently represents an integer of 1 to 600, preferably an integer of 8 to 100. When m is an integer of 2 or greater, each R ³ may be the same or different, and each R ⁴ may be the same or different.

In formulas (A2) and (A4), when there are two or more siloxane units (i.e., when m is an integer of 2 or greater), the siloxane units may all be the same, or the composition 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.

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.)

In formula (X1), n ¹ and n ² each independently represent an integer of 1 to 7, preferably 1.

In formula (X1), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and it is preferable that R ¹¹ and R ¹² both represent a hydrogen atom.

In formula (X1), L ¹ to L ⁴ each independently represent a saturated hydrocarbylene group having 1 to 8 carbon atoms, and some of the —CH ₂ — groups in the saturated hydrocarbylene group may be substituted with —O—, —S—, —SO ₂ — or —CO—. The —CH ₂ — groups in the saturated hydrocarbylene group may be located at the terminal thereof.

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

It is preferable that each of L ¹ to L ⁴ has one carbon atom (ie, a methanediyl group).

In formula (X1), R ¹³ to R ¹⁶ each independently represent a hydrogen atom, a group represented by formula (Y) below, or a group represented by formula (Z) below.
(In the formula, the dashed lines represent bonds.)

In formula (Y), ^L5 is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the _—CH2— groups in the hydrocarbylene group may be substituted with —O—, —S—, _—SO2— or —CO—. The _—CH2— groups in the hydrocarbylene group may be located at the terminals thereof.

The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,2-diyl group, pentane-1,2-diyl group, hexane-1,2-diyl group, heptane-1,2-diyl group, 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, Examples include 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 cyclohexene-1,2-diyl and norbornene-1,2-diyl; and aromatic hydrocarbylene groups having 6 to 14 carbon atoms, such as phenylene, methylphenylene, and naphthalenediyl.

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

In formula (Z), ^L6 is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the _-CH2- groups in the hydrocarbylene group may be substituted with -O-, -S-, _-SO2- or -CO-. The _-CH2- groups in the hydrocarbylene group may be located at the terminals thereof.

The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples 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.

^L6 is preferably a hydrocarbylene group having 2 to 10 carbon atoms.

Of all R ¹³ to R ¹⁶ in the polymer, at least 10 mol % of R ¹³ to R ¹⁶ are groups represented by formula (Y), but it is preferable that 20 mol % or more of R ¹³ to R ¹⁶ are groups represented by formula (Y), and it is more preferable that 25 mol % or more of R ¹³ to R ¹⁶ are groups represented by formula (Y).

Furthermore, of all R ¹³ to R ¹⁶ in the polymer, it is preferable that at least 10 mol % of R ¹³ to R ¹⁶ are groups represented by formula (Z), and it is more preferable that 20 mol % or more of R ¹³ to R ¹⁶ are groups represented by formula (Z), and it is more preferable that 25 mol % or more of R ¹³ to R ¹⁶ are groups represented by formula (Z).

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

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

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

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

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 greater, each R ²³ may be the same as or different from each other, and each R ²⁴ may be the same as or different from each other.

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

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

[Method of producing a 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 (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 which may further contain a repeating unit represented by the following formula (B3) and a repeating unit represented by the following formula (B4), 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).
(wherein R ¹ to R ⁴ , m, a, b, c, d and X ² are the same as defined above.)
(wherein L ⁵ , L ⁶ and R ¹⁷ are the same as defined above.)

In formulas (B1) and (B2), ^X3 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 to L ⁴ , n ¹ and n ² are the same as above. The dashed lines represent bonds.)

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

Specific examples of compounds 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.).

Specific examples of compounds represented by formula (2) include, but are not limited to, 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.), and 4-methylhexahydrophthalic anhydride (Rikacid MH-700, manufactured by New Japan Chemical Co., Ltd.).

The reaction conditions are not particularly limited, but first, polymer B and the compound represented by formula (1) are mixed in a solvent and heated if necessary. From the perspective of promoting the reaction while suppressing side reactions, it is preferable to use an aprotic polar solvent as the solvent. Ketones such as cyclopentanone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; and esters such as ethyl acetate and propylene glycol monomethyl ether acetate are particularly preferred. The reaction temperature is preferably, for example, 30 to 100°C, and more preferably 30 to 60°C, from the perspective of preventing side reactions and enabling the reaction to be completed in a short period of time. The reaction time, which varies depending on the type and amount of reactant, is preferably approximately 0.5 to 50 hours, and more preferably 3 to 24 hours.

In the reaction, the compounding ratio of polymer B and the compound represented by formula (1) is preferably 0.40 to 4.00, more preferably 0.80 to 3.20, in terms of molar ratio, relative to ^X3 in polymer B. Only one type of compound represented by formula (1) may be used, or two or more types of compounds may be used in combination.

A catalyst may optionally be used in the reaction. Examples of such catalysts 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.

The amount of the catalyst used is usually a catalytic amount, and is preferably an amount that is 0.1 to 20 mol % relative to ^X3 in the polymer B. The catalyst may be used alone or in combination of two or more kinds.

In the reaction, a polymerization inhibitor may optionally be 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).

After the reaction is complete, optional solvent may be added, the mixture may be washed with water, and the organic layer may then be heated under reduced pressure to remove the solvent, yielding the reaction intermediate.

Next, the reaction intermediate and the compound represented by formula (2) are mixed in a solvent and heated. From the perspective of promoting the reaction while suppressing side reactions, it is preferable to use an aprotic polar solvent as the solvent. Ketones such as cyclopentanone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; and esters such as ethyl acetate and propylene glycol monomethyl ether acetate are particularly preferable. The reaction temperature is preferably 35 to 130°C, and more preferably 60 to 110°C, from the perspective of preventing side reactions and completing the reaction in a short period of time. The reaction time varies depending on the type and amount of reactant, but is preferably approximately 0.5 to 50 hours, and more preferably 3 to 24 hours.

In the reaction, the compounding ratio of the reaction intermediate and the compound represented by formula (2) is preferably such that the molar ratio of the compound represented by formula (2) to ^X3 in the reaction intermediate is 0.80 to 8.00, 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.

A catalyst may optionally be used in the reaction. Examples of such catalysts 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.

The amount of the catalyst used is usually a catalytic amount, and is preferably an amount that is 0.1 to 20 mol % relative to ^X3 in the polymer B. The catalyst may be used alone or in combination of two or more kinds.

In the reaction, a polymerization inhibitor may optionally be 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 amount of (meth)acrylic groups in the reaction intermediate.

After the reaction is complete, optionally, additional solvent is added, the mixture is washed with water, and the organic layer is then heated under reduced pressure to remove the solvent, thereby obtaining the fluorene skeleton-containing polymer of the present invention. When washing with water, an acidic aqueous solution such as hydrochloric acid may also be used.

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.
(wherein R ¹ to R ⁴ and m are the same as above.)

(wherein R ¹¹ and R ¹² , n ¹ , n ² , and L ¹ to L ⁴ are the same as defined above.)

(wherein R ²¹ to R ²⁴ , k ¹ , k ² and p are the same as defined above.)

Examples of _the metal catalyst include platinum group metals such as _platinum (including _{platinum black )} , rhodium, _and palladium _{; H2PtCl4.xH2O} , _{H2PtCl6.xH2O , NaHPtCl6.xH2O} , _{KHPtCl6.xH2O , Na2PtCl6.xH2O , K2PtCl4.xH2O} , _PtCl4.xH2O , _{PtCl2 , and Na2HPtCl4.xH2O ;} 0 (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 with 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 a support such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinic acid with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes);

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. Preferred examples of the solvent include hydrocarbon solvents such as toluene and xylene. As polymerization conditions, from the viewpoint of not deactivating the catalyst and completing the polymerization in a short time, a polymerization temperature of, for example, 40 to 150°C is preferred, with 60 to 120°C being particularly preferred. The polymerization time varies depending on the type and amount of polymer, but is preferably approximately 0.5 to 100 hours, with 0.5 to 30 hours being particularly preferred, 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.

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 add the compound represented by formula (3) dropwise over 0.1 to 5 hours.

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.

In the polymerization reaction, a polymerization inhibitor may optionally be 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 (5).

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

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.
(wherein R ¹ to R ⁴ , m, a, b, c, d and X ² are the same as defined above.)

In formulas (C1) and (C2), ^X4 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 are the same as above. The dashed lines represent bonds.)

In formula (7), ^L7 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. The saturated hydrocarbylene group represented by ^L7 may be linear, branched or cyclic, but preferably has 1 to 7 carbon atoms.

In formula (7), ^L8 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. The saturated hydrocarbylene group represented by ^L8 may be linear, branched or cyclic, but preferably has 1 to 7 carbon atoms.

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

The reaction conditions are not particularly limited, but typically, polymer C and the compound represented by formula (7) are mixed in a solvent and heated. From the perspective of accelerating the reaction, a polar solvent is preferably used as the solvent, and an alcohol solvent such as propylene glycol monomethyl ether is particularly preferred. The reaction temperature is preferably 35 to 130°C, and more preferably 45 to 100°C, from the perspective of preventing side reactions and enabling the reaction to be completed in a short period of time. The reaction time varies depending on the type and amount of reactant, but is preferably approximately 0.5 to 50 hours, and more preferably 0.5 to 24 hours.

In the reaction, the raw material compounds are preferably blended so that the molar ratio of the compound represented by formula (7) is 1.0 to 8.0, more preferably 4.0 to 6.0, relative to ^X4 in polymer C. Only one type of compound represented by formula (7) may be used, or two or more types of compounds may be used in combination.

A catalyst may optionally be used in the reaction. Examples of such catalysts 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. Examples of suitable organic compounds include organotin compounds such as dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dibutyltin(IV) dilaurate), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride; organolead compounds such as lead octoate and lead naphthenate; organonickel compounds such as nickel naphthenate; organocobalt compounds such as cobalt naphthenate; organocopper compounds such as copper octenoate; organobismuth compounds such as bismuth octoate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

The amount of the catalyst used is usually a catalytic amount, and is preferably an amount that is 0.1 to 20 mol % relative to ^X4 in the polymer C. The catalyst may be used alone or in combination of two or more kinds.

In the reaction, a polymerization inhibitor may optionally be 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).

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

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.
(wherein R ¹ to R ⁴ and m are the same as above.)

(wherein R ¹¹ and R ¹² , n ¹ , n ² , and L ¹ to L ⁴ are the same as defined above.)

(wherein R ²¹ to R ²⁴ , k ¹ , k ² and p are the same as defined above.)

Examples of _the metal catalyst include platinum group metals such as _platinum (including _{platinum black )} , rhodium, _and palladium _{; H2PtCl4.xH2O} , _{H2PtCl6.xH2O , NaHPtCl6.xH2O} , _{KHPtCl6.xH2O , Na2PtCl6.xH2O , K2PtCl4.xH2O} , _PtCl4.xH2O , _{PtCl2 , and Na2HPtCl4.xH2O ;} 0 (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 with 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 a support such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinic acid with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes);

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. Preferred examples of the solvent include hydrocarbon solvents such as toluene and xylene. As polymerization conditions, from the viewpoint of not deactivating the catalyst and completing the polymerization in a short time, a polymerization temperature of, for example, 40 to 150°C is preferred, with 60 to 120°C being particularly preferred. The polymerization time varies depending on the type and amount of polymer, but is preferably approximately 0.5 to 100 hours, with 0.5 to 30 hours being particularly preferred, 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.

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, followed by dropwise addition of the compound represented by formula (3) over a period of 0.1 to 5 hours.

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.

In the polymerization reaction, a polymerization inhibitor may optionally be 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 (5').

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

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

The curing agent can be an isocyanate curing agent. Examples of the isocyanate curing agent include 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.

The content of the curing agent in the composition is preferably 5 to 50 parts by mass, and more preferably 5 to 45 parts by mass, per 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.

The composition may contain a solvent, if necessary. Examples of such solvents 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 may be used alone or in combination of two or more. The content of the solvent in the composition is preferably 50 to 2,000 parts by mass, more preferably 50 to 1,000 parts by mass, and even more preferably 50 to 100 parts by mass, per 100 parts by mass of the polymer of the present invention. The solvent may be used alone or in combination of two or more types.

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

By heating and curing the applied composition, a coating with excellent scratch resistance can be obtained. Heating conditions are selected appropriately depending on the type of fluorene skeleton-containing polymer and curing agent used, but it is usually preferable to heat at 50 to 250°C for approximately 10 minutes to 6 hours.

The present invention will be explained in more 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 the GPC column, with a flow rate of 0.6 mL/min, THF as the elution solvent, and a column temperature of 40°C, using monodisperse polystyrene as the standard.

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

[Synthesis Example 1] Synthesis of Polymer b1 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 to a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser, followed by the addition of 1500 g of toluene and heating 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 dissolved, and then 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 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 using gel permeation chromatography (GPC) using tetrahydrofuran as the eluent, using a polystyrene equivalent. Polymer b1 was confirmed to be a polymer containing a repeating unit represented by formula (B1) and a repeating unit represented by formula (B2) by ^1H -NMR (Bruker).

[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 chloroplatinic acid toluene solution (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. To this polymer, 2,000 g of propylene glycol monomethyl ether was added, and after confirming dissolution, 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 the eluent, using a polystyrene equivalent. Polymer b2 was confirmed to be ^a polymer containing repeating units represented by formula (B1), repeating units represented by formula (B2), repeating units represented by formula (B3), and repeating units represented by formula (B4) using 1H-NMR (Bruker).

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 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. Next, the reaction intermediate was 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 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 9,000. Polymer 1 was confirmed to be a polymer containing a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2) by ¹ H-NMR (manufactured by Bruker).
Furthermore, of R ¹³ to R ¹⁶ in formula (X1), 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Y), and 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Z).

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 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. Next, the reaction intermediate was 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 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 9,000. Polymer 2 was confirmed to be a polymer containing a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2) by ¹ H-NMR (manufactured by Bruker).
Furthermore, of R ¹³ to R ¹⁶ in formula (X1), 25 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Y), and 75 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Z).

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 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. Next, the reaction intermediate was 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 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 9,000. Polymer 3 was confirmed to be a polymer containing a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2) by ¹ H-NMR (manufactured by Bruker).
Furthermore, of R ¹³ to R ¹⁶ in formula (X1), 75 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Y), and 25 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Z).

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 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. Next, the reaction intermediate was 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 heated at 100°C for 12 hours. After the reaction was completed, 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. Polymer 4 was confirmed to be a polymer containing a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2) by ¹ H-NMR (manufactured by Bruker).
Furthermore, of R ¹³ to R ¹⁶ in formula (X1), 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Y), and 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Z).

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 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. Next, the reaction intermediate was 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 heated at 100°C for 12 hours. After the reaction was completed, 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. Polymer 5 was confirmed to be a polymer containing a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2) by ¹ H-NMR (manufactured by Bruker).
Furthermore, of R ¹³ to R ¹⁶ in formula (X1), 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Y), and 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Z).

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 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. Next, the reaction intermediate was 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 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. Polymer 6 was confirmed to be ^a polymer containing 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) by 1 H-NMR (manufactured by Bruker).
Furthermore, of R ¹³ to R ¹⁶ in formula (X1), 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Y), and 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Z).

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 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. Next, the reaction intermediate was 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 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. Polymer 7 was confirmed to be ^a polymer containing 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) by 1 H-NMR (manufactured by Bruker).
Furthermore, of R ¹³ to R ¹⁶ in formula (X1), 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Y), and 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Z).

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 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. Next, the reaction intermediate was 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 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. Polymer 8 was confirmed to be ^a polymer containing 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) by 1 H-NMR (manufactured by Bruker).
Furthermore, of R ¹³ to R ¹⁶ in formula (X1), 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Y), and 50 mol % of R ¹³ to R ¹⁶ were groups represented by formula (Z).

[Comparative Example 1] Synthesis of Comparative Polymer 1 Into a 10 L flask equipped with a stirrer, thermometer, nitrogen purge apparatus, and reflux condenser, 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, followed by 1,100 g of toluene, 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 distilled off under reduced pressure from the reaction solution to obtain Comparative Polymer 1. The Mw of Comparative Polymer 1 was 12,000.

[Comparative Example 2] Synthesis of Comparative Polymer 2 Into a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser, 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, followed by 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 completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 12 hours. 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.

[Scratch resistance evaluation]
To 100 parts by mass of each of Polymers 1-6 and Comparative Polymers 1-2, 20 parts by mass of Duranate TMA-100 (manufactured by Asahi Kasei Corporation) was added as an isocyanate curing agent, and 55 parts by mass of cyclopentanone was added and dissolved 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 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, and 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.

[Flexibility Evaluation]
To 100 parts by mass of Polymers 1-6 and Comparative Polymers 1-2, 20 parts by mass of Duranate TMA-100 (manufactured by Asahi Kasei Corporation) was added as an isocyanate curing agent, and 55 parts by mass of cyclopentanone was added and dissolved 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). Flexibility of these samples was evaluated using a cylindrical mandrel with a diameter of 32 mm according to JIS K5600-5-1. After bending, the samples were observed for cracks, with a ◎ representing no cracks, a ○ representing several small cracks, and an × representing the film itself being fractured. The measurement results for each composition are shown in Table 1.

[Chemical resistance evaluation]
To 100 parts by weight of Polymers 1-6 and Comparative Polymers 1-2, 20 parts by weight of Duranate TMA-100 (manufactured by Asahi Kasei Corporation) was added as an isocyanate curing agent, and 55 parts by weight of cyclopentanone was added and dissolved 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 chemical resistance of these samples 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.

[Heat resistance test]
To 100 parts by mass of Polymers 1-6 and Comparative Polymers 1-2, 20 parts by mass of Duranate TMA-100 (manufactured by Asahi Kasei Corporation) was added as an isocyanate curing agent, and 55 parts by mass of cyclopentanone was added and dissolved 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 to evaluate heat resistance. 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.

These results demonstrate that the polymer of the present invention has superior scratch resistance while maintaining flexibility compared to conventional polymers containing fluorene skeletons that include siloxane structures.

Claims (8)

A polymer having a silphenylene skeleton, polysiloxane skeleton, and fluorene skeleton in the main chain, and urethane bonds, carboxy groups, and acryloyl groups or methacryloyl groups in the side chains. 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 to R ⁴ each independently represent a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. Each m independently represents an integer of 1 to 600. When m is an integer of 2 or greater, each R ³ may be the same or different from each other, and each R ⁴ may be the same or different from each other. a, b, c, and d are numbers which 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). X ² is a divalent group represented by the following formula (X2).
(In the formula, ⁿ¹ and ⁿ² each independently represent an integer of 1 to 7. ^R11 and ^R12 each independently represent a hydrogen atom or a methyl group. ^L1 to ^L4 each independently represent a saturated hydrocarbylene group having 1 to 8 carbon atoms, and some of the _-CH2- groups in the saturated hydrocarbylene group may be substituted with -O-, -S-, _-SO2- , -CO-, or -CONH-. The _-CH2- groups in the saturated hydrocarbylene group may be located at the terminals thereof. ^R13 to ^{R16 each independently represent a hydrogen atom, a monovalent group represented by the following formula (Y) or a monovalent group represented by the following formula (Z), and of all R13 to R16 in the polymer, at least 10 mol% of R13 to R16 are groups} represented by the following formula (Y), and at least 10 mol% of ^{R13 to R16} are groups represented by the following formula (Z). ¹⁶ is a group represented by the following formula (Z): The dashed lines represent bonds.
(In the formula, ^L5 is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the _--CH2-- groups of the hydrocarbylene group may be substituted with --O--, --S--, _--SO2-- , or --CO--. The _--CH2-- groups of the hydrocarbylene group may be located at the terminal. ^R17 is a hydrogen atom or a methyl group. ^L6 is a saturated or unsaturated hydrocarbylene group having 2 to 14 carbon atoms, and some of the _--CH2-- groups of the hydrocarbylene group may be substituted with --O--, --S--, _--SO2-- , or --CO--. The _--CH2-- groups of the hydrocarbylene group may be located at the terminal. The dashed lines represent bonds.)
(In the formula, R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group. R ²³ and R ²⁴ each independently represent a hydrocarbyl group having 1 to 8 carbon atoms. ^{k 1} and k ² each independently represent an integer of 0 to 7. p represents an integer of 0 to 600. The dashed lines represent bonds.) The polymer according to claim 2, wherein, of all R ¹³ to R ¹⁶ in the polymer, at least 20 mol % of R ¹³ to R ¹⁶ are groups represented by formula (Y), and at least 20 mol % of R ¹³ to R ¹⁶ are groups represented by formula (Z). 4. The polymer according to claim 2, wherein ^L6 has 2 to 10 carbon atoms. 4. The polymer according to claim 2, wherein each of L ¹ to L ⁴ has one carbon atom. 4. The polymer according to claim 2, wherein ⁿ¹ and ⁿ² are both 1. 4. The polymer according to claim 2, wherein R ^{<11 >} and R ^<12 > are both hydrogen atoms. 4. The polymer according to claim 2, wherein ^R21 and ^R22 are both hydrogen atoms.