Polymer containing fluorene skeleton

Abstract

Provided is a polymer having a silicon phenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in a main chain, and containing an acryloyl group or a methacryloyl group in a side chain.

Description

Technical Field

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

[0002] Polymers containing a fluorene skeleton are known to have excellent heat resistance and electrical properties. An example is the functional epoxy resin represented by the following formula (X) disclosed in Patent Document 1. However, since this epoxy resin has no soft sites in its main chain, it is expected to crack during curing.

[0003] [Chemistry 1]

[0004]

[0005] In response to this, resins containing a fluorene skeleton that incorporate a divalent hydrocarbon group or a polysiloxane structure as a flexible portion have been proposed (Patent Documents 2 and 3), and are known to exhibit excellent flexibility. Furthermore, a resin containing a fluorene skeleton that incorporates a polysiloxane structure and a silphenylene structure has been proposed (Patent Document 4), and is known to exhibit not only flexibility but also excellent film properties and chemical resistance.

[0006] 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 reduced adhesion to the substrate. Therefore, there is a need for a new fluorene skeleton-containing resin that can maintain adhesion even after the introduction of a polysiloxane structure.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent No. 4873223

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 2014-47207

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 2014-62055

[0012] Patent Document 4: Japanese Patent Application Laid-Open No. 2008-184571 Summary of the Invention

[0013] Problems to be solved by the invention

[0014] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a novel fluorene skeleton-containing polymer that provides a coating film having better adhesion to a substrate than conventional fluorene skeleton-containing polymers even though it contains a polysiloxane structure.

[0015] Means for solving problems

[0016] The present inventors have conducted extensive research to achieve the above-mentioned objectives and have discovered that a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and containing an acryloyl group or a methacryloyl group in the side chain can provide a film having superior adhesion compared to conventional polymers containing a fluorene skeleton, thereby completing the present invention.

[0017] That is, the present invention provides the following fluorene skeleton-containing polymer.

[0018] 1. A polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain and containing an acryloyl group or a methacryloyl group in its side chain.

[0019] 2. The polymer of 1, comprising a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), may further comprise a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4).

[0020] [Chemistry 2]

[0021]

[0022] (Where R 1 ~R 4 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. m each independently represents an integer from 1 to 600. When m is an integer greater than 2, each R 3 They can be the same or different. 4 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. 1 is a divalent group represented by the following formula (X1). 2 is a divalent group represented by the following formula (X2).

[0023] [Chemistry 3]

[0024]

[0025] (where n 1 and n 2 Each independently represents an integer of 1 to 7. 11 ~R 14 are each independently a hydrogen atom or a methyl group. 1 and L 2 Each is independently a saturated alkylene group having 1 to 15 carbon atoms, wherein a portion of the -CH2- of the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO-, or -CONH-, and a portion or all of the hydrogen atoms of the saturated alkylene group may be replaced by hydroxyl groups. The dotted line represents the bonding end.)

[0026] [Chemistry 4]

[0027]

[0028] (Where R 21 and R 22 R are each independently a hydrogen atom or a methyl group. 23 and R 24 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms. 1 and k 2 Each independently represents an integer from 0 to 7. p represents an integer from 0 to 600. The dotted line represents the binding end.

[0029] 3.2 polymer, wherein L 1 and L 2 They are all saturated hydrocarbylene groups in which one or more hydrogen atoms are replaced by hydroxyl groups, or saturated hydrocarbylene groups in which one or more -CH2- groups are replaced by -CONH-.

[0030] 4. The polymer of 2 or 3, wherein L 1 and L 2 The carbon number of each is 1 to 8.

[0031] 5. The polymer according to any one of 2 to 4, wherein n 1 and n 2 Both are 1.

[0032] 6. The polymer according to any one of 2 to 5, wherein R 11 and R 12 They are all hydrogen atoms.

[0033] 7. The polymer according to any one of 2 to 6, wherein R 21 and R 22 They are all hydrogen atoms.

[0034] Effects of the Invention

[0035] The polymer of the present invention can provide a coating having superior adhesion compared to conventional fluorene skeleton-containing polymers including a siloxane structure. DETAILED DESCRIPTION

[0036] [Polymer containing a fluorene skeleton]

[0037] The fluorene skeleton-containing polymer of the present invention is a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain, and containing an acryloyl group or a methacryloyl group in the side chain.

[0038] Such a polymer is preferably a polymer containing 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).

[0039] [Chemistry 5]

[0040]

[0041] 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, preferably numbers that satisfy 0.1<a<0.8, 0.1<b<0.8, 0≦c<0.3, 0≦d<0.3 and a+b+c+d=1, and more preferably numbers that satisfy 0.35<a<0.75, 0.35<b<0.75, 0≦c<0.15, 0≦d<0.15 and a+b+c+d=1.

[0042] In formulas (A2) and (A4), R 1 ~R 4 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. m is each independently an integer of 1 to 600, preferably an integer of 8 to 100. When m is an integer of 2 or more, each R 3 They can be the same or different. 4 They can be the same or different.

[0043] In formulas (A2) and (A4), when there are two or more siloxane units (i.e., when m is an integer of 2 or more), the siloxane units may all be the same or may contain two or more different siloxane units. When containing two or more different siloxane units, the siloxane units may be randomly bonded or alternately bonded, and may contain multiple blocks of the same siloxane unit.

[0044] In formulas (A1) and (A2), X 1 It 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.

[0045] [Chemistry 6]

[0046]

[0047] (In the formula, the dotted line is the junction end.)

[0048] In formula (X1), n 1 and n 2 Each independently represents an integer of 1 to 7, and preferably 1.

[0049] In formula (X1), R 11 ~R 14 Each independently represents a hydrogen atom or a methyl group, preferably R 11 and R 12 They are all hydrogen atoms.

[0050] In formula (X1), L 1 and L 2 Each independently represents a saturated hydrocarbylene group having 1 to 15 carbon atoms, wherein a portion of the -CH2- radicals in the saturated hydrocarbylene group may be replaced by -O-, -S-, -SO2-, -CO-, or -CONH-, and a portion or all of the hydrogen atoms in the saturated hydrocarbylene group may be replaced by hydroxyl groups. Furthermore, the -CH2- radicals in the saturated hydrocarbylene group may be located at the terminal end.

[0051] The saturated alkylene group may be linear, branched, or cyclic. Specific examples thereof include alkanediyl groups having 1 to 15 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, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, and pentadecane-1,15-diyl; and cyclic saturated alkylene groups having 3 to 15 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl.

[0052] L 1 and L 2 Preferably, they all have 1 to 8 carbon atoms, and more preferably, one or more hydrogen atoms are substituted by a hydroxyl group or one or more -CH2- groups are substituted by -CONH-.

[0053] In formulas (A3) and (A4), X 2 It is a divalent group represented by the following formula (X2).

[0054] [Chemistry 7]

[0055]

[0056] (In the formula, the dotted line is the junction end.)

[0057] In formula (X2), R 21 and R 22 Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0058] In formula (X2), R 23 and R 24 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms.

[0059] In formula (X2), k 1 and k 2 Each independently represents an integer of 0 to 7, and preferably 0.

[0060] 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 They can be the same or different. 24 They can be the same or different.

[0061] 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 this range, the polymer can be obtained as a solid and film-forming properties can be ensured. It should be noted 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.

[0062] The fluorene skeleton-containing polymer of the present invention may be a product 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 bonded, or may be a product in which they are alternately bonded, or may contain a plurality of blocks of each unit.

[0063] [Method for producing a polymer containing a fluorene skeleton]

[0064] There is no particular limitation on the method for producing the fluorene skeleton-containing polymer. For example, it can be produced by subjecting a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), and, if necessary, a compound represented by the following formula (4) to addition polymerization in the presence of a metal catalyst.

[0065] [Chemistry 8]

[0066]

[0067] (Where R 1 ~R 4 and m are the same as above.)

[0068] [Chemistry 9]

[0069]

[0070] (Where R 11 ~R 14 、n 1 、n 2 、L 1 and L 2 Same as above.)

[0071] [Chemistry 10]

[0072]

[0073] (Where R 21 ~R 24 、k 1 、k 2 and p are the same as above.)

[0074] As the metal catalyst, platinum (including platinum black), rhodium, palladium and other platinum group metal elements can be used; platinum chloride, chloroplatinic acid and chloroplatinates such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2HPtCl4·xH2O (wherein x is preferably an integer from 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (e.g., U.S. Patent No. 5,477,666); No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,662, and U.S. Pat. No. 3,775,452); products in which platinum group metals such as platinum black and palladium are supported on supports such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinates and vinyl-containing siloxanes (particularly vinyl-containing cyclic siloxanes), etc.

[0075] The amount of the catalyst used is the catalyst amount, usually, in terms of platinum group metal, preferably 0.001 to 0.1 mass % relative to the total amount of the reaction polymer. In the above-mentioned polymerization reaction, a solvent can be used as needed. As a solvent, for example, hydrocarbon solvents such as toluene and xylene are preferred. As the above-mentioned polymerization conditions, from the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time, the polymerization temperature is preferably 40 to 150° C., particularly preferably 60 to 120° C. The polymerization time also depends on the type and amount of the polymer. In order to prevent moisture from intervening in the polymerization system, it is preferably about 0.5 to 100 hours, particularly preferably 0.5 to 30 hours. After the completion of the polymerization reaction, if a solvent is used, the above-mentioned polymer can be obtained by distilling it off.

[0076] The reaction method is not particularly limited. First, the compound represented by formula (2), the compound represented by formula (3) and, if necessary, the compound represented by formula (4) are mixed, heated, and a metal catalyst is added to the above mixed solution. Then, the compound represented by formula (1) is added dropwise over a period of 0.1 to 5 hours.

[0077] The raw material compounds are preferably blended so that the total molar ratio of the hydrosilyl groups possessed by the compound represented by formula (1) and the compound represented by formula (2) relative to the total molar ratio of the alkenyl groups possessed by the compound represented by formula (3) and the compound represented by formula (4) is 0.67 to 1.67, more preferably 0.83 to 1.25. The Mw of the polymer of the present invention can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight modifier.

[0078] In the polymerization reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxylamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the compound represented by formula (3).

[0079] After the reaction is completed, a solvent is optionally added, and after washing with water, the organic layer is heated under reduced pressure to distill off the solvent, thereby obtaining the polymer containing the fluorene skeleton of the present invention. In addition, 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 can be optionally used.

[0080] As another method for producing a polymer containing a fluorene skeleton of the present invention, the reaction of 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), 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 (5) can also be listed.

[0081] [Chemistry 11]

[0082]

[0083] (Where R 1 ~R 4 , m, a, b, c, d, and X 2 Same as above.)

[0084] [Chemistry 12]

[0085]

[0086] In formulas (B1) and (B2), X 3 It 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.

[0087] [Chemistry 13]

[0088]

[0089] (Where R 11 、R 12 、n 1 and n 2 Same as above. The dotted line indicates the junction end.)

[0090] In formula (5), R 31 is a hydrogen atom or a methyl group.

[0091] In formula (5), L 3 A saturated alkylene group having 1 to 14 carbon atoms, wherein a portion of -CH2- in the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, and a portion or all of the hydrogen atoms in the saturated alkylene group may be replaced by hydroxyl groups. 3 The saturated hydrocarbylene group represented by may be linear, branched, or cyclic, and preferably has 1 to 7 carbon atoms.

[0092] Specific examples of the compound represented by formula (5) include 2-acryloyloxyethyl isocyanate (Kalenzu AOI (registered trademark) manufactured by Showa Denko K.K.), 2-methacryloyloxyethyl isocyanate (Kalenzu MOI (registered trademark) manufactured by Showa Denko K.K.), and 2-(2-methacryloyloxyethoxy)ethyl isocyanate (Kalenzu MOI-EG (registered trademark) manufactured by Showa Denko K.K.), but are not limited to these.

[0093] The reaction conditions are not particularly limited. Generally, polymer B and the compound represented by formula (5) are mixed in a solvent and heated. As the solvent, from the perspective of promoting the reaction while suppressing side reactions, aprotic polar solvents are preferably used, and 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. From the perspective of preventing side reactions and completing the reaction in a short time, the reaction temperature is preferably 35 to 130°C, and particularly preferably 45 to 100°C. The reaction time also depends on the type and amount of the reaction substrate, but is preferably about 0.5 to 50 hours, and particularly preferably 0.5 to 24 hours.

[0094] In the above reaction, each raw material compound is preferably in an amount relative to X in polymer B. 3 The compound represented by formula (5) is blended in a molar ratio of 1.80 to 2.20, more preferably 1.95 to 2.10. The compound represented by formula (5) may be used alone or in combination of two or more.

[0095] In the above reaction, a catalyst may be optionally used. Examples of the above 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 tetraethylammonium hydroxide; 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 dimethyl dilaurate. Organotin compounds such as tin mononitrate, dibutyltin dilaurate, dibutyltin dimercaprol, dibutyltin maleate, dibutyltin dilaurate (dibutyltin (IV) dilaurate), dibutyltin diceneodecanoate, dioctyltin dimercaprol, 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 octenate; organobismuth compounds such as bismuth octoate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

[0096] The amount of catalyst used is usually the amount of catalyst relative to the X in polymer B. 3 The amount of the catalyst is preferably 0.1 to 20 mol%. The above catalysts may be used alone or in combination of two or more.

[0097] In the above reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxylamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the compound represented by formula (3).

[0098] After the reaction is completed, a solvent is optionally added, and after washing with water, the organic layer is heated under reduced pressure to distill off the solvent, thereby obtaining the polymer containing a fluorene skeleton of the present invention. In addition, 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 can be optionally used.

[0099] Furthermore, another method for producing the fluorene skeleton-containing polymer of the present invention may include a reaction between the polymer B and a compound represented by the following formula (6).

[0100] [Chemistry 14]

[0101]

[0102] In formula (6), R 41 is a hydrogen atom or a methyl group.

[0103] In formula (6), L 4 A divalent saturated alkylene group having 1 to 13 carbon atoms, wherein a portion of -CH2- in the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, and a portion or all of the hydrogen atoms in the saturated alkylene group may be replaced by hydroxyl groups. 3 The saturated hydrocarbylene group represented by may be linear, branched, or cyclic, and preferably has 1 to 6 carbon atoms.

[0104] The reaction conditions are not particularly limited. Generally, polymer B and the compound represented by formula (6) are mixed in a solvent and heated. As the solvent, from the perspective of promoting the reaction while suppressing side reactions, aprotic polar solvents are preferably used, and 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. From the perspective of preventing side reactions and completing the reaction in a short time, the reaction temperature is preferably 35 to 130°C, and particularly preferably 45 to 100°C. The reaction time also depends on the type and amount of the reaction substrate, but is preferably about 0.5 to 50 hours, and particularly preferably 0.5 to 24 hours.

[0105] In the above reaction, each raw material compound is preferably in an amount relative to X in polymer B. 3 The compound represented by formula (6) is mixed in a molar ratio of 1.60 to 3.00, more preferably 1.90 to 2.00. The compound represented by formula (6) may be used alone or in combination of two or more.

[0106] In the above 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 tetraethylammonium hydroxide; imidazoles such as imidazole and 2-ethyl-4-methylimidazole; potassium salts such as potassium hydroxide, potassium carbonate, potassium acetate, and potassium octoate; and sodium salts such as sodium hydroxide, sodium carbonate, sodium acetate, and sodium octoate.

[0107] The amount of catalyst used is usually the amount of catalyst relative to the X in polymer B. 3 The amount of the catalyst is preferably 0.1 to 20 mol%. The above catalysts may be used alone or in combination of two or more.

[0108] In the above reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxylamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the compound represented by formula (6).

[0109] After the reaction is completed, a solvent is optionally added, and after washing with water, the organic layer is heated under reduced pressure to distill off the solvent, thereby obtaining the polymer of the present invention. Furthermore, during the water washing, 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 be optionally used.

[0110] Another method for producing the polymer of the present invention is to react a polymer (hereinafter also referred to as polymer C) containing a repeating unit represented by the following formula (C1) and a repeating unit represented by the following formula (C2), which may further contain a repeating unit represented by the following formula (C3) and a repeating unit represented by the following formula (C4), with acrylic acid or methacrylic acid.

[0111] [Chemistry 15]

[0112]

[0113] (Where R 1 ~R 4 , m, a, b, c, d, and X 2 Same as above.)

[0114] In formulas (C1) and (C2), X 4 It 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.

[0115] [Chemistry 16]

[0116]

[0117] (Where R 11 、R 12 、n 1 and n 2 Same as above. The dotted line indicates the junction end.)

[0118] In formula (X4), L 5 and L 6 Each independently represents a saturated alkylene group having 1 to 13 carbon atoms, wherein a portion of -CH2- in the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, and a portion or all of the hydrogen atoms in the saturated alkylene group may be replaced by hydroxyl groups.5 and L 6 The saturated hydrocarbylene group represented by may be linear, branched, or cyclic, and preferably has 1 to 6 carbon atoms.

[0119] The reaction conditions are not particularly limited; generally, polymer C and acrylic acid or methacrylic acid are mixed in a solvent and heated. Polar solvents are preferred as the solvent to promote the reaction, with alcoholic solvents such as propylene glycol monomethyl ether being particularly preferred. The reaction temperature is preferably 35 to 130°C, particularly 60 to 110°C, to prevent side reactions and allow the reaction to complete in a short time. The reaction time, which also depends on the type and amount of the reaction substrate, is preferably approximately 0.5 to 50 hours, particularly 0.5 to 24 hours.

[0120] In the above reaction, each raw material compound is preferably in an amount relative to X in polymer C. 4 Acrylic acid or methacrylic acid is blended in a molar ratio of 2.00 to 10.00, more preferably 3.00 to 8.00. Acrylic acid and methacrylic acid may be used alone or in combination.

[0121] In the above 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 tetraethylammonium hydroxide; and imidazoles such as imidazole and 2-ethyl-4-methylimidazole.

[0122] The amount of catalyst used is usually the amount of catalyst relative to the X in polymer C. 4 The amount of the catalyst is preferably 0.1 to 20 mol%. The above catalysts may be used alone or in combination of two or more.

[0123] In the above reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxylamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, relative to acrylic acid or methacrylic acid.

[0124] After the reaction is completed, a solvent is optionally added, and after washing with water, the organic layer is heated under reduced pressure to distill off the solvent, thereby obtaining the polymer of the present invention. Furthermore, during the water washing, 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 be optionally used.

[0125] The polymer of the present invention can be prepared into a composition containing the polymer and a curing agent, and the composition is applied onto a substrate and then heated to obtain a cured film having excellent adhesiveness.

[0126] As the curing agent, an amine curing agent, a thiol curing agent, or the like can be used, and an amine curing agent is particularly preferably used.

[0127] Examples of the amine curing agent include aliphatic amines such as tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine; alicyclic amines such as isophoronediamine and bis(4-amino-3-methylcyclohexyl)methane; aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, and m-phenylenediamine; heterocyclic amines such as aminoethylpiperazine and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; dicyandiamide; and modified products thereof.

[0128] Examples of the thiol curing agent include alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol; ester compounds containing a terminal thiol group such as tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and trimethylolethane tris(3-mercaptobutyrate).

[0129] In the composition, the content of the curing agent is preferably 5 to 50 parts by mass, more preferably 5 to 45 parts by mass, relative to 100 parts by mass of the polymer of the present invention. The curing agent may be used alone or in combination of two or more.

[0130] The above composition may contain a solvent as needed. Examples of the above 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, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, and γ-butyrolactone. These solvents may be used alone or in combination. In the composition, the content of the solvent 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.

[0131] The composition can be applied to the substrate using a known method. For example, dipping, spin coating, roller coating, etc. The amount of coating can be appropriately selected depending on the intended purpose, and is preferably an amount that provides a film thickness of 0.1 to 100 μm.

[0132] By heating and curing the applied resin composition, a film with excellent adhesion can be obtained. The heating conditions are appropriately selected according to the types of the fluorene skeleton-containing polymer and curing agent used, and are generally preferably performed at 50 to 250°C for about 10 minutes to 6 hours.

[0133] Example

[0134] The present invention is described in detail below with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples. In the following Examples, Mw was measured by GPC using a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column, under analysis conditions of a flow rate of 0.6 mL / min, an eluent of THF, and a column temperature of 40°C, using monodisperse polystyrene as a standard.

[0135] The compounds used in the synthesis of the polymer are shown below.

[0136] [Chemistry 17]

[0137]

[0138] [Chemistry 18]

[0139]

[0140] [Chemistry 19]

[0141]

[0142] [Chemistry 20]

[0143]

[0144] [Chemistry 21]

[0145]

[0146] [Chemistry 22]

[0147]

[0148] [Example 1] Synthesis of polymer 1

[0149] In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 361g (0.45 mol) of the compound represented by formula (S-2a) and 715g (1.00 mol) of the compound represented by formula (S-3a) were added, and then 1800g of toluene was added and heated to 70°C. Then, 1.5g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 105g (0.54 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99:1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 7 hours. Then, the toluene was removed from the reaction solution under reduced pressure to obtain polymer 1. The Mw of polymer 1 is 12000. In addition, polymer 1 adopts 1 H-NMR (manufactured by Bruker) confirmed that the polymer was a polymer containing a repeating unit represented by the formula (A1) and a repeating unit represented by the formula (A2).

[0150] [Example 2] Synthesis of polymer 2

[0151] In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 1513g (0.50 mol) of the compound represented by formula (S-2b), 606g (0.85 mol) of the compound represented by formula (S-3b) and 28.0g (0.15 mol) of the compound represented by formula (S-4) were added, and then 3000g of toluene was added and heated to 80°C. Then, 2.5g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 95.3g (0.49 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups:total of alkenyl groups = 0.99:1 (molar ratio)). After the addition was completed, the mixture was heated to 105°C and aged for 10 hours. Then, the toluene was removed from the reaction solution under reduced pressure to obtain polymer 2. The Mw of polymer 2 was 18000. In addition, polymer 2 was prepared using 1H-NMR (manufactured by Bruker) confirmed 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).

[0152] [Example 3] Synthesis of polymer 3

[0153] In a 10 L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser, 908 g (0.30 mol) of the compound represented by formula (S-2b), 387 g (0.90 mol) of the compound represented by formula (S-5a), and 18.6 g (0.10 mol) of the compound represented by formula (S-4) were added. 2100 g of toluene was then added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 134 g (0.69 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl group:total alkenyl group = 0.99:1 (molar ratio)). After completion of the addition, the mixture was heated to 90°C and aged for 11 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain a polymer. To this polymer, 2500 g of propylene glycol monomethyl ether acetate was added. After confirming its dissolution, 279 g (1.80 moles) of the compound represented by formula (S-6a) and 5.06 g (0.05 moles) of triethylamine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was completed, propylene glycol monomethyl ether acetate and triethylamine were removed from the reaction solution under reduced pressure to obtain polymer 3. The Mw of polymer 3 was 14,000. In addition, polymer 3 was prepared by 1 H-NMR (manufactured by Bruker) confirmed 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).

[0154] [Example 4] Synthesis of polymer 4

[0155] A 10-liter flask equipped with a stirrer, thermometer, nitrogen exchange device, and reflux condenser was charged with 401 g (0.50 mol) of the compound represented by formula (S-2a) and 431 g (1.00 mol) of the compound represented by formula (S-5a). Then, 1900 g of toluene was added and the mixture was heated to 80°C. Then, 1.4 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 group:total alkenyl group = 0.99:1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 12 hours. The toluene was then distilled off under reduced pressure from the reaction solution to obtain a polymer. To this polymer, 1800 g of propylene glycol monomethyl ether acetate was added. After confirming its dissolution, 312 g (2.00 moles) of the compound represented by formula (S-6b) and 10.1 g (0.10 moles) of triethylamine were added, and the mixture was heated at 70°C for 10 hours. After the reaction was completed, propylene glycol monomethyl ether acetate and triethylamine were removed from the reaction solution under reduced pressure to obtain polymer 4. The Mw of polymer 4 was 13,000. In addition, polymer 4 was prepared by 1 H-NMR (manufactured by Bruker) confirmed 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).

[0156] [Example 5] Synthesis of Polymer 5

[0157] A 10-liter flask equipped with a stirrer, a thermometer, a nitrogen exchanger, and a reflux condenser was charged with 321 g (0.40 mol) of the compound represented by formula (S-2a), 499 g (0.92 mol) of the compound represented by formula (S-5b), and 14.9 g (0.08 mol) of the compound represented by formula (S-4). Then, 700 g of toluene was added and the mixture was heated to 90°C. Then, 1.3 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 115 g (0.59 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl group:total alkenyl group = 0.99:1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain a polymer. To this polymer, 1000 g of propylene glycol monomethyl ether was added, and after confirming its dissolution, 475 g (5.52 mol) of methacrylic acid and 24.1 g (0.092 mol) of triphenylphosphine were added, and the mixture was heated at 110°C for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and methacrylic acid were removed from the reaction solution under reduced pressure to obtain polymer 5. The Mw of polymer 5 was 15,000. 1H-NMR (manufactured by Bruker) confirmed 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).

[0158] [Comparative Example 1] Synthesis of Comparative Polymer 1

[0159] A 10-liter flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser was charged with 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-5b), and 18.6 g (0.10 mol) of the compound represented by formula (S-4). Then, 1100 g of toluene was added and the mixture was heated to 80°C. Then, 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 group:total alkenyl group = 0.99:1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain Comparative Polymer 1. The Mw of Comparative Polymer 1 was 12,000.

[0160] [Comparative Example 2] Synthesis of Comparative Polymer 2

[0161] A 10L flask equipped with a stirrer, thermometer, nitrogen exchanger, and reflux condenser was charged with 1362g (0.45 mol) of the compound represented by formula (S-2b), 215g (0.50 mol) of the compound represented by formula (S-5a), and 271g (0.50 mol) of the compound represented by formula (S-5b). Then, 2100g of toluene was added and the mixture was heated to 70°C. Then, 2.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 105g (0.54 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl group:total alkenyl group = 0.99:1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 12 hours. The toluene was then removed from the reaction solution under reduced pressure to obtain Comparative Polymer 2. The Mw of Comparative Polymer 2 was 14,000.

[0162] [Adhesion test]

[0163] With respect to 100 parts by mass of polymers 1 to 5 and comparative polymers 1 to 2, 20 parts by mass of JERCURE 113 (manufactured by Mitsubishi Chemical Corporation) were added as an amine curing agent, and 55 parts by mass of cyclopentanone were added and dissolved until uniform. Each solution was applied on a silicon wafer by spin coating and pre-baked at 120°C for 2 minutes to produce a film (thickness 30 μm). On each obtained film, a silicon wafer cut into 4 mm squares was thermocompressed at 180°C, 2 MPa, and 600 seconds, and then post-cured at 180°C and 4 hours. For this sample, die shear was performed using an adhesion tester DAGE4000PXY manufactured by Nordson DAGE Company at a measurement speed of 50.0 μm / second and a measurement height of 50.0 μm to evaluate the adhesion. The average value of 10 measurements for each composition is shown in Table 1.

[0164] [Table 1]

[0165]

[0166] The above results show that the film obtained from the polymer of the present invention has excellent adhesion.

Claims

1. A polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain and containing an acryloyl group or a methacryloyl group in its side chain.

2. The polymer according to claim 1, comprising a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), and further comprising a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4), [Chemistry 1] Where R 1 ~R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and m is each independently an integer of 1 to 600. When m is an integer of 2 or greater, each R 3 They can be the same or different. 4 They may be the same or different from each other. 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. 1 is a divalent group represented by the following formula (X1), X 2 is a divalent group represented by the following formula (X2), [Chemistry 2] Where n 1 and n 2 are each independently an integer of 1 to 7, R 11 ~R 14 are each independently a hydrogen atom or a methyl group, L 1 and L 2 Each independently represents a saturated alkylene group having 1 to 15 carbon atoms, a portion of the -CH2- of the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, a portion or all of the hydrogen atoms of the saturated alkylene group may be replaced by hydroxyl groups, the dotted line represents the bonding end, [Chemistry 3] Where R 21 and R 22 are each independently a hydrogen atom or a methyl group, R 23 and R 24 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms. 1 and k 2 Each independently represents an integer from 0 to 7, p represents an integer from 0 to 600, and the dotted line represents a bonding end.

3. The polymer according to claim 2, wherein L 1 and L 2 They are all saturated hydrocarbylene groups in which one or more hydrogen atoms are replaced by hydroxyl groups, or saturated hydrocarbylene groups in which one or more -CH2- groups are replaced by -CONH-.

4. The polymer according to claim 2 or 3, wherein L 1 and L 2 The carbon number of each is 1 to 8.

5. The polymer according to claim 2 or 3, wherein n 1 and n 2 Both are 1.

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

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

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