Method for manufacturing fluorine-containing copolymer

Abstract

To provide a method for manufacturing a fluorine-containing copolymer with which it is possible to efficiently introduce a fluoro(poly)ether group when manufacturing a fluorine-containing copolymer containing a fluoro(poly)ether group.SOLUTION: A method for manufacturing a fluorine-containing copolymer includes copolymerization in a state of containing at least one kind of fluoro(poly)ether group-containing monomer A and at least one kind of monomer B different from the monomer A. The copolymerization is carried out in a solvent containing a compound X that can form hydrogen bonding.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a fluorine-containing copolymer. [Background technology]

[0002] Since fluoro(poly)ether groups have low surface free energy, fluoropolymers containing such groups are expected to be used as water- and oil-repellent coating agents. For example, a fluorine-containing ether compound having a perfluoro(poly)ether group (hereinafter also referred to as a "PFPE group") in which all hydrogen atoms are replaced with fluorine atoms and a hydrolyzable silyl group can form a surface layer exhibiting high lubricity, water- and oil-repellency, etc. on the surface of a substrate, and is therefore suitable for use as a surface treatment agent. A surface treatment agent containing a fluorine-containing ether compound is used in applications requiring a long-term maintenance of the performance of the surface layer being less likely to lose water- and oil-repellency even when repeatedly rubbed with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability), for example, as a surface treatment agent for members constituting the surface of a touch panel that is touched by fingers, eyeglass lenses, and displays of wearable terminals.

[0003] On the other hand, since the fluoro(poly)ether group has a large molecular weight and low electronic polymerizability, the introduction efficiency of the fluoro(poly)ether group into a polymer is low. In addition, when copolymerizing with other monomers, if the other monomers have amide groups, the hydrogen bond interaction between the amide groups predominates, promoting the polymerization of the other monomers, making the introduction of the fluoro(poly)ether group even more difficult. Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a method for producing a fluorocopolymer which can efficiently introduce fluoro(poly)ether groups when producing a fluorocopolymer containing fluoro(poly)ether groups. [Means for solving the problem]

[0005] The present invention relates to the following process for producing a fluorine-containing copolymer. A method for producing a fluorine-containing copolymer by copolymerizing at least one type of each of a fluoro(poly)ether group-containing monomer A and a monomer B different from the monomer A, the copolymerization being carried out in a solvent containing a compound X capable of forming a hydrogen bond. Effect of the Invention

[0006] According to the present invention, when a fluorine-containing copolymer is produced, a fluoro(poly)ether group can be efficiently introduced. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In this specification, a compound represented by formula (x) may be referred to as "compound (x)". A group represented by formula (y) may be referred to as "group (y)". In this specification, the fluoro(poly)ether group means a (poly)oxyfluoroalkyl group, which is a general term for an oxyfluoroalkyl group and a polyoxyfluoroalkyl group. The perfluoro(poly)ether group means a (poly)oxyperfluoroalkyl group, which is a general term for an oxyperfluoroalkyl group and a polyoxyperfluoroalkyl group. The fluoroalkyl group means a group in which some or all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms, and the perfluoroalkyl group means a group in which all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms.

[0008] In this specification, the mass average molecular weight (Mw) means the mass average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran as the mobile phase and converted based on standard polymethyl methacrylate (PMMA), and the number average molecular weight (Mn) means the number average molecular weight measured by the same GPC.

[0009] In this specification, unless otherwise specified, % represents % by mass.

[0010] The production method according to an embodiment of the present invention is a method for producing a fluorine-containing copolymer by copolymerizing at least one each of a fluoro(poly)ether group-containing monomer A and a monomer B different from the fluoro(poly)ether group-containing monomer A. The copolymerization is carried out in a solvent containing a compound X capable of forming a hydrogen bond. This suppresses interactions between monomers B in the reaction system and promotes polymerization of monomer A and monomer B, making it possible to efficiently introduce fluoro(poly)ether groups into the fluorine-containing copolymer.

[0011] <Fluoro(poly)ether group-containing monomer A> The fluoro(poly)ether group-containing monomer A preferably has a (poly)oxyfluoroalkyl group and a polymerizable group. Monomer A is preferably a compound represented by the following formula (A-1) or formula (A-2).

[0012] (G 1 ) x1 -L 1 -(P 1 ) y1 Formula (A-1) G 1 : A monovalent group having a (poly)oxyfluoroalkylene chain L 1 : Single bond or (x1+y1)-valent organic group P 1 :Polymerizable group x1:1~6 y1:1~6

[0013] (P 2 ) x2 -L 2 -G 2 -L 3 -(P 3 ) y2 Formula (A-2) G 2 : A divalent group having a (poly)oxyfluoroalkylene chain L 2: Single bond or (x2+1)-valent organic group L 3 : Single bond or (y2+1)-valent organic group P 2 :Polymerizable group P 3 :Polymerizable group x2:0~6 y2:1~6

[0014] G 1 The monovalent group having a (poly)oxyfluoroalkylene chain in 1 (L 1 If is a single bond, P 1 ) at the terminal bonded to the fluoroalkyl group, or has an -O- between carbon atoms in a carbon chain having two or more carbon atoms, or has both of these. 1 As the alkyl group, a structure represented by the following formula (G1-1) is preferable. R f0 O-[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-(R f7 ) m7 - Formula (G1-1) R f0 is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having one carbon atom, R f2 is a fluoroalkylene group having 2 carbon atoms, R f3 is a fluoroalkylene group having 3 carbon atoms, R f4 is a fluoroalkylene group having 4 carbon atoms, R f5 is a fluoroalkylene group having 5 carbon atoms, R f6 is a fluoroalkylene group having 6 carbon atoms, R f7 is a fluoroalkylene group having 1 to 6 carbon atoms, m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more; m7 is an integer of 0 or 1; and m1+m2+m3+m4+m5+m6+m7 is an integer of 0-200.

[0015] In addition, (R f1 O)~(R f6 O) may be bonded in any order. In formula (G1-1), m1 to m6 are each represented by (R f1 O)~(R f6 O), not the arrangement. For example, (R f5 O) m5 is (R f5 O) is m5, and (R f5 O) m5 It does not represent the block arrangement structure of (R f1 O)~(R f6 The order of the units does not represent the bonding order of the units. When m7 is 0, G 1 The bond end of is -O-. When m7 is 1, G 1 The bond end of is a carbon atom (R f7 (the terminal carbon atom of Also R f0 Fluoroalkyl groups represented by R f1 ~R f7 The fluoroalkylene group represented by the following formula (I) may be linear, branched, or have a ring structure. In addition, each (R f1 O)~(R f6 The position of -O- in each (R f1 O)~(R f6 O) may have two or more -O-.

[0016] R f1 Specific examples include -CF2- and -CHF-. R f2Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, -CH2CHF-, etc. R f3 Specific examples of the compound include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)- CHF-, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F) -CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, -CH(CH2F)-CH2-, and the like. R f4 Specific examples of the formula include, -CF2CF2CF2CF2-, -CHFCF2CF2CF2-, -CH2CF2CF2CF2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2C Examples include HFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, -cycloC4F6-, and the like. R f5 Specific examples of the alkyl group include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, -cycloC5F8-, and the like. R f6 Specific examples of the compound include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, -cycloC6F 10 - etc. Also, R f0 and R f7 As a specific example of R f1 ~R f6 Examples of the above-mentioned examples are the same as those mentioned above. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group. -cycloC5F8- means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,3-diyl group. 10 "-" means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0017] When the obtained fluorine-containing copolymer is used as a surface treatment agent or a raw material thereof, 1Among them, it is preferable that the compound has any one of the structures represented by the following formulae (F1) to (F5) because it has excellent water and oil repellency, abrasion resistance, and fingerprint stain removability. R f0 O-(R f1 O) m1 -(R f2 O) m2 - Formula (F1) R f0 O-(R f2 O) m2 -(R f4 O) m4 - Formula (F2) R f0 O-(R f2 O) m2 -(R f6 O) m6 -(R f7 ) m7 - Formula (F3) R f0 O-(R f3 O) m3 - Formula (F4) R f0 O-(R f2 O) m2 -(R f7 ) m7 - Formula (F5) Here, each symbol in the formulas (F1) to (F5) is the same as in the formula (G1-1) above.

[0018] In the above formulas (F1) to (F3), (R f1 O) and (R f2 O), (R f2 O) and (R f4 O), (R f2 O) and (R f6 The order of bonds between (R f1 O) and (R f2 O) may be arranged alternately, (R f1 O) and (R f2 O) may be arranged in blocks or randomly. In formula (F1), m1 is preferably an integer of 0 to 30, and more preferably an integer of 0 to 20. Furthermore, m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. In formula (F2), m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m4 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. In formula (F3), m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m6 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. In formula (F4), m3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. In formula (F5), m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Also, m7 is 0 or 1.

[0019] G 2 The divalent group having a (poly)oxyfluoroalkylene chain in 1 (L 1 If is a single bond, P 1 ) or has -O- between carbon atoms in a carbon chain having 2 or more carbon atoms; 2 (L 2 If is a single bond, P 2 ) or a combination thereof. 2 As the alkyl group, a structure represented by the following formula (G2-1) is preferable. -(R f7 ) m7 -[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-(R f7 ) m7 - Formula (G2-1) R f1 ~R f7 The definition and preferred embodiments of R in formula (G1-1) are as follows: f1 ~R f7 is the same as: The definitions and preferred embodiments of m1 to m7 are the same as those of m1 to m7 in formula (G1-1).

[0020] When the obtained fluorine-containing copolymer is used as a surface treatment agent or a raw material thereof, 2 Among these, it is preferable that the compound has any one of the structures represented by the following formulae (F6) to (F9) because it has excellent water and oil repellency, abrasion resistance, and fingerprint stain removability. -(R f1 O) m1 -(R f2 O) m2 - Formula (F6) -(R f2 O) m2 -(R f4 O) m4 - Formula (F7) -(R f3 O) m3 - Formula (F8) -(R f7 ) m7 -(R f1 O) m1 -(R f2 O) m2 -(R f7 ) m7 - Formula (F9) However, each symbol in formula (F5) to formula (F9) is the same as in formula (G2-1) above.

[0021] Since the effect of the present invention is more pronounced as the fluorine content in monomer A is higher, it is preferable that the fluoro(poly)ether group is a perfluoro(poly)ether group (PFPE group), since this effect is more easily exhibited.

[0022] Polymerizable group P in monomer A 1 ~P 3 Each of the groups may independently include a group having a polymerizable unsaturated bond, a cyclic ether structure-containing group, and a hydrolyzable silane-containing group. The group having a polymerizable unsaturated bond may include an ethylenic double bond-containing group, and for example, an acrylic polymerizable group is preferred. The group having a cyclic ether structure may include a 3-membered or 4-membered ring ether-containing group, and for example, an epoxy polymerizable group is preferred. The hydrolyzable silane-containing group may include, for example, a siloxane polymerizable group.

[0023] x1 is an integer from 1 to 6, and the polymerizable group P 1 The structure of L 1 It can be set according to the valence of y1 is an integer of 1 to 6, and the polymerizable group P 1 The extent to which is incorporated can be determined depending on the application of monomer A, etc.

[0024] x2 is an integer of 0 to 6, and the polymerizable group P 2 The structure of L 1 It can be set according to the valence of y2 is an integer of 1 to 6, and the polymerizable group P 3 The extent to which is incorporated can be determined depending on the application of monomer A, etc.

[0025] Polymerizable group P 1 ~Polymerizable group P 3 Each of these independently includes a group having a polymerizable unsaturated bond, a group containing a cyclic ether structure, or a group containing a hydrolyzable silane. A group having a polymerizable unsaturated bond is preferred, and an acrylic polymerizable group is particularly preferred from the viewpoint of polymerization reactivity. The acrylic polymerizable group is preferably a group represented by the following formula: -OCOCR 21 =CH2 R 21 represents a hydrogen atom, an alkyl group, a chloro group or a fluoro group. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and one or more hydrogen atoms may be substituted with a halogen atom. The halogen atom is preferably a fluorine atom. The alkyl group is preferably a methyl group.

[0026] L 1 When is an organic group having a valence of (x1+y1), L 1 is a divalent or higher organic group, examples of which include an alkylene group, a heteroatom-containing divalent organic group, a group in which a heteroatom-containing divalent organic group is inserted inside or at the end of an alkylene group, or a combination of these, etc. In addition, 0 to 2 hydrogen atoms of the alkylene group may be substituted with a hydroxy group or a mercapto group. The alkylene group is -(CH2) i1 - (i1 is an integer of 1 to 8) is preferable. The heteroatom-containing divalent organic group is -C(O)NR 26 -, -C(O)O-, -C(O)-, -O-, -NR 26 -, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 26 -,-SO2NR 26 -, -Si(R 26 )2-, -OSi(R 26 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and divalent organopolysiloxane residues. 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 26 The alkyl group preferably has 1 to 3 carbon atoms, and particularly preferably has 1 or 2 carbon atoms. Also, L 1 The bonding direction is not limited. Such a L 1 Specific examples of the structure are shown below. The wavy line represents G 1 or P 1 This shows the joint with

[0027] [ka]

[0028] L 2 When is a single bond, x2 is 1. L 2 When L is an organic group having a valence of (x2+1), 2 is an organic group with a valence of 1 or more. L 2 For example, when L is a monovalent organic group, x2 is 0. 2 Examples of the alkyl group include a hydrogen atom, a monovalent alkyl group, an alkyl group having a valence of 1 to 10, or a monovalent alkyl group having a valence of 1 to 10. 2and a group in which a heteroatom-containing divalent organic group is inserted at the bonding end with the alkyl group. In addition, 0 to 3 hydrogen atoms of the monovalent alkyl group may be substituted with a hydroxy group or a mercapto group.

[0029] Such a L 2 Specific examples of the structure are shown below. The wavy line is G 2 This shows the joint with

[0030] [ka]

[0031] L 2 For example, when L is a divalent or higher organic group, 1 The same groups as those shown below can be mentioned.

[0032] L 3 When is a single bond, y2 is 1. L 3 When L is a (y2+1)-valent organic group, 3 is an organic group with a valence of 1 or more. L 3 For example, when L is a monovalent organic group, y2 is 0. 3 As the monovalent organic group, L 2 The same groups as those shown below can be mentioned. L 3 is a divalent or higher organic group, and L is a divalent or higher organic group. 2 The same groups as those shown below can be mentioned.

[0033] Preferred embodiments of the monomer A include the following compounds. R f0 O-(R f2 O) m2 -(R f6 O) m6 -(R f7 ) m7 -(CH2) i1 -OCOCR 21 =CH2 R f0 O-(Rf2 O) m2 -(R f7 ) m7 -(CH2) i1 -OCOCR 21 =CH2 R f0 O-(R f2 O) m2 -(R f7 ) m7 -(CH2) i1 -OCONH-(CH2) i1 -OCOCR 21 =CH2 CH2=CR 21 COO-(CH2) i1 -(R f7 ) m7 -(R f1 O) m1 (R f2 O) m2 -(R f7 ) m7 -(CH2) i1 -OCOCR 21 =CH2 CH2=CR 21 COO-(CH2) i1 -NHCOO-(CH2) i1 -(R f7 ) m7 -(R f1 O) m1 (R f2 O) m2 -(R f7 ) m7 -(CH2) i1 -OCONH-(CH2) i1 -OCOCR 21 =CH2 [CH2=CR 21 COO-(CH2) i1 ]2C(CH3)-NHCOO-(CH2) i1 -(R f7 ) m7 -(R f1 O) m1 (R f2 O) m2 -(R f7 ) m7 -(CH2) i1 -OCONH-C(CH3)[(CH2) i1-OCOCR 21 =CH2]2 In the above formula, R f0 , R f2 , R f4 , m4, R f6 , m6, R f7 , m7, R 21 The definitions of each of the above are as described above. i1 is an integer of 1 to 8.

[0034] Monomer A may be a commercially available product, or can be produced by referring to known methods described in JP-A-2021-135499 and the like.

[0035] <Monomer B> Monomer B is not limited as long as it is a monomer different from monomer A. From the viewpoint of easily exerting the effects of the present invention, it is preferable that the monomer B has a structure capable of forming a hydrogen bond. As a result, a hydrogen bond is also formed between the compound X and the monomer B, and therefore, a hydrogen bond is less likely to be formed between the monomers B, and the polymerization reaction between the monomer A and the monomer B is promoted.

[0036] Monomer B preferably has a structure capable of forming a hydrogen bond and a polymerizable group. Monomer B is preferably a compound represented by the following formula (B-1) or formula (B-2).

[0037] (S 21 ) x3 -L 4 -(P 4 ) y3 Formula (B-1) S 21 : A monovalent group having a structure capable of forming a hydrogen bond L 4 : Single bond or (x3+y3)-valent organic group P 4 :Polymerizable group x3:1~6 y3:1~6

[0038] (P 5 ) x4 -L 5-S 22 -L 6 -(P 6 ) y4 Formula (B-2) S 22 : A divalent group having a structure capable of forming a hydrogen bond L 5 : Single bond or (x4+1)-valent organic group L 6 : Single bond or (y4+1)-valent organic group P 5 :Polymerizable group P 6 :Polymerizable group x4:1~6 y4:1~6

[0039] S 21 and S 22 The structure capable of forming a hydrogen bond in the above is preferably one or more structures selected from an amide bond, a urethane bond, a urea bond, a sulfonamide bond, a sulfonic acid, a carboxylic acid, a hydroxy group, a mercapto group, and an amino group, and more preferably one or more structures selected from an amide bond, a urethane bond, and a hydroxy group. 21 and S 22 may have one or more structures capable of forming hydrogen bonds.

[0040] S 21 and S 22 may have a structure other than the structure capable of forming a hydrogen bond. The other structure is preferably a monovalent or divalent organic group having 1 to 30 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have an ethereal oxygen atom, or a divalent hydrocarbon group having 1 to 30 carbon atoms which may have an ethereal oxygen atom, or a combination thereof.

[0041] The monovalent hydrocarbon group having 1 to 30 carbon atoms which may have an etheric oxygen atom is preferably an alkyl group having 1 to 30 carbon atoms which may have an etheric oxygen atom, an alkenyl group having 2 to 30 carbon atoms which may have an etheric oxygen atom, an alkynyl group having 2 to 30 carbon atoms which may have an etheric oxygen atom, or an aryl group having 6 to 30 carbon atoms which may have an etheric oxygen atom.

[0042] The alkyl group may have any of a linear, branched, or cyclic structure. The alkyl group preferably has 1 to 30 carbon atoms, and more preferably has 1 to 10 carbon atoms. Examples of the alkyl group include the following structures. CH3(CH2) s1 - (s1:0~9)

[0043] Examples of the alkyl group having an etheric oxygen atom include the following structures. CH3-O x -(CH2) s2 -O y -(CH2) s3 -O z -(CH2) s4 - x: 0 or 1 s2:1~6 y: 0 or 1 s3:1~6 z: 0 or 1 s4:1~6

[0044] The alkenyl group may have any of a linear, branched, or cyclic structure. The number of carbon atoms in the alkenyl group is preferably 2 to 30, and more preferably 2 to 10. The alkenyl group may contain multiple carbon-carbon double bonds. Examples of the alkenyl group include the following structures. CH2=CH-(CH2) t1 - (t1:1~18) H(CH2) t2 -CH=CH-(CH2) t3 - (t2: 1~10, t3: 0~10, 1 <t2+t3<7)

[0045] The alkynyl group may have any of a linear, branched, or cyclic structure. The number of carbon atoms in the alkynyl group is preferably 2 to 30, and more preferably 2 to 10. The alkynyl group may contain multiple carbon-carbon triple bonds. Examples of the alkynyl group include the following structures. t1: 1 to 18, t2: 1 to 10, t3: 0 to 10, 1 <t2+t3<7、である。

[0046] [ka]

[0047] The aryl group includes a phenyl group and a naphthyl group.

[0048] The divalent hydrocarbon group having 1 to 30 carbon atoms which may have an etheric oxygen atom is preferably an alkylene group having 1 to 30 carbon atoms which may have an etheric oxygen atom, an alkenylene group having 2 to 30 carbon atoms which may have an etheric oxygen atom, an alkynylene group having 2 to 30 carbon atoms which may have an etheric oxygen atom, or an arylene group having 6 to 30 carbon atoms which may have an etheric oxygen atom.

[0049] The alkylene group may have any of a linear, branched, or cyclic structure. The alkylene group preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 10 carbon atoms. Examples of the alkylene group include the following structures. -(CH2) s1 - (s1:1~10)

[0050] Examples of the alkylene group having an etheric oxygen atom include the following structures. -CH2-O x -(CH2) s2 -O y -(CH2) s3 -O z -(CH2) s4 - x: 0 or 1 s2:1~6 y: 0 or 1 s3:1~6 z: 0 or 1 s4:1~6

[0051] The alkenylene group may have any of a linear, branched, or cyclic structure. The number of carbon atoms in the alkenylene group is preferably 2 to 30, and more preferably 2 to 10. The alkenyl group may contain multiple carbon-carbon double bonds. Examples of the alkenylene group include the following structures. -CH=CH-(CH2) t1 - (t1:1~18) -(CH2) t2 -CH=CH-(CH2) t3 - (t2: 1~10, t3: 0~10, 1 <t2+t3<7)

[0052] The alkynylene group may have any of a linear, branched, or cyclic structure. The number of carbon atoms in the alkynylene group is preferably 2 to 30, and more preferably 2 to 10. The alkynylene group may contain multiple carbon-carbon triple bonds. Examples of the alkynylene group include the following structures. In addition, t1: 1 to 18, t2: 1 to 10, t3: 0 to 10, 1 <t2+t3<7、である。

[0053] [ka]

[0054] Examples of the arylene group include a phenylene group and a naphthylene group.

[0055] S 21 Examples of the structure include the following. CH3(CH2) s1 -NHC(O)O- (s1:0~9) CH3(CH2) s1 -OC(O)NH- (s1:0-9) CH3(CH2) s1 -NHC(O)- (s1:0~9) CH3(CH2)s1 -C(O)NH- (s1:0-9) CH3(CH2) s1 -NHC(O)NH- (s1:0-9) CH3(CH2) s1 -SO2NH- (s1:0~9) CH3(CH2) s1 -NHSO2- (s1:0~9) HO-(CH2) s1 -NHC(O)O- (s1:1-10) HO-(CH2) s1 -OC(O)NH- (s1:1-10) HO-(CH2) s1 -NHC(O)- (s1:1-10) HO-(CH2) s1 -C(O)NH- (s1:1-10) HO-(CH2) s1 -NHC(O)NH- (s1:1-10) HO-(CH2) s1 -SO2NH- (s1:1~10) HO-(CH2) s1 -NHSO2- (s1:1~10)

[0056] S 22 Examples of the structure include the following. -(CH2) s1 -NHC(O)O- (s1:1-10) -(CH2) s1 -OC(O)NH- (s1:1-10) -(CH2) s1 -NHC(O)- (s1:1-10) -(CH2) s1 -C(O)NH- (s1:1-10) -(CH2) s1 -NHC(O)NH- (s1:1-10) -(CH2) s1 -SO2NH- (s1:1~10) -(CH2) s1 -NHSO2- (s1:1~10)

[0057] Polymerizable group P 5 and P 6 As the group, P in the above formula (A-1) or formula (A-2) 1 ~P 3 The same groups as those shown in the above can be mentioned, and the preferred embodiment is also P 1 ~P 3 From the viewpoint of polymerizability, it is preferable that the polymerizable group in the monomer B is the same as the polymerizable group in the monomer A.

[0058] L 4 When is an organic group having a valence of (x3+y3), L 4 is a divalent or higher organic group, examples of which include an alkylene group, a heteroatom-containing divalent organic group, a group in which a heteroatom-containing divalent organic group is inserted inside or at the end of an alkylene group, etc. In addition, 0 to 2 hydrogen atoms of the alkylene group may be substituted with a hydroxy group or a mercapto group. The alkylene group and the heteroatom-containing divalent organic group are, for example, L in the above formula (A-1). 1 The same groups as those shown in the above can be mentioned, and preferred embodiments are also the same as those shown in the above. 1 is the same as:

[0059] L 5 When L is an organic group having a valence of (x4+1), 6 is a divalent or higher organic group, in which case, L 1 The same groups as those shown below can be mentioned.

[0060] L 6 When L is a (y4+1)-valent organic group, 6 is a divalent or higher organic group, in which case, L 1 The same groups as those shown below can be mentioned.

[0061] Monomer B may be a commercially available product, or can be produced by referring to known methods.

[0062] The amount of monomer B added varies depending on the structures of monomer A and monomer B. The amount of monomer B added is preferably 10 to 100 times by mol, more preferably 50 to 100 times by mol, based on the amount of monomer A.

[0063] <Solvent> The solvent for the copolymerization is not limited as long as it can dissolve the monomer A and the monomer B. The solvent is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both. The organic solvent may be one or more of the solvents listed below.

[0064] Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and hydrochlorofluoroolefins. The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. Commercially available products include, for example, C6F 13 H (ASAHIKLIN (registered trademark) AC-2000, manufactured by AGC), C6F 13 Examples include C2H5 (ASAHIKLIN (registered trademark) AC-6000, manufactured by AGC Corporation) and C2F5CHFCHFCF3 (VERTREL (registered trademark) XF, manufactured by Chemours Corporation). Examples of the fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having a carbon number of 4 to 12. Examples of commercially available products include CF3CH2OCF2CF2H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300). Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. Examples of the hydrochlorofluoroolefin include 1-chloro-2,3,3-trifluoro-1-propene and 1-chloro-3,3-difluoro-1-propyne.

[0065] As the non-fluorinated organic solvent, a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferable, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents and ester organic solvents.

[0066] In the production method according to the embodiment of the present invention, even if a solvent in which monomer B is likely to aggregate due to hydrogen bonding (for example, a fluorine-based organic solvent) is used as the polymerization reaction solvent, the aggregation can be prevented by the presence of the below-described compound X, and the progress of copolymerization is not hindered. Therefore, for example, when the fluorine chain of monomer A is long, the copolymerization reaction can be progressed even if a fluorine-based organic solvent is used to increase solubility.

[0067] <Compound X> Compound X is a compound capable of forming hydrogen bonds, and the presence of compound X in the copolymerization reaction system suppresses the interaction between monomers B, and promotes the polymerization of fluoro(poly)ether group-containing monomer A and monomer B, resulting in efficient introduction of fluoro(poly)ether groups into the fluorine-containing copolymer. In particular, the presence of compound X is highly effective in a reaction system in which interactions between monomers B are likely to occur. Such a reaction system may be, for example, a case in which monomer B has a structure capable of forming hydrogen bonds as described above, or a case in which a fluorine-based organic solvent is used. For example, when monomer B has a structure capable of forming hydrogen bonds, monomer B is likely to form hydrogen bonds with compound X in the solvent, and can be stably dispersed in the solvent. It is preferable that the compound X itself does not have a polymerizable group and does not function as a polymerizable monomer. From the viewpoint of increasing the solubility or dispersibility in a solvent, the molecular weight of the compound X is preferably 300 or less.

[0068] The compound X is preferably a compound having one or more structures selected from an amide bond, a urethane bond, a urea bond, a sulfonamide bond, a sulfonic acid, a carboxylic acid, a hydroxy group, a mercapto group, and an amino group.

[0069] Compound X is preferably a protic solvent or a compound having a double bond between different atoms.

[0070] The protic solvent is a solvent having a proton-donating group such as OH or NH, and is preferably, for example, a fluoroalcohol, specifically, trifluoroethanol or hexafluoroisopropanol. Note that the use of a fluoroalcohol as a protic solvent is limited to the case where a fluoroalcohol is not used as a solvent for copolymerization.

[0071] The case where there is a double bond between different atoms means that different atoms selected from C, S, N, and O are bonded to each other via a double bond. The compound having a double bond between different atoms is preferably a compound having a structure selected from -C(=O)-, -N=O, and -S(=O)(=O)-, and examples thereof include methyl ethyl ketone and N,N-dimethylformamide.

[0072] The amount of compound X added is preferably 1 to 20 in terms of the volume ratio of solvent / compound X from the viewpoint of polymerizability.

[0073] <Initiator> In the method for producing the fluorine-containing copolymer according to this embodiment, it is preferable to use an initiator in the copolymerization. The initiator can be appropriately selected depending on the polymerizable groups of the monomer A and the monomer B, and for example, an organic peroxide, an inorganic peroxide, an azo compound, etc. can be preferably used.

[0074] In the polymerization reaction, the order of addition of each material is not limited, and a reaction solution is prepared by adding monomer A, monomer B, and if necessary, other monomers, compound X, and an initiator to a reaction solvent. The polymerization reaction is allowed to proceed by heating the reaction solution to preferably 30 to 100°C and shaking or stirring the solution for preferably 1 to 48 hours.

[0075] <Fluorine-containing copolymer> The fluorine-containing copolymer obtained by the production method according to the present embodiment contains fluoro(poly)ether groups and has a fluorine atom content of preferably 4% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. As described above, the fluorine-containing copolymer according to the present embodiment exhibits a high fluorine atom content.

[0076] Furthermore, when monomer B has a structure capable of forming hydrogen bonds, the fluorinated copolymer obtained by the production method according to the present embodiment has a structure capable of forming hydrogen bonds, and therefore has high solubility in non-fluorinated organic solvents. For example, the fluorinated copolymer can be dissolved in a non-fluorinated organic solvent at preferably 1% by mass or more, more preferably 5% by mass or more.

[0077] Based on the above, this specification discloses the following method for producing a fluorine-containing copolymer, etc. [1] A method for producing a fluorocopolymer by copolymerizing a fluoro(poly)ether group-containing monomer A and a monomer B different from the monomer A in a state containing at least one type each of the monomers, comprising the steps of: The copolymerization is carried out in a solvent containing a compound X capable of forming a hydrogen bond. [2] The method according to [1], wherein the monomer B has a structure capable of forming a hydrogen bond. [3] The method according to [1] or [2], wherein the monomer B has one or more structures selected from an amide bond, a urethane bond, a urea bond, a sulfonamide bond, a sulfonic acid, a carboxylic acid, a hydroxy group, a mercapto group, and an amino group. [4] The method according to any one of [1] to [3], wherein the monomer B has one or more structures selected from an amide bond, a urethane bond, and a hydroxy group. [5] The method according to any one of [1] to [4], wherein the content of the compound X is 0.1 equivalents or more relative to the content of the monomer B. [6] The method according to any one of [1] to [5], wherein the compound X is a protic solvent or a compound having a double bond between different atoms. [7] The method according to any one of [1] to [6], wherein the fluorine atom content in the fluorine-containing copolymer is 4 mass% or more. [8] The method according to any one of [1] to [7], wherein the fluorine-containing copolymer is soluble in the non-fluorine-based organic solvent at 1 mass % or more. [9] A fluorine-containing copolymer which contains a fluoro(poly)ether group and has a fluorine atom content of 4 mass% or more. EXAMPLES

[0078] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0079] Each measurement was carried out by the following method. [Mass average molecular weight (Mw)] Gel permeation chromatography (GPC) of several monodisperse polystyrene polymers with different degrees of polymerization, which are commercially available as standard samples for molecular weight measurement, was performed using a commercially available GPC measurement device (Tosoh Corporation, device name: HLC-8320GPC), and a calibration curve was created based on the relationship between the molecular weight of polymethyl methacrylate (PMMA) and the retention time. The sample was diluted to 1.0% by mass with tetrahydrofuran and passed through a 0.5 μm filter, and then the GPC of the sample was measured using the above-mentioned GPC measurement device. The GPC spectrum of the sample was analyzed by computer using the calibration curve to determine the mass average molecular weight (Mw) of the sample.

[0080] [Fluorine atom content (mass%)] The fluorine atom content was calculated by 19F NMR measurement using 1,4-bis(trifluoromethyl)benzene as a standard substance.

[0081] [Monomer A1: CF3OCF2CF2O (CF2CF2CF2CF2OCF2CF2O) 13 Synthesis of CF2CF2CF2CH2OCOC(CH3)=CH2 In a 100 ml glass flask, add AC-2000 (AGC, 70 g) and CF3OCF2CF2O (CF2CF2CF2CF2OCF2CF2O). 13 CF2CF2CF2CH2OH (35.0 g, n=13), triethylamine (1.41 g), N,N-dimethyl-4-aminopyridine (DMAP) (0.11 g), and dibutylhydroxytoluene (BHT) (0.08 g) were charged and bubbled with N2. Methacrylic anhydride (1.51 g) was slowly added and stirred at room temperature for 1 hour. Methanol was added, and the organic layer was washed with water, and then concentrated to obtain a crude product. The product was purified by silica gel chromatography to obtain Monomer A1 (31.7 g). 1 H NMR(400MHz, CDCl3)δ6.23(s,1H),5.75(s,1H),4.68(t,J=13.4Hz,2H),2.02(s,3H).

[0082] [Monomer A2: CF3OCF2CF2O (CF2CF2CF2CF2OCF2CF2O) 13 Synthesis of CF2CF2CF2CH2OCOCH=CH2 In a 100 ml glass flask, add AE-3000 (AGC, 20 g) and CF3OCF2CF2O (CF2CF2CF2CF2OCF2CF2O). 13CF2CF2CF2CH2OH (10.0 g, n=13) and triethylamine (0.42 g) were charged and N2 was bubbled through. The mixture was cooled to 0°C, and acrylic acid chloride (0.32 g) was slowly added, followed by stirring at room temperature for 3 hours. Methanol was added, and the organic layer was washed with water, and then concentrated to obtain a crude product. The product was purified by silica gel chromatography to obtain Monomer A2 (8.0 g). 1 H NMR(400MHz,CDCl3)δ6.12(dd,J=17.0,11.0Hz,1H),6.05(dd,J=17.0,3.1Hz,1H),5.89(dd,J=11.0,3.1Hz,1H),4.71(t,J=13.0Hz,2H).

[0083] [Monomer A3: CF3OCF2CF2O (CF2CF2CF2CF2OCF2CF2O) 13 Synthesis of CF2CF2CF2CH2OCONHCH2CH2OCOC(CH3)=CH2 In a 100 ml glass flask, add 1,3-bistrifluoromethylbenzene (AGC, 5.9 g), CF3OCF2CF2O (CF2CF2CF2CF2OCF2CF2O) 13 CF2CF2CF2CH2OH (10.0 g, n=13), 2-isocyanatoethyl methacrylate (Karends (registered trademark) MOI, manufactured by Resonac, 0.41 g), and dibutyltin dilaurate (0.018 g) were added and stirred at 40° C. for 2 hours. The mixture was then concentrated to obtain a crude product. The product was purified by silica gel chromatography to obtain Monomer A3 (8.7 g). 1 H NMR(400MHz,CDCl3)δ6.26(s,1H),5.67(s,1H),5.31(s,1H),4.75(t,J=13.6Hz,2H),4.40(t,J=5.2Hz,2H),3.69(q,J=5.5Hz,2H),2.06(s,3H).

[0084] [Synthesis of Monomer A4: CH2=C(CH3)COOCH2-(CF2O)7(CF2CF2O)9-CH2OCOC(CH3)=CH2] In a 200 ml glass flask, add AC-2000 (AGC, 90 g), HOCH2 (CF2O), n (CF2CF2O) m CH2OH (fomblin D2, Solvay, 45 g, n=7, m=9), triethylamine (7.3 g), DMAP (0.38 g), and BHT (0.03 g) were charged and bubbled with N2. Methacrylic anhydride (11.1 g) was slowly added and stirred at room temperature for 1 hour. Methanol was added, and the organic layer was washed with water, and then concentrated to obtain a crude product. The product was purified by silica gel chromatography to obtain Monomer A4 (43.9 g). 1 H NMR(400MHz,CDCl3)δ6.22(s,1H),5.65(s,1H),4.54(m,2H),1.96(s,3H).

[0085] [Monomer A5: CH2=C(CH3)COOCH2-(CF2O) 22 (CF2CF2O) 24 Synthesis of -CH2OCOC(CH3)=CH2 In a 200 ml glass flask, add AC-2000 (AGC, 100 g) and HOCH2 (CF2O). n (CF2CF2O) m CH2OH (Solvay fomblin D4000, 50 g, n=22, m=24), triethylamine (2.8 g), and DMAP (0.15 g) were charged and bubbled with N2. Methacrylic anhydride (4.3 g) was slowly added and stirred at room temperature for 2 hours. Methanol was added, and the organic layer was washed with water, and then concentrated to obtain a crude product. The product was purified by silica gel chromatography to obtain Monomer A5 (46.5 g). 1 H NMR(400MHz,CDCl3)δ6.22(s,1H),5.65(s,1H),4.54(m,2H),1.96(s,3H).

[0086] [Synthesis of Monomer A6: CH2=C(CH3)COOCH2CH2NHCOOCH2-(CF2O)7(CF2CF2O)9-CH2OCONHCH2CH2OCOC(CH3)=CH2] In a 100 ml glass flask, 1,3-bistrifluoromethylbenzene (AGC, 6.0 g), HOCH2(CF2O) n (CF2CF2O) m CH2OH (fomblin D2 manufactured by Solvay, 20 g, n=7, m=9), 2-isocyanatoethyl methacrylate (Karenz (registered trademark) MOI manufactured by Resonac, 0.80 g), and dibutyltin dilaurate (0.030 g) were charged and stirred at 40°C for 2 hours. The mixture was then concentrated to obtain a crude product. The product was purified by silica gel chromatography to obtain Monomer A6 (12.0 g). 1 H NMR(400MHz,CDCl3)δ6.15(s,2H),5.56(s,2H),5.19(t,J=6.2Hz,2H),4.60(t,J=9.0Hz,2 H),4.58(t,J=8.8Hz,2H),4.29(t,J=5.3Hz,2H),3.58(td,J=5.5,5.5Hz,2H),1.95(s,3H).

[0087] [Synthesis of Monomer A7: (CH2=CHCOOCH2CH2)2C(CH3)NHCOOCH2-(CF2O)7(CF2CF2O)9-CH2OCONHC(CH3)(CH2CH2OCOCH=CH2)2] In a 100 ml glass flask, 1,3-bistrifluoromethylbenzene (AGC, 6.0 g), HOCH2(CF2O) n (CF2CF2O) m CH2OH (fomblin D2 manufactured by Solvay, 20 g, n=7, m=9), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Kalends (registered trademark) BEI manufactured by Resonac, 1.2 g), and dibutyltin dilaurate (0.030 g) were charged and stirred at 40°C for 2 hours. The mixture was then concentrated to obtain a crude product. The product was purified by silica gel chromatography to obtain Monomer A7 (11.7 g). 1H NMR(400MHz,CDCl3)δ6.12(dd,J=17.0,11.0Hz,4H),6.05(dd,J=17.0,3.1Hz,4H),5.89(dd,J=11.0,3. 1Hz,4H),5.30(t,J=6.2Hz,2H),4.59(t,J=9.0Hz,2H),4.55(t,J=8.8Hz,2H),4.30(s,8H),1.45(s,6H).

[0088] [Synthesis of Monomer B1: CH3(CH2)5NHCOOCH2CH2OCOC(CH3)=CH2] Dibutyltin dilaurate (0.110 g), BHT (0.380 g), hexyl isocyanate (25.0 ml), and hydroxyethyl methacrylate (22.0 g) were charged into a 100 ml glass flask and stirred at 25° C. for 24 hours. The mixture was then concentrated to obtain a crude product. The product was purified by silica gel chromatography to obtain Monomer B1 (43.5 g). 1H-NMR(400MHz,CDCl3)δ6.13(s,1H),5.59-5.58(m,1H),5.00(s,1H),4.32(s,4H),3.17(q, J=6.7Hz,2H),1.95(s,3H),1.49(t,J=6.6Hz,2H),1.35-1.29(m,6H),0.88(t,J=6.9Hz,3H).

[0089] [Synthesis of Fluorine-Containing Copolymer] [Example 1] In a 500 mL glass flask, 1,3-bistrifluoromethylbenzene (86 g), hexafluoroisopropanol (4 g), monomer A1 (3.1 g), monomer B1 (7.0 g), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V65, 0.2 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged as an initiator, and the polymerization liquid was bubbled with nitrogen for 1 minute, and then heated and stirred at 50°C for 18 hours under nitrogen. Thereafter, the polymerization liquid was returned to room temperature and poured into 500 g of Asahiklin AC-2000 (manufactured by AGC) to precipitate a solid. Thereafter, the mixture was suction filtered, the solid was washed with AC-2000, and dried under reduced pressure at 80°C to obtain a fluorine-containing copolymer C1 (2.3 g). The fluorine atom content of the polymer was 17% compared to the fluorine atom content of the charged fluorine atom content of 20%. The mass average molecular weight was 13,000, and it was sufficiently dissolved in PGMEA at 5% by mass. The blending amounts and results are summarized in Table 1.

[0090] [ka]

[0091] [Example 2] A fluorine-containing copolymer C2 was obtained in the same manner as in the synthesis of the fluorine-containing copolymer C1, except that compound X was changed from hexafluoroisopropanol to 2,2,2-trifluoroethanol.

[0092] [Example 3] A fluorine-containing copolymer C3 was obtained in the same manner as in the synthesis of the fluorine-containing copolymer C1, except that the compound X was changed from hexafluoroisopropanol to methyl ethyl ketone.

[0093] [Example 4] Fluorine-containing copolymer C4 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that compound X was changed from hexafluoroisopropanol to dimethylformamide.

[0094] [Example 5] In the synthesis of fluorine-containing copolymer C1, the initiator was changed from 2,2'-azobis(2,4-dimethylvaleronitrile) to 2,2'-azobis(2-methylbutyronitrile), the reaction temperature was changed from 50°C to 70°C, and the amounts of raw materials were changed as shown in Table 1. The same procedure was repeated to obtain fluorine-containing copolymer C5.

[0095] [Example 6] The synthesis of fluorocopolymer C5 was carried out in the same manner except that the amounts of raw materials used were changed as shown in Table 1, to obtain fluorocopolymer C6.

[0096] [Example 7] The synthesis of fluorocopolymer C5 was carried out in the same manner except that the amounts of raw materials used were changed as shown in Table 1, to obtain fluorocopolymer C7.

[0097] [Example 8] The synthesis of fluorocopolymer C5 was carried out in the same manner except that the amounts of raw materials used were changed as shown in Table 1, to obtain fluorocopolymer C8.

[0098] [Example 9] The synthesis of fluorocopolymer C5 was carried out in the same manner except that the amounts of raw materials used were changed as shown in Table 1, thereby obtaining fluorocopolymer C9.

[0099] [Example 10] Fluorine-containing copolymer C10 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer B1 was changed to 2-hydroxyethyl methacrylate.

[0100] [Example 11] Fluorine-containing copolymer C11 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer B1 was changed to methacrylic acid.

[0101] [Example 12] Fluorocopolymer C12 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer A1 was changed to monomer A2.

[0102] [Example 13] Fluorocopolymer C13 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer A1 was changed to monomer A3.

[0103] [Example 14] Fluorine-containing copolymer C14 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer A1 was changed to monomer A4.

[0104] [ka]

[0105] [Example 15] Fluorocopolymer C15 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer A1 was changed to monomer A5.

[0106] [Example 16] Fluorine-containing copolymer C16 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer A1 was changed to monomer A6.

[0107] [Example 17] Fluorocopolymer C17 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer A1 was changed to monomer A7.

[0108] [Example 18] Fluorocopolymer C18 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer B1 was changed to methacrylic acid.

[0109] [Example 19] The synthesis of fluorocopolymer C18 was carried out in the same manner as above, except that the amounts of the raw materials were changed as shown in Table 1, to obtain fluorocopolymer C19.

[0110] [Example 20] The synthesis of fluorocopolymer C18 was carried out in the same manner except that the amounts of the raw materials were changed as shown in Table 1, to obtain fluorocopolymer C20.

[0111] [Example 21] The synthesis of fluorocopolymer C18 was carried out in the same manner except that the amounts of raw materials used were changed as shown in Table 1, to obtain fluorocopolymer C21.

[0112] [Example 22] Fluorine-containing copolymer C22 was obtained in the same manner as in the synthesis of fluorine-containing copolymer C1, except that monomer B1 was changed to 2-hydroxyethyl methacrylate and methacrylic acid.

[0113] [Example 23] The synthesis of fluorine-containing copolymer C1 was carried out in the same manner except that hexafluoroisopropanol was not used and the blending amount of the solvent was changed as shown in Table 1, thereby obtaining fluorine-containing copolymer C23.

[0114] [Example 24] The synthesis of fluorine-containing copolymer C1 was carried out in the same manner except that hexafluoroisopropanol was not used and the blending amounts of the raw materials were changed as shown in Table 1, thereby obtaining fluorine-containing copolymer C24.

[0115] The yield, charged fluorine atom content, fluorine atom content of the obtained copolymer, fluorine atom introducibility, mass average molecular weight, and solubility in PGMEA of the fluorinated copolymers obtained by the methods of Examples 1 to 24 are shown in Tables 1 and 2 below. Examples 1 to 22 are working examples, and Examples 23 and 24 are comparative examples. In addition, in Tables 1 and 2 below, PFPE1 and PFPE2 are abbreviations for the following structures. PFPE1:F3OCF2CF2O(CF2CF2CF2CF2OCF2CF2O) 13 CF2CF2CF2- PFPE2:-(CF2O) n (CF2CF2O) m - (n=7, m=9 or n=22, m=24)

[0116] F atom introduction property: The ratio ((Fb / Fa)×100) of the fluorine atom content (Fa) of the charged copolymer to the fluorine atom content (Fb) of the copolymer obtained was calculated and evaluated according to the following criteria. ◎: 60% or more ○: 30% or more but less than 60% ×: Less than 30%

[0117] PGMEA solubility: The solubility of the resulting copolymer in PGMEA was evaluated according to the following criteria. ◎: Solubility is 5% by mass or more ○: Solubility is 2% by mass or more and less than 5% by mass ×: Solubility is less than 2% by mass

[0118] [Table 1]

[0119] [Table 2]

[0120] From the above results, in the production methods of Examples 1 to 22 in which copolymerization was carried out in a solvent containing hexafluoroisopropanol, 2,2,2-trifluoroethanol, methyl ethyl ketone, or dimethylformamide, the fluorine content in the obtained fluorine-containing copolymer was increased compared to the production methods of Examples 23 to 24 in which copolymerization was carried out in a solvent not containing such a compound. This shows that fluoro(poly)ether groups can be efficiently introduced into the copolymer by carrying out copolymerization in a solvent containing compound X capable of forming hydrogen bonds. [Industrial Applicability]

[0121] According to the present invention, when a fluorocopolymer containing a fluoro(poly)ether group is produced, the fluoro(poly)ether group can be efficiently introduced. The obtained fluorocopolymer is expected to be used as a water- and oil-repellent coating agent.

Claims

1. A method for producing a fluorine-containing copolymer by copolymerizing a fluoro(poly)ether group-containing monomer A and a monomer B different from the monomer A in a state containing at least one kind of each monomer, comprising the steps of: The copolymerization is carried out in a solvent containing a compound X capable of forming a hydrogen bond.

2. The method according to claim 1 , wherein the monomer B has a structure capable of forming a hydrogen bond.

3. The method according to claim 1 , wherein the monomer B has one or more structures selected from an amide bond, a urethane bond, a urea bond, a sulfonamide bond, a sulfonic acid, a carboxylic acid, a hydroxy group, a mercapto group, and an amino group.

4. The method according to claim 1 , wherein the monomer B has one or more structures selected from an amide bond, a urethane bond, and a hydroxy group.

5. The method according to claim 1 , wherein the content of the compound X is 0.1 equivalents or more relative to the content of the monomer B.

6. The method according to claim 1 , wherein the compound X is a protic solvent or a compound having a double bond between different atoms.

7. The process according to claim 1 , wherein the fluorine atom content in the fluorinated copolymer is 4% by mass or more.

8. The process according to claim 1 , wherein the fluorine-containing copolymer is soluble in the non-fluorine-based organic solvent at 1% by mass or more.

9. A fluorine-containing copolymer which contains a fluoro(poly)ether group and has a fluorine atom content of 4 mass% or more.

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