Determination method for molecular weight of fluorine-containing polymer

Abstract

The purpose of the present invention is to provide a method for measuring the molecular weight of a fluorine-containing polymer, said method having both the stability of a liquid-passing state and the solubility of a fluorine-containing polymer sample in a mobile phase solvent, and being capable of achieving stable measurement. The present invention is a method for measuring the molecular weight of a fluorine-containing polymer by size exclusion chromatography, the method comprising a step in which a solution obtained by dissolving the fluorine-containing polymer in a mobile phase solvent is passed through a separation carrier, the mobile phase solvent contains a fluorine-containing solvent, the fluorine-containing solvent does not contain chlorine atoms, and the boiling point of the fluorine-containing solvent is 58 DEG C or higher.

Description

Technical Field

[0001] The present invention relates to a method for determining the molecular weight of a fluorine-containing polymer. Background Art

[0002] Size exclusion chromatography is a method for measuring molecular weight by utilizing the property that the sample retains different time in the separation carrier due to differences in molecular weight. During the measurement, the sample is dissolved in a mobile phase solvent to form a uniform solution, which is then introduced into the separation carrier. When measuring the molecular weight of a fluorine-based polymer, solvents used as mobile phase solvents, such as dichloropentafluoropropane (Patent Documents 1 to 3) and hydrochlorofluoroolefins (Patent Documents 4 to 5) have been proposed.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2001-208736

[0006] Patent Document 2: Japanese Patent Application Laid-Open No. 11-174034

[0007] Patent Document 3: Japanese Patent Application Publication No. 2000-74892

[0008] Patent Document 4: Japanese Patent Application Publication No. 2021-67479

[0009] Patent Document 5: Japanese Patent Application Publication No. 2021-9038 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Here, when measuring by size exclusion chromatography (SEC), firstly, a mobile phase solvent is continuously introduced into a separation carrier, and after bubbles are no longer generated and the liquid can be stably passed, a solution obtained by dissolving the sample in the mobile phase solvent is introduced. From the viewpoint of measurement accuracy, the sample needs to be completely dissolved in the mobile phase solvent, but when the measurement temperature is increased in order to maintain the solubility of the sample, the liquid passing state becomes unstable. In particular, fluorinated polymers are not soluble in conventional (halogen-free) solvents in most cases, and therefore, it is very difficult to take into account both the solubility of the sample and the stability of the liquid passing state.

[0012] An object of the present invention is to provide a method for measuring the molecular weight of a fluorinated polymer which can achieve stable measurement and which can achieve both stability in the liquid flow state and solubility of the sample fluorinated polymer in a mobile phase solvent.

[0013] Technical solutions to solve problems

[0014] That is, the invention includes the following contents.

[0015] [1] A method for measuring the molecular weight of a fluorinated polymer, the method comprising measuring the molecular weight of a fluorinated polymer by size exclusion chromatography,

[0016] The method comprises the steps of dissolving the fluorine-containing polymer in a mobile phase solvent to obtain a solution which is passed into a separation carrier,

[0017] The mobile phase solvent contains a fluorinated solvent.

[0018] The above fluorinated solvent does not contain chlorine atoms.

[0019] The boiling point of the fluorinated solvent is 58° C. or higher.

[0020] [2] The method for measuring the molecular weight of a fluorinated polymer according to [1], wherein:

[0021] The measurement temperature is 25°C to 40°C.

[0022] [3] The method for measuring the molecular weight of a fluorinated polymer according to [1] or [2], wherein:

[0023] The fluorinated solvent includes at least one selected from the group consisting of fluorinated ethers, fluorinated alcohols and fluorocarbons.

[0024] [4] The method for measuring the molecular weight of a fluorinated polymer according to any one of [1] to [3], wherein

[0025] The volume ratio of the chlorine-containing solvent in the mobile phase solvent is 50 volume % or less.

[0026] [5] The method for measuring the molecular weight of a fluorinated polymer according to any one of [1] to [4], wherein

[0027] The boiling point of the fluorinated solvent is 120° C. or lower.

[0028] [6] The method for measuring the molecular weight of a fluorinated polymer according to any one of [1] to [5], wherein

[0029] The fluorine-containing polymer is a fluorinated polyether group-containing compound, a fluorine-containing carbon compound or a fluorine-containing vinyl polymer.

[0030] [7] The method for measuring the molecular weight of a fluorinated polymer according to [6], wherein:

[0031] The above-mentioned fluorinated polyether group-containing compound is a compound represented by formula (A1), (A2), (B1), (B2), (C1), (C2), (D1), (D2), (E1) or (E2).

[0032]

[0033] (Rf-PFPE) β′ -X 3 -Q β …(B1)

[0034] Q β -X 3 -PFPE-X 3 -Q β …(B2)

[0035] (Rf-PFPE) γ′ -X 4 (SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 ) γ …(C1)

[0036] (R d1 n1 R c1 m1 R b1 l1 R a1 k1 Si) γ -X 4 -PFPE-X 4 -(SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 ) γ …(C2)

[0037] (Rf-PFPE) δ′ -X 6 (CR a2 k2 R b2 l2 R c2 m2 R d2 n2 ) δ …(D1)

[0038] (R d2 n2 R c2 m2 R b2 l2 R a2 k2 C)8-X6 -PFPE-X 6 -(CR a2 k2 R b2 l2 R c2 m2 R d2 n2 ) δ …(D2)

[0039] (Rf-PFPE) ε′ -X 8 -R 50 ε …(E1)

[0040] R 50 ε -X 8 -PFPE-X s -R 50 ε …(E2)

[0041] [In formulas (A1) and (A2),

[0042] Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0043] PFPE are each independently a divalent fluorinated polyether group;

[0044] Q each independently represents -SiR 1 n R 2 3-n or -YA,

[0045] R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0046] R 2 Each independently represents a hydroxyl group or a hydrolyzable group,

[0047] n in each (-SiR 1 n R 2 3-n ) are independently an integer from 0 to 3,

[0048] Y each independently represents a single bond, -O-, -CO-, -O-CO-, -CO-O-, -NR 3 -CO-, -CO-NR 3 - or a divalent hydrocarbon group having 1 to 22 carbon atoms,

[0049] R 3each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0050] A represents independently -CR 4 =CH2 or -C≡CH,

[0051] R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0052] R 11 each independently represents a hydrogen atom or a halogen atom,

[0053] R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0054] X 1 Each independently represents a single bond or a di- to decavalent organic group,

[0055] X 2 Each independently represents a single bond or a divalent organic group,

[0056] t are each independently an integer of 2 to 10,

[0057] α is an integer of 1 to 9 independently.

[0058] α' is an integer from 1 to 9,

[0059] At least one Q is -SiR 1 n R 2 3－n In the case of, in formula (A1) or (A2) there is at least one R 2 ;

[0060] In formulas (B1) and (B2),

[0061] X 3 Each independently represents a single bond or a di- to decavalent organic group,

[0062] β is an integer of 1 to 9 independently.

[0063] β' is an integer from 1 to 9,

[0064] At least one Q is -SiR 1 n R 2 3－n In the case of, in formula (B1) or (B2) there is at least one R 2 ,

[0065] Rf, PFPE, Q, R 1 and R 2has the same meaning as above;

[0066] In formulas (C1) and (C2),

[0067] X 4 Each independently represents a single bond or a di- to decavalent organic group,

[0068] γ is an integer of 1 to 9 independently.

[0069] γ' is an integer from 1 to 9,

[0070] R a1 Each independently represents -Z-SiR 31 p1 R 32 q1 R 33 r1 R 34 s1 ,

[0071] Z each independently represents an oxygen atom or a divalent organic group,

[0072] R 31 R a' ,

[0073] R a' The meaning of R a same,

[0074] R 32 Represents -X independently 5 -Q,

[0075] X 5 Each independently represents a single bond or a divalent organic group,

[0076] R 33 Each independently represents a hydroxyl group or a hydrolyzable group,

[0077] R 34 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0078] In each -Z-SiR 31 p1 R 32 q1 R 33 r1 R 34 s1 middle,

[0079] p1, q1, r1 and s1 are each independently an integer from 0 to 3,

[0080] The sum of p1, q1, r1 and s1 is 3,

[0081] R a1 In the example, the maximum number of Si atoms connected in a straight chain via a -Z- group is 5.

[0082] R b1 Indicates -X 5 -Q,

[0083] R c1 Each independently represents a hydroxyl group or a hydrolyzable group,

[0084] R d1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0085] In each -SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 middle,

[0086] k1, l1, m1 and n1 are each independently an integer of 0 to 3,

[0087] The sum of k1, l1, m1 and n1 is 3,

[0088] Rf, PFPE and Q have the same meanings as above.

[0089] In formula (C1) and (C2), there is at least one -Q group;

[0090] In formulas (D1) and (D2),

[0091] X 6 Each independently represents a single bond or a di- to decavalent organic group,

[0092] δ are each independently an integer of 1 to 9,

[0093] δ' is an integer from 1 to 9,

[0094] R a2 Represents -Z independently 2 -CR 41 p2 R 42 q2 R 43 r2 R 44 s2 ,

[0095] Z 2 each independently represents an oxygen atom or a divalent organic group,

[0096] R41 R a2' ,

[0097] R a2' The meaning of R a2 same,

[0098] R 42 Represents -X independently 7 -Q,

[0099] X 7 Each independently represents a single bond or a divalent organic group,

[0100] R 43 Each independently represents a hydroxyl group or a hydrolyzable group,

[0101] R 44 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0102] In each -Z 2 -CR 41 p2 R 42 q2 R 43 r2 R 44 s2 middle,

[0103] p2, q2, r2 and s2 are each independently an integer from 0 to 3,

[0104] The sum of p2, q2, r2 and s2 is 3,

[0105] R a2 In, via -Z 2 The maximum number of carbon atoms connected in a straight chain is 5.

[0106] R b2 Represents -X independently 7 -Q,

[0107] R c2 Each independently represents a hydroxyl group or a hydrolyzable group,

[0108] R d2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0109] In each -CR a2 k2 R b2 l2 R c2 m2 R d2 n2 middle,

[0110] k2, l2, m2 and n2 are each independently an integer of 0 to 3,

[0111] The sum of k2, l2, m2 and n2 is 3,

[0112] In (CR a2 k2 R b2 l2 R c2 m2 R d2 n2 ) δ There is at least one Q in

[0113] Rf, PFPE and Q have the same meanings as above;

[0114] In formulas (E1) and (E2),

[0115] X 8 Each independently represents a single bond or a di- to decavalent organic group,

[0116] ε is an integer of 1 to 9 independently.

[0117] ε′ is an integer from 1 to 9,

[0118] R 50 Represents -OR independently 51 、-SR 51 、-NR 51 2. -COOR 51 、-SO3R 51 or -(Si 52 2O) n3 -SiR 52 3.

[0119] R 51 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0120] R 52 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms,

[0121] n3 are each independently an integer from 0 to 100;

[0122] Rf and PFPE have the same meanings as above.]

[0123] [8] The method for measuring the molecular weight of a fluorinated polymer according to [6], wherein:

[0124] The fluorine-containing compound is a compound represented by formula (F1) or (F2).

[0125] (R61 -Rf′) φ′ -X 9 -Q φ …(F1)

[0126] Q φ -X 9 -Rf′-X 9 -Q φ …(F2)

[0127] [In formulas (F1) and (F2),

[0128] X 9 Each independently represents a single bond or a di- to decavalent organic group,

[0129] φ are each independently an integer from 1 to 9,

[0130] φ′ is an integer from 1 to 9,

[0131] R 61 each independently represents a fluorine atom, -CHF2 or -CF3,

[0132] Rf' each independently represents a perfluoroalkylene group having 1 to 30 carbon atoms,

[0133] Q each independently represents -SiR 1 n R 2 3-n or -YA,

[0134] R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0135] R 2 Each independently represents a hydroxyl group or a hydrolyzable group,

[0136] n in each (-SiR 1 n R 2 3-n ) are independently an integer from 0 to 3,

[0137] Y each independently represents a single bond, -O-, -CO-, -O-CO-, -CO-O-, -NR 3 -CO-, -CO-NR 3 - or a divalent hydrocarbon group having 1 to 22 carbon atoms,

[0138] R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0139] A represents independently -CR 4=CH2 or -C≡CH,

[0140] R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0141] At least one Q is -SiR 1 n R 2 3－n In the case of, in formula (F1) or formula (F2), there is at least one R 2 . ]

[0142] [9] The method for measuring the molecular weight of a fluorinated polymer according to [6], wherein:

[0143] The fluorine-containing vinyl polymer is a polymer having one or more units represented by the formula (G1), (G2) or (G3).

[0144]

[0145] [In formulas (G1), (G2), and (G3),

[0146] R a3 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, or a fluorinated alkyl group having 1 to 22 carbon atoms,

[0147] R b3 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, or a fluorinated alkyl group having 1 to 22 carbon atoms,

[0148] R c3 represents an alkyl group having 1 to 22 carbon atoms, an alicyclic hydrocarbon group having 3 to 22 carbon atoms, an aromatic hydrocarbon group having 6 to 22 carbon atoms, or a group having 4 to 22 carbon atoms in which an alicyclic hydrocarbon group or an aromatic hydrocarbon group is bonded to an alkylene group, wherein -CH2- contained in these groups may be replaced by an oxygen atom, and hydrogen atoms contained in these groups may be replaced by fluorine atoms,

[0149] Y 2 Represents -O-, -CO-, -O-CO-, -CO-O-, -NR 6 -CO- or -CO-NR 6 -

[0150] R 6 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0151] Y 3 represents a single bond or an oxygen atom,

[0152] R d3represents an alkyl group having 1 to 22 carbon atoms, wherein the -CH2- contained in the above alkyl group may be replaced by an oxygen atom, and the hydrogen atom contained in the above alkyl group may be replaced by a fluorine atom,

[0153] R e3 represents an alkylene group having 3 to 22 carbon atoms, wherein -CH2- contained in the above alkylene group may be replaced by an oxygen atom, and the hydrogen atom contained in the above alkylene group may be replaced by a fluorine atom,

[0154] X 10 represents a single bond, an alkylene group having 1 to 22 carbon atoms, or a fluorinated alkylene group having 1 to 22 carbon atoms.]

[0155] Effects of the Invention

[0156] According to the method for measuring the molecular weight of a fluorinated polymer of the present invention, it is possible to achieve both stability in the liquid flow state and solubility of the sample fluorinated polymer in the mobile phase solvent, thereby enabling stable measurement. DETAILED DESCRIPTION

[0157] The method for determining the molecular weight of the fluorine-containing polymer of the present invention is a method for determining the molecular weight by size exclusion chromatography, which comprises the step of passing a solution obtained by dissolving the fluorine-containing polymer in a mobile phase solvent into a separation carrier.

[0158] The mobile phase solvent includes a fluorine-containing solvent. The fluorine-containing solvent does not contain chlorine atoms and is a solvent containing at least fluorine atoms in the molecule.

[0159] The mobile phase solvent may be one kind or two or more kinds.

[0160] The boiling point of the mobile phase solvent is 58° C. or higher, 59° C. or higher, preferably 120° C. or lower, and 118° C. or lower. When the boiling point of the mobile phase solvent is within the above range, both the stability of the liquid flow state and the solubility of the sample fluorinated polymer in the mobile phase solvent can be achieved.

[0161] When the mobile phase solvent contains two or more solvents, the boiling point of the mobile phase solvent is a weighted average value based on the boiling points and volume ratios of the respective solvents.

[0162] The fluorinated solvent preferably contains at least one selected from the group consisting of fluorinated ethers, fluorinated alcohols and hydrofluorocarbons, and more preferably contains at least one selected from the group consisting of fluorinated ethers and hydrofluorocarbons.

[0163] The fluorine-containing ether contains at least a fluorine atom and an ether bond (—O—) in the molecule. Examples of the fluorine-containing ether include a compound in which a fluoroalkyl group is bonded to a fluoroalkyl group via an ether bond, and a compound in which a fluoroalkyl group is bonded to an alkyl group via an ether bond.

[0164] Examples of the fluorine-containing ether include compounds represented by formula (1), but are not limited to a specific embodiment.

[0165] R s1 -O-R s2 ···(1)

[0166] [In formula (1),

[0167] R s1 It represents a fluorinated alkyl group having 1 to 6 carbon atoms.

[0168] R s2 represents a fluorinated alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms.]

[0169] R s1 The fluorinated alkyl group shown may be a straight chain or a branched chain, and may be a perfluorinated alkyl group or a partially fluorinated alkyl group. s1 The fluorinated alkyl group shown preferably has 2 to 6 carbon atoms.

[0170] R s2 The fluorinated alkyl group shown may be a straight chain or a branched chain, and may be a perfluorinated alkyl group or a partially fluorinated alkyl group. s2 The fluorinated alkyl group shown preferably has 1 to 4 carbon atoms.

[0171] R s1 The number of carbon atoms and R s2 The total number of carbon atoms in the moiety is preferably 3-7, more preferably 4-7.

[0172] As R s1 and R s2 The combination of R s1 is a perfluoroalkyl group having 1 to 6 carbon atoms, R s2 is a combination of alkyl groups having 1 to 6 carbon atoms; R s1 is a non-fully fluorinated fluoroalkyl group having 1 to 6 carbon atoms, R s2 A combination of incompletely fluorinated fluoroalkyl groups having 1 to 6 carbon atoms, etc.

[0173] In the above fluorine-containing ether, the total number of fluorine atoms in the total number of hydrogen atoms and fluorine atoms is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more.

[0174] As the above-mentioned fluorine-containing ether, at least one selected from (CF3)CH2-O-CF2CF2H, CF3CF2CF2CF2-O-CH3, (CF3)2CF-O-CH3, CHF2CF2CH2-O-CF2CHF2, CF3CHFCF2-O-CH3, CF3CHFCF2-O-CH2CH3, and CF3CF2-CF(OCH3)CF2CF2CF3 is preferred.

[0175] The boiling point of the fluorine-containing ether is preferably 58 to 120°C, more preferably 59 to 118°C.

[0176] In the above-mentioned fluorinated solvent, the volume proportion of the above-mentioned fluorinated ether is preferably 50 volume % or more, more preferably 60 volume % or more, further preferably 70 volume % or more; preferably 99 volume % or less, more preferably 95 volume % or less, further preferably 90 volume % or less.

[0177] In the present invention, when two or more solvents are mixed to form a mixed solvent, the volume ratio of the solvents in the mixed solvent refers to the volume ratio before the two or more solvents are mixed.

[0178] The fluorine-containing alcohol contains at least a fluorine atom and a hydroxyl group in the molecule. Examples of the fluorine-containing alcohol include compounds in which a fluoroalkyl group and a hydroxyl group are bonded.

[0179] Examples of the fluorine-containing alcohol include compounds represented by formula (3), but are not limited to a specific embodiment.

[0180] C(R s5 ) w H 3－w -OH···(3)

[0181] [In formula (3), R s5 represents a fluorinated alkyl group having 1 to 18 carbon atoms or a fluorinated aryl group having 6 to 18 carbon atoms. w represents an integer of 1 to 2.]

[0182] R s5 The fluorinated alkyl group shown may be a straight chain or a branched chain, and may be a perfluorinated alkyl group or a partially fluorinated alkyl group. s5 The fluorinated alkyl group shown preferably has 1 to 10 carbon atoms.

[0183] R s5 The fluorinated aryl group shown may be monocyclic or polycyclic and may be a perfluorinated aryl group or a partially fluorinated aryl group.

[0184] In the above fluorine-containing alcohol, the total number of fluorine atoms in the total number of hydrogen atoms and fluorine atoms is preferably 50% or more, more preferably 60% or more.

[0185] Examples of the fluorine-containing alcohol include 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,4,4,4-heptafluorobutanol, 2,2,3,4,4,4-hexafluorobutanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 3,3,4,4,4-pentafluorobutanol, and 3,3,4,4-tetrafluorobutanol.

[0186] The boiling point of the fluorine-containing alcohol is preferably 58 to 120°C, more preferably 59 to 118°C.

[0187] In the fluorinated solvent, the volume ratio of the fluorinated alcohol is preferably 5 volume % or less, more preferably 20 volume % or less, further preferably 30 volume % or less.

[0188] In the fluorinated solvent, the total volume ratio of the fluorinated ether and the fluorinated alcohol is preferably 50% by volume or more, more preferably 70% by volume or more, further preferably 80% by volume or more, and is 100% by volume or less.

[0189] The fluorocarbon is a compound in which at least one of the hydrogen atoms contained in the hydrocarbon compound is replaced by a fluorine atom. The hydrocarbon compound may be an aliphatic hydrocarbon compound, an alicyclic hydrocarbon compound, an aromatic hydrocarbon compound, or a compound of a combination thereof. The number of carbon atoms in the hydrocarbon compound is, for example, 4 to 20, preferably 4 to 15, and more preferably 4 to 10.

[0190] Examples of the fluorocarbon compound include compounds represented by formula (2), but the fluorocarbon compound is not limited to a specific embodiment.

[0191] (R s3 ) x1 -R s4 ···(2)

[0192] [In formula (2),

[0193] R s3 It represents a fluorinated alkyl group having 1 to 12 carbon atoms or a fluorinated cycloalkyl group having 3 to 12 carbon atoms.

[0194] R s4 It represents a hydrogen atom, a monovalent to hexavalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a monovalent to hexavalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0195] x represents an integer from 1 to 6.]

[0196] R s3 The fluorinated alkyl group shown may be a straight chain or a branched chain, and may be a perfluorinated alkyl group or a partially fluorinated alkyl group. s3 The fluorinated alkyl group has preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms.

[0197] R s3 The fluorinated cycloalkyl group shown is a perfluorinated cycloalkyl group or a partially fluorinated cycloalkyl group. s3 The fluorinated cycloalkyl group has preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.

[0198] R s4 The aliphatic hydrocarbon group shown in formula (2) may be a straight chain or a branched chain, and may be an alkyl group or an unsaturated aliphatic hydrocarbon group. The double bond or triple bond of the unsaturated aliphatic hydrocarbon group is preferably present at the end of the molecular chain in the compound shown in formula (2). The aliphatic hydrocarbon group may be a monovalent group or a divalent or higher group, and is preferably a monovalent group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 to 6.

[0199] R s4 The aromatic hydrocarbon group shown may be monocyclic or polycyclic. The aromatic hydrocarbon group may be a monovalent group or a divalent or higher group, preferably a divalent to hexavalent group, more preferably a divalent to tetravalent group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 10.

[0200] Preferably, x is 1-4.

[0201] As R s3 , R s4 The combination of and x can be listed as: R s3 is a perfluoroalkyl group having 1 to 6 carbon atoms, R s4 is a hydrogen atom, x is 1; R s3 is a fluorinated cycloalkyl group having 3 to 6 carbon atoms which is not fully fluorinated, R s4 is a hydrogen atom, x is 1; R s3 is a perfluoroalkyl group having 1 to 6 carbon atoms, R s4 is an aromatic hydrocarbon group having 6 to 10 carbon atoms, and x is a combination of 2 to 4.

[0202] In the above fluorocarbon compound, the total number of fluorine atoms in the total number of hydrogen atoms and fluorine atoms is preferably 50% or more, more preferably 60% or more.

[0203] As the fluorocarbon compound, it is preferred to be selected from n-C5F 13 At least one of c-H, c-C5F7H3, and CF3-C6H4-CF3.

[0204] The boiling point of the fluorocarbon is preferably 58 to 120°C, more preferably 59 to 118°C.

[0205] When the fluorocarbon compound is contained, the volume ratio of the fluorocarbon compound in the fluorine-containing solvent is, for example, 10% by volume or more, or 30% by volume or more; for example, 90% by volume or less, or 70% by volume or less.

[0206] In the above-mentioned fluorine-containing solvent, the total volume ratio of the above-mentioned fluorine-containing ether, fluorine-containing alcohol and fluorocarbon is preferably 50 volume % or more, more preferably 70 volume % or more, further preferably 90 volume % or more; preferably 100 volume % or less.

[0207] The fluorinated solvent may contain a fluorinated solvent other than the fluorinated ether, fluorinated alcohol and fluorocarbon. Specifically, it may contain, for example, a fluorinated solvent having a boiling point lower than 58° C. In the fluorinated solvent, the volume ratio of the fluorinated solvent having a boiling point lower than 58° C. is preferably 50% by volume or less, more preferably 30% by volume or less, and further preferably 10% by volume or less.

[0208] The fluorine-containing solvent does not contain chlorine atoms. By not containing chlorine atoms, it is easy to achieve both stability of the liquid flow state and solubility of the sample.

[0209] The volume ratio of the fluorinated solvent in the mobile phase solvent is preferably 50 volume % or more, more preferably 70 volume % or more, further preferably 90 volume % or more, particularly preferably 100 volume %.

[0210] In the above-mentioned mobile phase solvent, the volume ratio of the solvent containing chlorine atoms in the molecule, i.e., the chlorinated solvent, is preferably 50 volume % or less, more preferably 30 volume % or less, further preferably 10 volume % or less, and particularly preferably 0 volume %. That is, it is particularly preferred not to contain a chlorinated solvent. The above-mentioned chlorinated solvent can be any solvent containing chlorine atoms in the molecule, for example, a solvent containing fluorine atoms and chlorine atoms also belongs to the technical category of the above-mentioned chlorinated solvent.

[0211] In a solution obtained by dissolving the fluorinated polymer in the mobile phase solvent (hereinafter sometimes referred to as "sample solution"), the concentration of the fluorinated polymer is preferably 1 mass % or more, more preferably 0.5 mass % or more, further preferably 0.1 mass % or more.

[0212] The measurement temperature when the sample solution is passed through the separation support is preferably 25° C. to 40° C. The measurement temperature refers to the temperature of the separation support and the detector, and the measurement is performed with the separation support and the detector being at the same temperature.

[0213] The flow rate when the sample solution is passed into the separation carrier is, for example, 0.3 mL / min or more, preferably 0.5 mL / min or more, more preferably 1 mL / min or more, and for example, may be 20 mL / min or less.

[0214] As the above-mentioned separation carrier, the separation carrier used in the SEC method can be appropriately used, preferably a polymer porous gel. As the above-mentioned polymer, silicon dioxide, polyvinyl alcohol, styrene / divinylbenzene copolymers etc. can be listed. The above-mentioned separation carrier can be appropriately selected based on the molecular weight of the fluorinated polymer to be measured.

[0215] The outflow of the sample (fluoropolymer) from the separation carrier can be detected using a detector commonly used in the SEC method. Examples of the detector include a differential refractometer, an ultraviolet absorption detector, a visible light absorption detector, an infrared spectrophotometer, a light scattering detector, an evaporative infrared spectrophotometer, an evaporative light scattering detector, and a mass spectrometer.

[0216] When the sample solution is passed through the separation carrier, the molecular weight can be obtained based on the time (retention time) required for the sample fluorinated polymer to pass through the separation carrier. When obtaining the molecular weight, a standard sample with a known molecular weight can be used to plot the molecular weight against the retention time (the time required for the sample to pass through the separation carrier) to prepare a calibration curve, and the relative molecular weight of the sample can be calculated based on the calibration curve.

[0217] As the standard sample, a fluorine-containing polymer or polymethyl methacrylate (PMMA) is preferred, a perfluoropolyether or polymethyl methacrylate (PMMA) is more preferred, and a linear perfluoropolyether or polymethyl methacrylate (PMMA) is further preferred.

[0218] Before the sample solution is passed through the separation carrier, only the mobile phase solvent can be continuously passed through the separation carrier until the flow state is stable. The temperature (temperature of the separation carrier) and flow rate during continuous flow are preferably the same as the measurement temperature (temperature of the separation carrier) and flow rate. The stability of the flow state when only the mobile phase solvent is passed can be confirmed by the absence of change in the signal intensity from the detector.

[0219] In the measurement method of the present invention, the fluorine-containing polymer to be measured may be any polymer containing fluorine atoms. Examples of the fluorine-containing polymer include fluorinated polyether group-containing compounds, fluorine-containing carbon compounds, and fluorine-containing acrylic resins.

[0220] The fluorinated polyether group-containing compound is a compound having a group (fluorinated polyether group) in which one or more hydrogen atoms contained in a polyether group are substituted with fluorine atoms, and is preferably a perfluoro polyether group-containing compound.

[0221] The above-mentioned fluorinated polyether group-containing compound is preferably represented by any one of the formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1), (D2), (E1) and (E2).

[0222]

[0223] (Rf-PFPE) β′ -X 3 -Q β …(B1)

[0224] Q β -X 3 -PFPE-X 3 -Q β …(B2)

[0225] (Rf-PFPE) γ′ -X 4 -(SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 ) γ …(C1)

[0226] (R d1 n1 R c1 m1 R b1 l1 R a1 k1 Si) γ -X 4 -PFPE-X 4 -(SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 ) γ …(C2)

[0227] (Rf-PFPE) δ′ -X 6 -(CR a2 k2 R b2 l2 R c2 m2 R d2 n2 ) δδ …(D1)

[0228] (R d2 n2 R c2 m2 R b2 12R a2 k2 C) δ -X 6 -PFPE-X 6 -(CR a2 k2 R b2 l2 R c2 m2 R d2 n2 )8…(D2)

[0229] (Rf-PFPE) ε′ -X 8 -R 50 ε …(E1)

[0230] R 50 ε -X 8 -PFPE-X 8 -R 50 ε …(E2)

[0231] [In formulas (A1) and (A2),

[0232] Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0233] PFPE are each independently a divalent fluorinated polyether group;

[0234] Q each independently represents -SiR 1 n R 2 3-n or -YA,

[0235] R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0236] R 2 Each independently represents a hydroxyl group or a hydrolyzable group,

[0237] n in each (-SiR 1 n R 2 3-n ) are independently an integer from 0 to 3,

[0238] Y each independently represents a single bond, -O-, -CO-, -O-CO-, -CO-O-, -NR 3 -CO-, -CO-NR 3 - or a divalent hydrocarbon group having 1 to 22 carbon atoms,

[0239] R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0240] A represents independently -CR 4 =CH2 or -C≡CH,

[0241] R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0242] R 11 each independently represents a hydrogen atom or a halogen atom,

[0243] R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0244] X 1 Each independently represents a single bond or a di- to decavalent organic group,

[0245] X 2 Each independently represents a single bond or a divalent organic group,

[0246] t are each independently an integer of 2 to 10,

[0247] α is an integer of 1 to 9 independently.

[0248] α' is an integer from 1 to 9,

[0249] At least one Q is -SiR 1 n R 2 3－n In the case of, in formula (A1) or (A2) there is at least one R 2 .

[0250] In formulas (B1) and (B2),

[0251] X 3 Each independently represents a single bond or a di- to decavalent organic group,

[0252] β is an integer of 1 to 9 independently.

[0253] β' is an integer from 1 to 9,

[0254] At least one Q is -SiR 1 n R 2 3－n In the case of, in formula (B1) or (B2) there is at least one R 2 ,

[0255] Rf, PFPE, Q, R 1 and R 2 Same meaning as above.

[0256] In formulas (C1) and (C2),

[0257] X 4 Each independently represents a single bond or a di- to decavalent organic group,

[0258] γ is an integer of 1 to 9 independently.

[0259] γ' is an integer from 1 to 9,

[0260] R a1 Each independently represents -Z-SiR 31 p1 R 32 q1 R 33 r1 R 34 s1 ,

[0261] Z each independently represents an oxygen atom or a divalent organic group,

[0262] R 31 R a' ,

[0263] R a' The meaning of R a same,

[0264] R 32 Represents -X independently 5 -Q,

[0265] X 5 Each independently represents a single bond or a divalent organic group,

[0266] R 33 Each independently represents a hydroxyl group or a hydrolyzable group,

[0267] R 34 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0268] In each -Z-SiR 31 p1 R 32 q1 R 33 r1 R 34 s1 middle,

[0269] p1, q1, r1 and s1 are each independently an integer from 0 to 3,

[0270] The sum of p1, q1, r1 and s1 is 3,

[0271] R a1 In the example, the maximum number of Si atoms connected in a straight chain via a -Z- group is 5.

[0272] R b1 Indicates -X 5 -Q,

[0273] R c1 Each independently represents a hydroxyl group or a hydrolyzable group,

[0274] R d1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0275] In each -SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 middle,

[0276] k1, l1, m1 and n1 are each independently an integer of 0 to 3,

[0277] The sum of k1, l1, m1 and n1 is 3,

[0278] Rf, PFPE and Q have the same meanings as above.

[0279] In formula (C1) and (C2), there is at least one -Q group.

[0280] In formulas (D1) and (D2),

[0281] X 6 Each independently represents a single bond or a di- to decavalent organic group,

[0282] δ are each independently an integer of 1 to 9,

[0283] δ' is an integer from 1 to 9,

[0284] R a2 Represents -Z independently 2 -CR 41 p2 R 42 q2 R 43 r2 R 44 s2 ,

[0285] Z 2each independently represents an oxygen atom or a divalent organic group,

[0286] R 41 R a2' ,

[0287] R a2' The meaning of R a2 same,

[0288] R 42 Represents -X independently 7 -Q,

[0289] X 7 Each independently represents a single bond or a divalent organic group,

[0290] R 43 Each independently represents a hydroxyl group or a hydrolyzable group,

[0291] R 44 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0292] In each -Z 2 -CR 41 p2 R 42 q2 R 43 r2 R 44 s2 middle,

[0293] p2, q2, r2 and s2 are each independently an integer from 0 to 3,

[0294] The sum of p2, q2, r2 and s2 is 3,

[0295] R a2 In, via -Z 2 The maximum number of carbon atoms connected in a straight chain is 5.

[0296] R b2 Represents -X independently 7 -Q,

[0297] R c2 Each independently represents a hydroxyl group or a hydrolyzable group,

[0298] R d2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0299] In each -CR a2 k2 R b2 l2 R c2m2 R d2 n2 middle,

[0300] k2, l2, m2 and n2 are each independently an integer of 0 to 3,

[0301] The sum of k2, l2, m2 and n2 is 3,

[0302] In (CR a2 k2 R b2 l2 R c2 m2 R d2 n2 ) δ There is at least one Q in

[0303] Rf, PFPE and Q have the same meanings as above.

[0304] In formulas (E1) and (E2),

[0305] X 8 Each independently represents a single bond or a di- to decavalent organic group,

[0306] ε is an integer of 1 to 9 independently.

[0307] ε' is an integer from 1 to 9,

[0308] R 50 Represented independently -OR 51 , -SR 51 , -NR 51 2. -COOR 51 ,-SO3R 51 or -(Si 52 2O) n3 -SiR 52 3.

[0309] R 51 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0310] R 52 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms,

[0311] n3 are each independently an integer from 0 to 100;

[0312] Rf and PFPE have the same meanings as above.]

[0313] Formula (A1) and (A2):

[0314]

[0315] The "alkyl" in Rf may be a straight chain or a branched chain. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 5. The "alkyl" in Rf is preferably a straight chain or a branched chain alkyl group having 1 to 6 carbon atoms, more preferably a straight chain or a branched chain alkyl group having 1 to 3 carbon atoms, and further preferably a straight chain alkyl group having 1 to 3 carbon atoms.

[0316] Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, more preferably CF2H—C 1－15 The fluorinated alkylene group is more preferably a perfluoroalkyl group having 1 to 16 carbon atoms.

[0317] The perfluoroalkyl group represented by Rf may be a straight chain or a branched chain. The number of carbon atoms of the perfluoroalkyl group represented by Rf is preferably 1 to 6, and more preferably 1 to 3. The perfluoroalkyl group represented by Rf is preferably a straight chain or a branched chain perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a straight chain or a branched chain perfluoroalkyl group having 1 to 3 carbon atoms, and further preferably a straight chain perfluoroalkyl group having 1 to 3 carbon atoms, and specifically may be -CF3, -CF2CF3 or -CF2CF2CF3.

[0318] PFPE, at each occurrence, independently represents a divalent fluorinated polyether group, preferably a perfluoro(poly)ether group.

[0319] PFPE is preferably a group represented by the following formula:

[0320] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f -

[0321] [Wherein,

[0322] R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

[0323] a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit indicated by a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.]

[0324] a, b, c, d, e, and f are each independently an integer of 0 or 1 or more, and the sum of a, b, c, d, e, and f is at least 1. a, b, c, d, e, and f are each independently an integer of 0 or more and 200 or less, for example, an integer of 1 or more and 200 or less, and more preferably, each independently an integer of 0 or more and 100 or less, for example, an integer of 1 or more and 100 or less. It is further preferred that the sum of a, b, c, d, e, and f is 10 or more, preferably 20 or more, and 200 or less, preferably 100 or less. In addition, the order of presence of each repeating unit marked a, b, c, d, e, and f and enclosed in parentheses in the formula is arbitrary. At each occurrence, PFPE is preferably -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f The oxygen atom at the left end of - is bonded to the Rf group.

[0325] Each repeating unit may be linear or branched, and may also contain a ring structure. 12 )-, including -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc.

[0326] As - (OC5F 10 )-, including -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc.

[0327] As -(OC4F8)-, there can be listed -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and -(OCF2CF(C2F5))-.

[0328] Examples of -(OC3F6)- include -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-.

[0329] As -(OC2F4)-, -(OCF2CF2)- and -(OCF(CF3))- can be listed.

[0330] The above ring structure may be a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring.

[0331]

[0332] [Wherein, * indicates the binding position.]

[0333] The ring structure is preferably a four-membered ring, a five-membered ring or a six-membered ring, and more preferably a four-membered ring or a six-membered ring.

[0334] The repeating unit having a ring structure is preferably the following unit.

[0335]

[0336] [Wherein, * indicates the binding position.]

[0337] In one embodiment, the repeating unit is linear.

[0338] In one embodiment, the repeating unit is branched.

[0339] In one embodiment, the PFPE is:

[0340] -(OC3F6) d -(OC2F4) e -(f1).

[0341] (wherein, d is an integer of 1 to 200, preferably 10 to 100, and e is 0 or 1), preferably -(OCF2CF2CF2) d -(wherein, d has the same meaning as above).

[0342] OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2) or (OCF2CF(CF3)), and more preferably (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), and more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0343] In another embodiment, PFPE may also be:

[0344] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2).

[0345] (In the formula, c and d are each independently an integer of 0 or more or 1 or more and 30 or less, preferably 0 or more and 10 or less, and e and f are each independently an integer of 1 or more and 200 or less, preferably 10 or more and 100 or less. The sum of c, d, e and f is 10 or more, preferably 20 or more, and 200 or less, preferably 100 or less. The order of existence of each repeating unit marked with subscript c, d, e or f and enclosed in parentheses in the formula is arbitrary.) In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f -(wherein c, d, e and f have the same meanings as above). In another embodiment, the above formula (f2) is -(OCF2CF2) e -(OCF2) f -(wherein, e and f have the same meanings as above).

[0346] In yet another embodiment, the PFPE is:

[0347] -(R 6 -R 7 ) g - (f3).

[0348] [Where R 6 For OCF2 or OC2F4,

[0349] R 7 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0350] g is an integer from 2 to 100.]

[0351] In the formula, R 6 Preferably, it is OC2F4. In the above (f3), R 7It is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It may be a straight chain or a branched chain, preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or-(OC2F4-OC4F8) g -

[0352] In yet another aspect, PFPE represents:

[0353] -(R 6 -R 7 ) g -R r -(R 7' -R 6' ) g' - (f4).

[0354] [Where R 6 For OCF2 or OC2F4,

[0355] R 7 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0356] R 6'For OCF2 or OC2F4,

[0357] R 7' is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0358] g is an integer from 2 to 100,

[0359] g' is an integer from 2 to 100,

[0360] R r for

[0361]

[0362] (In the formula, * indicates the binding position.)]

[0363] In this method, R 6 , R 7 and g have the same meanings as those described in the above formula (f3) and have the same aspects. 6' , R 7' and g' respectively have the same meanings as R described in the above formula (f3). 6 , R 7 Same as g, in the same way. r Preferably:

[0364]

[0365] [Wherein, * indicates the binding position.]

[0366] More preferably:

[0367]

[0368] [Wherein, * indicates the binding position.]

[0369] In yet another aspect, PFPE represents:

[0370] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5).

[0371] [In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0372] In this embodiment, e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0373] In yet another aspect, PFPE represents:

[0374] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6).

[0375] [In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0376] In this embodiment, f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0377] In one embodiment, Q can be -SiR 1 n R 2 3－n .

[0378] In another embodiment, Q can be -Y-A.

[0379] R 1 The alkyl group shown may be straight chain or branched. 1 The number of carbon atoms in the alkyl group represented by is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 4. 1 , preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.

[0380] R 2The hydrolyzable group shown in is a group that can be removed from the main skeleton of the compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR 5 , -OCOR 5 、-O-N=CR 5 2. -NR 5 2. -NHR 5 , -NCO, halogen (in these formulas, R 5 represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), etc., preferably -OR 5 (i.e. alkoxy). 5 Examples include non-substituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; and substituted alkyl groups such as chloromethyl. Among them, alkyl groups, especially non-substituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. The hydroxyl group is not particularly limited and may be generated by hydrolysis of a hydrolyzable group.

[0381] n is preferably an integer of 0 to 3, more preferably an integer of 1 to 3, further preferably an integer of 2 to 3, and particularly preferably 3.

[0382] In one embodiment, at least one Q is -SiR 1 n R 2 3－n In the case of, there is at least one R in formula (A1) or (A2) 2 .

[0383] -O-, -CO-, -O-CO-, -CO-O-, -NR in Y 3 -CO-, -CO-NR 3 - Use the valence bonds on the right side to combine with A respectively.

[0384] Examples of the divalent hydrocarbon group represented by Y include divalent aliphatic hydrocarbon groups, divalent alicyclic hydrocarbon groups, divalent aromatic hydrocarbon groups, and divalent groups formed by combinations thereof. Examples of the divalent aliphatic hydrocarbon groups include alkylene groups and divalent unsaturated aliphatic hydrocarbon groups. The number of carbon atoms in the divalent hydrocarbon group represented by Y is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 4.

[0385] R 3 The alkyl group shown may be straight chain or branched. 3 The number of carbon atoms in the alkyl group represented is preferably 1-20, more preferably 1-6, and even more preferably 1-4.

[0386] Y is preferably -O-, -CO-, -O-CO-, -CO-O-, -NR 3 -CO-, -CO-NR 3- or an alkylene group having 1 to 22 carbon atoms, more preferably -CO-, -O-CO-, -NR 3 -CO- or an alkylene group having 1 to 6 carbon atoms.

[0387] As A, preferably -CR 4 =CH2.

[0388] R 4 The alkyl group shown may be straight chain or branched. 4 The number of carbon atoms in the alkyl group represented by is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 4. 4 , preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.

[0389] R 11 The halogen atom shown is preferably an iodine atom, a chlorine atom or a fluorine atom.

[0390] R 12 The alkyl group shown may be straight chain or branched. 12 The alkyl group represented by the above-mentioned has preferably 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms.

[0391] α and α' can be calculated based on X 1 The valence of is determined by, in formula (A1), the sum of α and α' is X 1 For example, X 1 When X is a devalent organic group, the sum of α and α' is 10, for example, α is 9 and α' is 1, α is 5 and α' is 5, or α is 1 and α' is 9. 1 When X is a divalent organic group, α and α' are 1. In formula (A2), α is 1 The value of the valence minus 1.

[0392] X 1 It can be understood that in the compounds represented by formula (A1) and (A2), the perfluoropolyether part (Rf-PFPE part or -PFPE- part) which mainly provides water repellency and surface smoothness, and the silane part or the group having a carbon-carbon unsaturated bond (specifically, the Q group or the group containing the Q group) which provides the bonding energy with the substrate are connected to the connecting part. Therefore, as long as the compounds represented by formula (A1) and (A2) can exist stably, X 1 It can be any organic group.

[0393] X 1 The organic group is preferably a di- to hepta-valent group, more preferably a di- to tetra-valent group, and still more preferably a divalent group.

[0394] As X 1 and the following X 3 , X4 , X 6 , X 8 and X 9 , is not particularly limited, and examples thereof include a divalent group represented by the following formula.

[0395] -(R 13 ) p' -(X a ) q' -R 14 -

[0396] [Wherein,

[0397] R 13 Represents a single bond, -(CH2) s' - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH2) s' -

[0398] R 14 Represents a single bond, -(CH2) t' - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH2) t' -

[0399] s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and further preferably 1 or 2.

[0400] t' is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3, X a Indicates - (X b ) r' -

[0401] X b Each occurrence independently represents a group selected from -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -C(O)O-, -CONR 16 -、-O-CONR 16 -, -NR 16 -、-Si(R 15 )2-、-(Si(R 15 )2O) m' -Si(R 15 )2- and -(CH2) n' - in the group,

[0402] R 15 Each occurrence independently represents phenyl, C 1－6 Alkyl or C 1－6 Alkoxy, preferably C 1－6 Alkyl, more preferably methyl,

[0403] R16 Each occurrence independently represents a hydrogen atom, a phenyl group or a C 1－6 Alkyl (preferably methyl),

[0404] m' is independently an integer of 1 to 100 at each occurrence, preferably an integer of 1 to 20,

[0405] n' is independently an integer of 1 to 20 at each occurrence, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,

[0406] r' is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3,

[0407] p' is 0 or 1,

[0408] q' is 0 or 1,

[0409] Here, at least one of p' and q' is 1, and the order of existence of each repeating unit indicated by p' or q' and enclosed in parentheses is arbitrary.]

[0410] Preferred X 1 for:

[0411] C 1－20 Alkylene,

[0412] -R 13 -X c -R 14 -,or

[0413] -X d -R 14 -

[0414] [Where R 13 and R 14 has the same meaning as above.]

[0415] More preferably X 1 for:

[0416] C 1－20 Alkylene,

[0417] -(CH2) s' -X c -

[0418] -(CH2) s' -X c -(CH2) t' -

[0419] -X d -,or

[0420] -X d -(CH2) t'-

[0421] [Wherein, s' and t' have the same meanings as above.]

[0422] In the above formula, X c express:

[0423] -O-,

[0424] -S-,

[0425] -C(O)O-,

[0426] -CONR 16 -

[0427] -O-CONR 16 -

[0428] -Si(R 15 )2-、

[0429] -(Si(R 15 )2O) m' -Si(R 15 )2-、

[0430] -O-(CH2) u' -(Si(R 15 )2O) m' -Si(R 15 )2-、

[0431] -CONR 16 -(CH2) u' -(Si(R 15 )2O) m' -Si(R 15 )2-、

[0432] -CONR 16 -(CH2) u' -N(R 16 )-,or

[0433] -CONR 16 -(o-phenylene, m-phenylene or p-phenylene)-Si(R 15 )2-.

[0434] [Where R 15 , R 16 The meaning of m' is the same as above.

[0435] u' is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. c Preferred is -O-.

[0436] In the above formula, X d express:

[0437] -S-,

[0438] -C(O)O-,

[0439] -CONR 16 -

[0440] -CONR 16 -(CH2) u' -(Si(R 15 )2O) m' -Si(R 15 )2-、

[0441] -CONR 16 -(CH2) u' -N(R 16 )-,or

[0442] -CONR 16 -(o-phenylene, m-phenylene or p-phenylene)-Si(R 15 )2-.

[0443] More preferably X 1 for:

[0444] C 1－20 Alkylene,

[0445] -(CH2) s' -X c -(CH2) t' -,or

[0446] -X d -(CH2) t' -

[0447] [In the formula, the meanings of the symbols are the same as above.]

[0448] Further optimization of X 1 for:

[0449] C 1－20 Alkylene,

[0450] -(CH2) s' -O-(CH2) t' -

[0451] -(CH2) s' -Si(R 15 )2-(CH2) t' -

[0452] -(CH2) s' -(Si(R 15 )2O) m' -Si(R15 )2-(CH2) t' -

[0453] -(CH2) s' -O-(CH2) u' -(Si(R 15 )2O) m' -Si(R 15 )2-(CH2) t' -,or

[0454] -(CH2) s' -O-(CH2) t' -Si(R 15 )2-(CH2) u' -Si(R 15 )2-(C v H 2v )-.

[0455] [In the formula, each symbol has the same meaning as above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.]

[0456] In the above formula, -(C v H 2v )- may be a straight chain or a branched chain, for example, it may be -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, or -CH(CH3)CH2-.

[0457] X 1 can be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 Fluorinated alkyl (preferably C 1－3 The alkylene group is substituted with one or more substituents in the alkylene group (perfluoroalkyl group).

[0458] As X 1 Specific examples include:

[0459] -CH2O(CH2)2-,

[0460] -CH2O(CH2)3-,

[0461] -CH2O(CH2)6-,

[0462] -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,

[0463] -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,

[0464] <h2 style=";text-align:left;direction:ltr">-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0465] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0466] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2(CH2)2-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0467] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)<h2 style=";text-align:left;direction:ltr"> 20 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2(CH2)2-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0468] <h2 style=";text-align:left;direction:ltr"> CH2OCF2CHFOCF2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0469] <h2 style=";text-align:left;direction:ltr"> -CH2OCF2CHFOCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0470] <h2 style=";text-align:left;direction:ltr"> -CH2OCF2CHFOCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0471] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0472] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0473] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0474] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0475] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0476] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0477] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0478] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0479] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0480] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0481] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-,

[0482] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-

[0483] -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-,

[0484] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-,

[0485] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-,

[0486] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-,

[0487] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-,

[0488] -(CH2)2-,

[0489] -(CH2)3-,

[0490] -(CH2)4-,

[0491] -(CH2)5-,

[0492] -(CH2)6-,

[0493] -(CH2)2-Si(CH3)2-(CH2)2-

[0494] -CONH-(CH2)3-,

[0495] -CON(CH3)-(CH2)3-,

[0496] -CON(Ph)-(CH2)3- (where Ph means phenyl),

[0497] -CONH-(CH2)6-,

[0498] -CON(CH3)-(CH2)6-,

[0499] -CON(Ph)-(CH2)6- (where Ph means phenyl),

[0500] <h2 style=";text-align:left;direction:ltr">-CONH-(CH2)2NH(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0501] <h2 style=";text-align:left;direction:ltr"> -CONH-(CH2)6NH(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0502] <h2 style=";text-align:left;direction:ltr"> CH2O-CONH-(CH2)3-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0503] <h2 style=";text-align:left;direction:ltr"> CH2O-CONH-(CH2)6-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0504] <h2 style=";text-align:left;direction:ltr"> -S-(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0505] <h2 style=";text-align:left;direction:ltr"> (CH2)2S(CH2)3)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0506] <h2 style=";text-align:left;direction:ltr"> -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0507] <h2 style=";text-align:left;direction:ltr"> -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0508] <h2 style=";text-align:left;direction:ltr"> -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0509] <h2 style=";text-align:left;direction:ltr"> -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0510] <h2 style=";text-align:left;direction:ltr"> -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2(CH2)2-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0511] <h2 style=";text-align:left;direction:ltr"> -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)<h2 style=";text-align:left;direction:ltr"> 20 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2(CH2)2-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0512] <h2 style=";text-align:left;direction:ltr"> -C(O)O-(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0513] <h2 style=";text-align:left;direction:ltr"> -C(O)O-(CH2)6-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0514] <h2 style=";text-align:left;direction:ltr"> -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0515] <h2 style=";text-align:left;direction:ltr"> -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0516] <h2 style=";text-align:left;direction:ltr"> -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、

[0517] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-,

[0518] -OCH2-,

[0519] -O(CH2)3-,

[0520] -OCFHCF2-,

[0521] wait.

[0522] In addition, as another X 1 Examples of the group include the following groups:

[0523]

[0524] [Where R 17 are independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1－6 Alkoxy, preferably methyl;

[0525] D is a group selected from the following groups:

[0526] -CH2O(CH2)2-,

[0527] -CH2O(CH2)3-,

[0528] -CF2O(CH2)3-,

[0529] -(CH2)2-,

[0530] -(CH2)3-,

[0531] -(CH2)4-,

[0532] -CONH-(CH2)3-,

[0533] -CON(CH3)-(CH2)3-,

[0534] -CON(Ph)-(CH2)3- (where Ph means phenyl), and

[0535]

[0536] [Where R 18 Each independently represents a hydrogen atom, a C 1－6 Alkyl or C 1－6 The alkoxy group is preferably a methyl group or a methoxy group, and more preferably a methyl group. )

[0537] E is -(CH2)n4 -(n4 is an integer from 2 to 6),

[0538] D is bonded to the PFPE on the main chain of the molecule, and E is bonded to the group on the opposite side of the PFPE.]

[0539] As another X 1 Examples of groups include the following:

[0540]

[0541] [Where R 17 are independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1－6 Alkoxy, preferably methyl;

[0542] Each X 1 In the group, any of T is the following group that is bonded to the PFPE of the main chain of the molecule:

[0543] -CH2O(CH2)2-,

[0544] -CH2O(CH2)3-,

[0545] -CF2O(CH2)3-,

[0546] -(CH2)2-,

[0547] -(CH2)3-,

[0548] -(CH2)4-,

[0549] -CONH-(CH2)3-,

[0550] -CON(CH3)-(CH2)3-,

[0551] -CON(Ph)-(CH2)3- (where Ph means phenyl), or

[0552]

[0553] [Where R 18 Each independently represents a hydrogen atom, a C 1－6 Alkyl or C 1－6 Alkoxy preferably represents methyl or methoxy, more preferably represents methyl.]

[0554] Some of the other Ts are -(CH2) groups bonded to the main chain of the molecule and opposite to PFPE. n” -(n" is an integer of 2 to 6), and when present, the remaining ones are each independently methyl or phenyl.

[0555] In another way, X1 Formula: -(R 19 ) x -(CFR 20 ) y -(CH2) z - In the formula, x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each repeating unit enclosed in brackets is arbitrary in the formula.

[0556] In the above formula, R 19 Each occurrence is independently an oxygen atom, a phenylene group, a carbazolyl group, -NR 21 -(where R 21 represents a hydrogen atom or an organic group) or a divalent organic group. Preferably R 19 It is an oxygen atom or a divalent polar group.

[0557] As the above R 19 The "bivalent polar group" in the above is not particularly limited, and examples thereof include -C(O)-, -C(=NR 22 )- and -C(O)NR 22 -(In these formulas, R 22 represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, and n-propyl, which may be substituted with one or more fluorine atoms.

[0558] In the above formula, R 20 Each occurrence is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and still more preferably a trifluoromethyl group.

[0559] In this method, X 1 Preferred is the formula: -(O) x -(CF2) y -(CH2) z -(wherein, x, y and z have the same meanings as above, and the order of existence of each repeating unit enclosed in brackets in the formula is arbitrary).

[0560] As the above formula: -(O) x -(CF2) y -(CH2) z -, for example, -(O) x′ -(CH2) z″ -O-[(CH2) z″′ -O-] z″″and -(O) x′ -(CF2) y″ -(CH2) z″ -O-[(CH2) z″′ -Q-] z″″ (wherein x' is 0 or 1, y", z" and z'" are each independently an integer of 1 to 10, and z"" is 0 or 1). The left ends of these groups are bonded to the PFPE side.

[0561] In another way, X 1 For-O-CFR 23 -(CF2) e -.

[0562] The above R 23 Each independently represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and still more preferably a trifluoromethyl group.

[0563] The above e's are each independently 0 or 1.

[0564] In one specific example, R 23 is a fluorine atom, and e is 1.

[0565] In the above formula, t is independently an integer of 2-10, preferably an integer of 2-6.

[0566] In the above formula, X 2 Each occurrence of X independently represents a single bond or a divalent organic group. 2 It is preferably an alkylene group having 1 to 20 carbon atoms, more preferably -(CH2) u -(wherein, u is an integer from 0 to 2).

[0567] Formula (B1) and (B2):

[0568] (Rf-PFPE) β′ -X 3 -Q β …(B1)

[0569] Q β -X 3 -PFPE-X 2 -Q β …(B2)

[0570] In formulae (B1) and (B2), Rf, PFPE and Q have the same meanings as described in formulae (A1) and (A2).

[0571] X 3It can be understood that in the compounds represented by formula (B1) and (B2), the perfluoropolyether part (Rf-PFPE part or -PFPE- part) which mainly provides water repellency and surface smoothness, etc. and the silane part or the group having a carbon-carbon unsaturated bond (specifically, the Q group or the group containing the Q group) which provides the bonding energy with the substrate, etc. are connected to the connecting part. Therefore, as long as the compounds represented by formula (B1) and (B2) can exist stably, X 3 It can be any organic group.

[0572] β and β′ can be calculated based on X 3 The valence of is determined by, in formula (B1), the sum of β and β′ is X 3 For example, X 3 When X is a devalent organic group, the sum of β and β' is 10, for example, β is 9 and β' is 1, β is 5 and β' is 5, or β is 1 and β' is 9. 3 When X is a divalent organic group, β and β' are 1. In formula (B2), β is 3 The value of the valence minus 1.

[0573] X 3 The organic group is preferably a di- to hepta-valent group, more preferably a di- to tetra-valent group, and still more preferably a divalent group.

[0574] As X 3 , without particular limitation, for example, 1 The same groups as those described above.

[0575] In one embodiment, at least one Q is -SiR 1 n R 2 3-n In the case of, in formula (B1) or (B2) there is at least one R 2 .

[0576] Formula (C1) and (C2):

[0577] (Rf-PFPE) γ′ -X 4 -(SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 ) γ …(C1)

[0578] (R d1 n1 R c1 m1R b1 l1 R a1 k1 Si) γ -X 4 -PFPE-X 4 -(SiR a1 k1 R b1 l1 R c1 m1 R d 1 n1 ) γ …(C2)

[0579] In formulae (C1) and (C2), Rf and PFPE have the same meanings as described for formulae (A1) and (A2).

[0580] X 4 It can be understood that in the compounds represented by formula (C1) and (C2), the perfluoropolyether part (Rf-PFPE part or -PFPE- part) which mainly provides water repellency and surface smoothness, etc. and the silane part or the group having a carbon-carbon unsaturated bond (specifically, the Q group or the group containing the Q group (the group marked with γ and enclosed in brackets)) which provides the bonding energy with the substrate, etc. are connected to the connecting part. Therefore, as long as the compounds represented by formula (C1) and (C2) can exist stably, the X 4 It can be any organic group.

[0581] γ and γ′ can be calculated based on X 4 The valence of is determined by, in formula (C1), the sum of γ and γ′ is X 4 For example, X 4 When X is a devalent organic group, the sum of γ and γ′ is 10, and for example, γ is 9 and γ′ is 1, γ is 5 and β′ is 5, or γ is 1 and γ′ is 9. 4 When X is a divalent organic group, γ and γ' are 1. In formula (C2), γ is 4 The value of the valence minus 1.

[0582] X 4 The organic group is preferably a di- to hepta-valent group, more preferably a di- to tetra-valent group, and still more preferably a divalent group.

[0583] As X 4 Examples of X are not particularly limited, for example, 1 The same groups as those described above.

[0584] R a1 Each occurrence represents -Z-SiR independently 31 p1R 32 q1 R 33 r1 R 34 s1 .

[0585] Z, at each occurrence, independently represents an oxygen atom or a divalent organic group.

[0586] Z is preferably a divalent organic group, excluding any Si atom (bonded to R) at the end of the main chain of the molecule in formula (C1) or (C2). a1 A group that forms a siloxane bond.

[0587] Z is preferably C 1－6 Alkylene, -(CH2) g -O-(CH2) h -(wherein g is an integer of 1 to 6, and h is an integer of 1 to 6) or -phenylene-(CH2) i - (where i is an integer from 0 to 6), more preferably C 1－3 These groups can be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 The alkynyl group is substituted with one or more substituents.

[0588] R 31 Each occurrence represents R independently a' . R a' The meaning of R a1 same.

[0589] R a1 In the embodiment, the number of Si groups connected in a straight chain via the Z group is at most 5. a1 In the presence of at least one R 31 In the case of R a1 There are two or more Si atoms connected in a straight chain via a Z group, but the maximum number of Si atoms connected in a straight chain via a Z group is 5. a1 The number of Si atoms connected in a straight chain via the Z group is related to the number of Si atoms in R a1 The number of repetitions of -Z-Si- connected in a straight chain is equal.

[0590] For example, the following represents R a1 An example of Si atoms being connected via a Z group.

[0591]

[0592] In the above formula, * indicates the site that is bonded to Si of the main chain, and ... means the site that is bonded to a specified group other than ZSi, that is, when the three valence bonds of the Si atom are all ..., it means the site where the repetition of ZSi ends. In addition, the number on the upper right corner of Si means the number of occurrences of Si connected in a straight chain from * through the Z group. That is, in the case of ZSi repeating with Si 2 The chain ends with "R a1 The number of Si atoms connected in a straight chain via the Z group is 2. Similarly, in ZSi, Si is repeated 3 、Si 4 and Si 5 The chain ends with "R a1 The number of Si atoms connected in a straight chain via the Z group is 3, 4 and 5 respectively. Among them, it can be seen from the above formula that R a1 There are multiple ZSi chains in the network, but they do not need to be of the same length and can be of any length.

[0593] In a preferred embodiment, as described below, "R a1 The number of Si atoms connected in a straight chain via the Z group is 1 (left-hand formula) or 2 (right-hand formula) in all chains.

[0594]

[0595] In one approach, R a1 The number of Si atoms connected in a straight chain via the Z group is 1 or 2, preferably 1.

[0596] In the formula, R 32 Indicates -X independently at each occurrence 5 -Q. The meaning of Q is the same as above.

[0597] X 5 Each occurrence of is independently a single bond or a divalent organic group. 5 Preferably a single bond, C 1－6 Alkylene, -(CH2) g -O-(CH2) h -(wherein, g is an integer of 1 to 6, and h is an integer of 1 to 6) or -phenylene-(CH2) i - (wherein i is an integer from 0 to 6), more preferably a single bond or C 1－3 These groups can be selected, for example, from fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 The alkynyl group is substituted with one or more substituents.

[0598] R 32 Preferred is -CH2-CH=CH2.

[0599] R 33 Each occurrence independently represents a hydroxyl group or a hydrolyzable group.

[0600] The above-mentioned "hydrolyzable group" when used in this specification refers to a group that can undergo a hydrolysis reaction. Examples of hydrolyzable groups include -OR 35 , -OCOR 35 , -O-N=C(R 35 )2.-N(R 35 2. -NHR 35 , -NCO, halogen (in these formulas, R 35 represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), etc., preferably -OR 35 (alkoxy). 35 Examples include non-substituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; and substituted alkyl groups such as chloromethyl. Among them, alkyl groups, especially non-substituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. The hydroxyl group is not particularly limited and may be generated by hydrolysis of a hydrolyzable group.

[0601] Preferred R 33 For -OR 36 (Where R 36 represents substituted or unsubstituted C 1－3 Alkyl, more preferably means methyl).

[0602] R 34 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. The alkyl group having 1 to 22 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

[0603] p1 is an integer from 0 to 3 independently at each occurrence; q1 is an integer from 0 to 3 independently at each occurrence; r1 is an integer from 0 to 3 independently at each occurrence; s1 is an integer from 0 to 3 independently at each occurrence. Among them, p1+q1+r1+s1 (the sum of p1, q1, r1 and s1) is 3.

[0604] In a preferred embodiment, in R a1 The R at the end of a' (There is no R a' When R a1 ) in which q1 is preferably greater than 2, for example, 2 or 3, more preferably 3.

[0605] R b1 Indicates -X independently at each occurrence 5-Q.X 5 and Q have the same meaning as above. b1 Preferred is -CH2-CH=CH2.

[0606] R c1 Each occurrence independently represents a hydroxyl group or a hydrolyzable group.

[0607] R c1 Preferably, hydroxyl group, -OR 37 , -OCOR 37 , -O-N=C(R 37 )2.-N(R 37 2. -NHR 37 , -NCO, halogen (where R 37 represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), preferably -OR 37 . R 37 The alkyl group includes non-substituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; and substituted alkyl groups such as chloromethyl. Among them, alkyl groups, especially non-substituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. The hydroxyl group is not particularly limited and may be generated by hydrolysis of a hydrolyzable group. More preferably, R c1 For -OR 38 (Where R 38 represents substituted or unsubstituted C 1－3 Alkyl, more preferably means methyl).

[0608] R d1 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. The alkyl group having 1 to 22 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

[0609] k1 is an integer from 0 to 3 independently at each occurrence; l1 is an integer from 0 to 3 independently at each occurrence; m1 is an integer from 0 to 3 independently at each occurrence; n1 is an integer from 0 to 3 independently at each occurrence. k1+l1+m1+n1 (the sum of k, l, m and n) is 3.

[0610] In formulas (C1) and (C2), in -(SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 ) r There are at least 2 Q groups in .

[0611] Formula (D1) and (D2):

[0612] (Rf-PFPE) δ′ -X 6 -(CR a2 k2 R b2 l2 R c2 m2 R d2 n2 ) δ …(D1)

[0613] (R d2 n2 R c2 m2 R b2 l2 R a2 k2 C) δ -X 6 -PFPE-X 6 -(CR a2 k2 R b2 l2 R c2 m2 R d2 n2 ) δ …(D2)

[0614] In formulae (D1) and (D2), Rf and PFPE have the same meanings as described for formulae (A1) and (A2).

[0615] X 6 It can be understood that in the compounds represented by formulas (D1) and (D2), the perfluoropolyether part (i.e., the Rf-PFPE part or the -PFPE- part) that mainly provides water repellency and surface smoothness, etc. and the silane part or the group having a carbon-carbon unsaturated bond (specifically, the Q group or the group containing the Q group (the group marked with δ and enclosed in brackets)) that provides the bonding energy with the substrate, etc., connects the connecting part. Therefore, as long as the compounds represented by formulas (D1) and (D2) can exist stably, the X 6 It can be any organic group.

[0616] δ and δ′ can be determined according to the valence of X6. In formula (D1), the sum of δ and δ′ is equal to X 6 The valences are equal. For example, in X 6 When X is a devalent organic group, the sum of δ and δ' is 10, and for example, δ is 9 and δ' is 1, δ is 5 and δ' is 5, or δ is 1 and δ' is 9. 6 When X is a divalent organic group, δ and δ' are 1. In formula (D2), δ is6 The value of the valence minus 1.

[0617] X 6 The organic group is preferably a di- to hepta-valent group, more preferably a di- to tetra-valent group, and still more preferably a divalent group.

[0618] In one approach, X 6 It is a divalent to tetravalent organic group, δ is 1 to 3, and δ' is 1.

[0619] As the above X 6 Examples of X are not particularly limited, for example, 1 The same groups as those described above.

[0620] R a2 Indicates -Z independently at each occurrence 2 -CR 41 p2 R 42 q2 R 43 r2 R 44 s2 .

[0621] Z 2 Each occurrence independently represents an oxygen atom or a divalent organic group.

[0622] Z 2 Preferably C 1-6 Alkylene, -(CH2) g2 -O-(CH2) h2 -(wherein, g2 is an integer of 0 to 6, for example, an integer of 1 to 6, and h2 is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene-(CH2) i2 - (wherein i2 is an integer from 0 to 6), more preferably C 1-3 These groups can be selected, for example, from fluorine atoms, C 1-6 Alkyl, C 2-6 Alkenyl and C 2－6 The alkynyl group is substituted with one or more substituents.

[0623] R 41 Each occurrence represents R independently a2' . R a2' The meaning of R a2 same.

[0624] R a2 In, through Z 2 The maximum number of carbon atoms connected in a straight chain is 5. a2 There is at least one R 41 When Ra2 There are more than 2 via Z 2 The carbon atoms are connected to form a straight chain, but such 2 The maximum number of carbon atoms connected in a straight chain is 5. a2 Via Z 2 The number of carbon atoms connected to form a straight chain is related to the number of carbon atoms in R a2 -Z connected in a straight chain 2 The number of repetitions of -C- is equal.

[0625] In a preferred embodiment, "R a2 Via Z 2 The "number of carbon atoms connected in a straight chain" is 1 (left-hand formula) or 2 (right-hand formula) in all chains.

[0626] In one approach, R a2 Via Z 2 The number of carbon atoms connected in a straight chain is 1 or 2, preferably 1.

[0627] R 42 Indicates -X 7 -Q.

[0628] X 7 Each occurrence independently represents a divalent organic group.

[0629] In a preferred embodiment, X 7 C 1－6 Alkylene, -(CH2) g' -O-(CH2) h' -(wherein, g' is an integer of 0 to 6, for example, an integer of 1 to 6, and h' is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene-(CH2) i' - (wherein i' is an integer from 0 to 6). These groups can be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 The alkynyl group is substituted with one or more substituents.

[0630] In one approach, X 7 Can be C 1－6 Alkylene, -O-(CH2) h' - or -phenylene-(CH2) i' -

[0631] Q has the same meaning as Q in formulae (A1) and (A2).

[0632] R 43 Each occurrence independently represents a hydroxyl group or a hydrolyzable group.

[0633] The above-mentioned "hydrolyzable group" when used in this specification refers to a group that can undergo a hydrolysis reaction. Examples of hydrolyzable groups include -OR 45 , -OCOR 45 , -O-N=C(R 45 )2.-N(R 45 2. -NHR 45 , -NCO, halogen (in these formulas, R 45 represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), etc., preferably -OR (alkoxy). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl, etc. Among them, alkyl groups, especially unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. The hydroxyl group is not particularly limited and may be generated by hydrolysis of a hydrolyzable group.

[0634] Preferred R 43 For -OR 46 (Where R 46 represents substituted or unsubstituted C 1－3 Alkyl, more preferably represents ethyl or methyl, particularly preferably represents methyl).

[0635] R 44 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. The alkyl group having 1 to 22 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

[0636] p2 is an integer from 0 to 3 at each occurrence; q2 is an integer from 0 to 3 at each occurrence; r2 is an integer from 0 to 3 at each occurrence; s2 is an integer from 0 to 3 at each occurrence. The sum of p2, q2, r2 and s2 is 3.

[0637] In a preferred embodiment, in R a2 The R at the end of a2' (There is no R a2' When R a2 ) in which q2 is preferably greater than 2, for example, 2 or 3, more preferably 3.

[0638] In a preferred embodiment, R a2 At least one of the terminal parts of can be -C(-X 7 -Q)2R 41 q2 R 43 r2 R 44 s2(where the sum of q2, r2 and s2 is 1) or -C(-X 7 -Q)3, preferably -C(-X 7 -Q)3.

[0639] R b2 Indicates -X independently at each occurrence 7 -Q. Among them, Q and X 7 The meaning is the same as above R 42 The records in are the same.

[0640] R c2 Each occurrence independently represents a hydroxyl group or a hydrolyzable group. The meaning of "hydroxyl group or a hydrolyzable group" is the same as that of R 43 The records in are the same.

[0641] R d2 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. The alkyl group having 1 to 22 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

[0642] k2 is independently an integer from 0 to 3 at each occurrence; l2 is independently an integer from 0 to 3 at each occurrence; m2 is independently an integer from 0 to 3 at each occurrence; n2 is independently an integer from 0 to 3 at each occurrence. The sum of k2, l2, m2 and n2 is 3.

[0643] In one embodiment, at least one k2 is 2 or 3, preferably 3.

[0644] In one embodiment, k2 is 2 or 3, preferably 3.

[0645] In one embodiment, l2 is 2 or 3, preferably 3.

[0646] In formulae (D1) and (D2), at least one q2 is 2 or 3, or at least one l is 2 or 3. That is, there are at least two -X 7 -Q base.

[0647] Formula (E1) and (E2):

[0648] (Rf-PFPE) ε′ -X 8 -R 50 ε …(E1)

[0649] R 50 ε -X 8 -PFPE-X 8 -R 50ε …(E2)

[0650] In formulae (E1) and (E2), Rf and PFPE have the same meanings as described for formulae (A1) and (A2).

[0651] X 8 It can be understood that in the compounds represented by formula (E1) and (E2), the perfluoropolyether part (i.e., the Rf-PFPE part or -PFPE- part) which mainly provides water repellency and surface slip, and the functional group (specifically, R 50 Therefore, as long as the compounds represented by formula (E1) and (E2) can exist stably, the X 8 It can be any organic group.

[0652] ε and ε′ can be calculated based on X 8 The valence of is determined by, in formula (D1), the sum of ε and ε′ and X 8 The valences of are equal. For example, X 8 When X is a devalent organic group, the sum of ε and ε′ is 10, for example, ε is 9 and ε′ is 1, ε is 5 and ε′ is 5, or ε is 1 and ε′ is 9. 8 When X is a divalent organic group, ε and ε′ are 1. In formula (E2), ε is 8 The value of the valence minus 1.

[0653] X 8 The organic group is preferably a di- to hepta-valent group, more preferably a di- to tetra-valent group, and still more preferably a divalent group.

[0654] In one approach, X 8 It is a divalent to tetravalent organic group, ε is 1 to 3, and ε' is 1.

[0655] As X 8 Examples of X are not particularly limited, for example, 1 The same groups as those described above.

[0656] R 50 Indicates -OR independently at each occurrence 51 、-SR 51 、-NR 51 2. -COOR 51 , -SO3H or -(SiR 52 2O) n3 -SiR 52 3(where R 51 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, R 52 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, R53 represents a hydrocarbon group having 1 to 22 carbon atoms).

[0657] R 51 The alkyl group having 1 to 22 carbon atoms represented by is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group. 51 , preferably a hydrogen atom or a methyl group.

[0658] As R 52 The alkyl group having 1 to 22 carbon atoms shown in R includes an aliphatic hydrocarbon group having 1 to 22 carbon atoms and an aromatic hydrocarbon group having 6 to 22 carbon atoms. 52 The aliphatic hydrocarbon group in R may be an alkyl group or an unsaturated aliphatic hydrocarbon group, and is preferably an alkyl group. 52 The number of carbon atoms of the aliphatic hydrocarbon group in R is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 2. 52 The aromatic hydrocarbon group in may be a monocyclic ring or a polycyclic ring. 52 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-20, more preferably 6-10.

[0659] As R 52 , preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, further preferably an alkyl group having 1 to 2 carbon atoms or a monocyclic aromatic hydrocarbon group having 6 to 10 carbon atoms, particularly preferably a methyl group or a phenyl group.

[0660] The fluorine-containing carbon compound is a compound containing a hydrocarbon group in which one or more hydrogen atoms are substituted with fluorine atoms.

[0661] The fluorocarbon-containing compound is preferably represented by formula (F1) or (F2).

[0662] (R 61 -Rf′) φ′ -X 9 -Q φ …(F1)

[0663] Q φ -X 9 -Rf′-X 9 -Q φ …(F2)

[0664] [In formulas (F1) and (F2),

[0665] X 9 Each independently represents a single bond or a di- to decavalent organic group,

[0666] φ are each independently an integer from 1 to 9,

[0667] φ′ is an integer from 1 to 9,

[0668] R 61 each independently represents a fluorine atom, -CHF2 or -CF3,

[0669] Rf' each independently represents a perfluoroalkylene group having 1 to 30 carbon atoms,

[0670] Q each independently represents -SiR 1 n R 2 3-n or -YA,

[0671] R1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0672] R 2 Each independently represents a hydroxyl group or a hydrolyzable group,

[0673] n in each (-SiR 1 n R 2 3-n ) are independently an integer from 0 to 3,

[0674] Y each independently represents a single bond, -O-, -CO-, -O-CO-, -CO-O-, -CO-NR 3 -、-NR 3 -CO- or a divalent hydrocarbon group having 1 to 22 carbon atoms,

[0675] R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0676] A represents independently -CR 4 =CH2 or -C≡CH,

[0677] R4 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0678] At least 1 Q is -SiR 1 n R 2 3-n In the case of, in formula (F1) or formula (F2), there is at least one R 2 . ]

[0679] In formulae (F1) and (F2), Q has the same meaning as described for formulae (A1) and (A2).

[0680] X 9It can be understood that in the compounds represented by formulae (F1) and (F2), the fluoroalkyl moiety (R 61 -Rf′- or -Rf′- part) and a group having a carbon-carbon unsaturated bond (specifically, an A group or a group containing an A group) that provides bonding energy to the substrate. Therefore, as long as the compounds represented by formulas (F1) and (F2) can exist stably, X 9 It can be any organic group.

[0681] φ can be calculated based on X 9 For example, X 9 In the case of a devalent organic group, φ is 9, X 9 In the case of a divalent organic group, φ is 1.

[0682] φ and φ' can be calculated based on X 9 The valence of is determined. In formula (F1), the sum of φ and φ' is X 9 For example, X 9 In the case of a devalent organic group, the sum of φ and φ' is 10, for example, φ is 9 and φ' is 1, φ is 5 and is 5, or φ is 1 and φ' is 9. In addition, X 9 When X is a divalent organic group, φ and φ' are 1. In formula (F2), φ is 9 The value of the valence minus 1.

[0683] X 9 The organic group is preferably a di- to hepta-valent group, more preferably a di- to tetra-valent group, and still more preferably a divalent group.

[0684] As X 9 Examples of X are not particularly limited, for example, 1 The same groups as those described above.

[0685] R 61 It represents a fluorine atom, -CHF2 or -CF3, and is preferably a fluorine atom or -CF3.

[0686] Rf' represents a perfluoroalkylene group having 1 to 20 carbon atoms. Rf' preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, and still more preferably has 3 to 6 carbon atoms. Specific examples of Rf' include -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF(CF3)-, -CF2CF2CF2CF2-, -CF2CF(CF3)-, -C(CF3)-, -(CF2)4CF2-, -(CF2)2CF(CF3)-, -CF2C(CF3)-, -CF(CF3)CF2CF2CF2-, -(CF2)5CF2-, -(CF2)3CF(CF3)2, -(CF2)4CF(CF3)2, -C8CF 17 Among them, linear perfluoroalkylene groups having 3 to 6 carbon atoms are preferred, such as -CF2CF2CF2CF2-, -CF2CF2CF2-, etc.

[0687] In one embodiment, at least one Q is -SiR 1 n R 2 3－n In the case of, in formula (F1) or (F2) there is at least one R 2 .

[0688] The fluorine-containing vinyl polymer has a unit derived from a fluorine-containing vinyl monomer. The unit derived from the fluorine-containing vinyl monomer is preferably represented by the formula (G1), (G2) or (G3).

[0689]

[0690] [In formulas (G1), (G2) and (G3),

[0691] R a3 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, or a fluorinated alkyl group having 1 to 22 carbon atoms,

[0692] R b3 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, or a fluorinated alkyl group having 1 to 22 carbon atoms,

[0693] R c3 represents an alkyl group having 1 to 22 carbon atoms, an alicyclic hydrocarbon group having 3 to 22 carbon atoms, an aromatic hydrocarbon group having 6 to 22 carbon atoms, or a group having 4 to 22 carbon atoms in which an alicyclic hydrocarbon group or an aromatic hydrocarbon group is bonded to an alkylene group, wherein -CH2- contained in these groups may be replaced by an oxygen atom, and hydrogen atoms contained in these groups may be replaced by fluorine atoms,

[0694] Y 2 Represents -O-, -CO-, -O-CO-, -CO-O-, -NR6 -CO- or -CO-NR 6 -

[0695] R 6 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,

[0696] Y 3 represents a single bond or an oxygen atom,

[0697] R d3 represents an alkyl group having 1 to 22 carbon atoms, wherein -CH2- contained in the alkyl group may be replaced by an oxygen atom, and the hydrogen atom contained in the alkyl group may be replaced by a fluorine atom,

[0698] R e3 represents an alkylene group having 3 to 22 carbon atoms, wherein -CH2- contained in the alkylene group may be replaced by an oxygen atom, and wherein a hydrogen atom contained in the alkylene group may be replaced by a fluorine atom,

[0699] X 10 represents a single bond, an alkylene group having 1 to 22 carbon atoms, or a fluorinated alkylene group having 1 to 22 carbon atoms.]

[0700] R a3 , R b3 , R c3 , R d3 or R 6 The alkyl group shown may be straight chain or branched. a3 , R b3 , R c3 , R d3 or R 6 The number of carbon atoms in the alkyl group represented is preferably 1-20, more preferably 1-6, and even more preferably 1-4.

[0701] R a3 , R b3 The fluoroalkyl group and R c3 , R d3 A group in which a hydrogen atom of an alkyl group represented by the formula (hereinafter, a ... a3 , R b3 The fluoroalkyl group and R c3 , R d3 The groups in which the hydrogen atoms of the alkyl groups are replaced by fluorine atoms are collectively referred to as "R a3 , R b3 , R c3 , R d3 The fluoroalkyl group shown in the figure ", etc.) can be a straight chain or a branched chain. a3 , R b3 , R c3 , R d3The number of carbon atoms in the fluorinated alkyl group represented by R is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 4. a3 , R b3 , R c3 , R d3 The fluorinated alkyl group shown may be a perfluorinated alkyl group or a partially fluorinated alkyl group.

[0702] R c3 The alicyclic hydrocarbon group in may be a saturated or unsaturated group, and may be a monocyclic or polycyclic (bridged) group. The alicyclic hydrocarbon group may have an alkyl group having 1 to 22 carbon atoms, -OR 6 , -COOR 6 , -COR 6 , -CONR 6 2. -SO3R 6 The alkyl group as the above substituent may be linear or branched, and the number of carbon atoms of the alkyl group as the above substituent is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 4.

[0703] R c3 In the group in which hydrogen atoms contained in the alicyclic hydrocarbon group are substituted with fluorine atoms (hereinafter sometimes simply referred to as "fluorinated alicyclic hydrocarbon group"), part or all of the hydrogen atoms may be substituted with fluorine atoms.

[0704] R c3 The aromatic hydrocarbon group in may be monocyclic or polycyclic. The aromatic hydrocarbon group may have an alkyl group having 1 to 22 carbon atoms, -OR 6 , -COOR 6 , -COR 6 , -CONR 6 2. -SO3R 6 The alkyl group as the above substituent may be linear or branched, and the number of carbon atoms of the alkyl group as the above substituent is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 4.

[0705] R c3 The group in which hydrogen atoms contained in the aromatic hydrocarbon group are substituted with fluorine atoms (hereinafter sometimes simply referred to as "fluorinated aryl group") may be a perfluorinated aryl group or a fluorinated aryl group in which a part of hydrogen atoms are substituted with fluorine atoms.

[0706] R c3 The alkylene group in R may be a straight chain or a branched chain. c3 The number of carbon atoms of the alkylene group in the group is preferably 1-20, more preferably 1-6, and even more preferably 1-4.

[0707] R d3When the -CH2- contained in the alkyl group shown is replaced by an oxygen atom, the adjacent -CH2- is not replaced by an oxygen atom at the same time. 2 The bound -CH2- is not replaced by an oxygen atom. d3 In the group where -CH2- contained in the alkyl group represented by is replaced by an oxygen atom, it is preferred that 1 or more and 4 or less -CH2- are present between the oxygen atoms. d3 The group in which -CH2- contained in the alkyl group is replaced by an oxygen atom (hereinafter sometimes referred to as "polyether group") may be linear or branched, and the number of carbon atoms in the polyether group is preferably 1-15, more preferably 1-12.

[0708] R d3 In a group in which a -CH2- in the alkyl group represented by the above is replaced by an oxygen atom and a hydrogen atom in the group is further replaced by a fluorine atom (hereinafter sometimes referred to as a "fluoropolyether group"), adjacent -CH2- are not replaced by oxygen atoms at the same time, and Y 2 The bonded -CH2- is not replaced by an oxygen atom. In the above-mentioned fluoropolyether group, preferably there are 1 or more but 4 or less -CH2- between oxygen atoms. It can be a straight chain or a branched chain, and the number of carbon atoms in the above-mentioned fluoropolyether group is preferably 1 to 15, and more preferably 1 to 12.

[0709] R e3 The alkylene group shown may be straight chain or branched. e3 The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-6, and even more preferably 1-4.

[0710] R e3 When the -CH2- contained in the alkylene group shown is replaced by an oxygen atom, the adjacent -CH2- is not replaced by an oxygen atom at the same time. 3 The bound -CH2- is not replaced by an oxygen atom. e3 In the group where -CH2- contained in the alkylene group represented by is replaced by an oxygen atom, it is preferred that 1 or more and 4 or less -CH2- are present between the oxygen atoms. e3 The group in which -CH2- contained in the alkylene group is replaced by an oxygen atom (hereinafter sometimes referred to as "(divalent) polyether group") preferably has 1 to 15 carbon atoms, and more preferably 1 to 12 carbon atoms.

[0711] R e3 The group in which the hydrogen atom of the alkylene group is replaced by a fluorine atom (hereinafter sometimes referred to as "fluoroalkylene group") may be a straight chain or a branched chain. 10 , R e3 The number of carbon atoms in the fluorinated alkylene group represented by R is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 4. e3The fluorinated alkylene group shown may be a perfluorinated alkylene group or a partially fluorinated alkylene group.

[0712] R e3 In a group in which -CH2- contained in the alkylene group represented by the above is replaced by an oxygen atom and a hydrogen atom contained in the group is further replaced by a fluorine atom (hereinafter sometimes referred to as a "(divalent) fluoropolyether group"), adjacent -CH2- are not replaced by oxygen atoms at the same time, and Y 3 The bonded -CH2- is not replaced by an oxygen atom. In the above-mentioned fluoropolyether group, preferably there are 1 or more and 4 or less -CH2- between oxygen atoms. The above-mentioned fluoropolyether group may be a straight chain or a branched chain, and the number of carbon atoms in the above-mentioned fluoropolyether group is preferably 1 to 15, and more preferably 1 to 12.

[0713] X 10 The alkylene group shown may be a straight chain or a branched chain. 10 The number of carbon atoms in the alkylene group is preferably 1-20, more preferably 1-6, and even more preferably 1-4.

[0714] X 10 The alkylene group represented by the formula (a) may have an alkyl group having 1 to 22 carbon atoms, -OR 6 , -COOR 6 , -COR 6 , -CONR 6 2. -SO3R 6 The alkyl group as the above substituent may be linear or branched, and the number of carbon atoms of the alkyl group as the above substituent is preferably 1 to 20, more preferably 1 to 6, and further preferably 1 to 4. In addition, -CH2- contained in the alkyl group as the above substituent may be replaced by an oxygen atom, and the hydrogen atom contained in the alkyl group as the above substituent may be replaced by a fluorine atom.

[0715] X 10 The fluoroalkylene group shown may be a straight chain or a branched chain. 10 The number of carbon atoms in the fluorinated alkylene group represented by X is preferably 1 to 20, more preferably 1 to 6, and even more preferably 1 to 4. 10 The fluorinated alkylene group shown may be a perfluorinated alkylene group or a partially fluorinated alkylene group.

[0716] As R a3 , preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms or a fluoroalkyl group having 1 to 22 carbon atoms, more preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a fluorine atom.

[0717] As R b3, preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, or a fluoroalkyl group having 1 to 22 carbon atoms, more preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, further preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0718] As R c3 , preferably an alkyl group having 1 to 22 carbon atoms, a polyether group having 1 to 15 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, a fluoropolyether group having 1 to 15 carbon atoms, a group in which hydrogen atoms contained in an alicyclic hydrocarbon group having 3 to 22 carbon atoms are substituted with fluorine atoms (hereinafter sometimes referred to as a "fluorinated alicyclic hydrocarbon group"), a fluorinated aryl group having 6 to 22 carbon atoms, a group in which an alicyclic hydrocarbon group having 3 to 21 carbon atoms, a fluorinated alicyclic hydrocarbon group having 3 to 21 carbon atoms, an aromatic hydrocarbon group having 6 to 21 carbon atoms, or a fluorinated aryl group having 6 to 21 carbon atoms is bonded to an alkylene group having 1 to 10 carbon atoms or a fluorinated alkylene group having 1 to 10 carbon atoms.

[0719] As R d3 , preferably an alkyl group having 1 to 22 carbon atoms, a polyether group having 1 to 15 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or a fluoropolyether group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, a polyether group having 1 to 15 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having 1 to 15 carbon atoms, further preferably a fluoroalkyl group having 1 to 20 carbon atoms or a fluoropolyether group having 1 to 15 carbon atoms.

[0720] As R e3 , preferably an alkylene group having 1 to 22 carbon atoms, a polyether group having 1 to 15 carbon atoms, a fluoroalkylene group having 1 to 22 carbon atoms, or a fluoropolyether group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, a polyether group having 1 to 15 carbon atoms, a fluoroalkylene group having 1 to 20 carbon atoms, or a fluoropolyether group having 1 to 15 carbon atoms, further preferably a fluoroalkylene group having 1 to 20 carbon atoms or a fluoropolyether group having 1 to 15 carbon atoms.

[0721] As R 6 , preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0722] As X 10 , preferably a single bond or a fluorinated alkylene group having 1 to 22 carbon atoms, more preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.

[0723] In formula (G3), e3 The ring binds X 10The two carbon atoms bonded by the two valence bonds may be adjacent to each other, or an alkylene group having 1 to 4 carbon atoms or a fluoroalkylene group having 1 to 4 carbon atoms may exist between the two carbon atoms.

[0724] In the present invention, the molecular weight of the fluorine-containing polymer may be, for example, 200 or more, preferably 400 or more, more preferably 1,000 or more, and may be, for example, 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less.

[0725] The dispersion degree (weight average molecular weight / number average molecular weight (Mw / Mn)) of the fluorinated polymer may be, for example, 1.0 or more, preferably 3.0 or less, more preferably 2.0 or less, and further preferably 1.5 or less.

[0726] According to the method for measuring the molecular weight of a fluorinated polymer of the present invention, the stability of the liquid flow state and the solubility of the sample fluorinated polymer in the mobile phase solvent can be combined to achieve stable measurement. The method for measuring the molecular weight of the present invention is applicable to a wide range of fluorinated polymers.

[0727] Example

[0728] The present invention is described in more detail by the following examples, but the present invention is not limited thereto.

[0729] (Example 1)

[0730] As the mobile phase solvent, 3M TM Novec TM A mixed solution (mobile phase solvent 1) was prepared by mixing 7200 and hexafluoro-2-propanol (HFIP) in a volume ratio of 80 / 20. Before the measurement, the temperature of the separation carrier and the detector was maintained at 30°C, and the mobile phase solvent was passed at a flow rate of 0.75 mL / min in this state to stabilize the baseline. After that, 100 μL of a solution in which the fluorinated polymer 1 represented by the following formula was dissolved in the mobile phase solvent 1 at a solid content concentration of 1% by mass was passed, and the molecular weight of the fluorinated polymer 1 was determined by the SEC method.

[0731]

[0732] (In the formula, m is an integer from 1 to 6.)

[0733] At this time, the calibration curve was based on a perfluoropolyether oil of known molecular weight (DEMNUM, manufactured by Daikin Industries, Ltd.). TM The curve made.

[0734] The measurement conditions when measuring by the SEC method are as follows.

[0735] Separation carrier: Showa Denko K.K. ShodexTM GPC KF-806L(8.0mmI.Dx 300mm)x 3

[0736] Flow rate: 0.75mL / min

[0737] Measurement temperature (temperature of separation carrier and detector): 30℃ or 40℃

[0738] Detector: RI (differential refractive index detector)

[0739] Chromatography (device): SPECTRIS Corporation Viscotek TDA 305

[0740] (Example 2)

[0741] The molecular weight measurement was carried out under the same conditions as in Example 1 except that the temperature of the separation carrier and the detector was maintained at 40°C.

[0742] At this time, the calibration curve was based on a perfluoropolyether oil of known molecular weight (DEMNUM, manufactured by Daikin Industries, Ltd.). TM The curve made.

[0743] (Example 3)

[0744] As the mobile phase solvent, 3M TM Novec TM The molecular weight was measured under the same conditions as in Example 1 except that a mixed solution (mobile phase solvent 2) of 7100 and hexafluoro-2-propanol (HFIP) in a volume ratio of 80 / 20 was used and a fluorinated polymer 2 represented by the following formula was used as a measurement sample.

[0745]

[0746] At this time, a curve prepared using polymethyl methacrylate (PMMA) having a known molecular weight was used as the calibration curve.

[0747] (Comparative Example 1)

[0748] The molecular weight measurement was carried out in the same manner as in Example 1 except that a mixed solution of dichloropentafluoropropane and HFIP in a volume ratio of 90 / 10 was used as the mobile phase solvent.

[0749] At this time, the calibration curve was based on a perfluoropolyether oil of known molecular weight (DEMNUM, manufactured by Daikin Industries, Ltd.). TM The curve made.

[0750] The calibration curve when using each mobile phase solvent uses the following perfluoropolyether oil with known molecular weight or commercially available standard PMMA as a standard sample, and measures the time from the time each standard sample is injected into the separation carrier to the time when the detector can detect the outflow (retention time) under the same conditions as in Example 1. The number average molecular weight of each standard sample is plotted against the retention time measured for each standard sample to prepare a calibration curve.

[0751] [Perfluoropolyether oil of known molecular weight]

[0752] Standard sample 1: DEMNUM TM S-200, number average molecular weight 7,250, weight average molecular weight 7,902

[0753] Standard sample 2: DEMNUM TM S-65, number average molecular weight 4,180, weight average molecular weight 4,598

[0754] Standard sample 3: DEMNUM TM S-20, number average molecular weight 2,725, weight average molecular weight 2,998

[0755] [PMMA]

[0756] GL Science Co., Ltd. Polymer Kit MM-10PMMA (Polymethyl Methacrylate)

[0757] Standard sample 4: number average molecular weight 659,000, weight average molecular weight 685,400

[0758] Standard sample 5: number average molecular weight 254,100, weight average molecular weight 264,300

[0759] Standard sample 6: number average molecular weight 55,600, weight average molecular weight 56,710

[0760] Standard sample 7: number average molecular weight 24,830, weight average molecular weight 25,330

[0761] Standard sample 8: number average molecular weight 5,200, weight average molecular weight 5,510

[0762] Standard sample 9: number average molecular weight 1,140, ​​weight average molecular weight 1,322

[0763] (evaluate)

[0764] The solubility of the fluorinated polymer in the mobile phase solvent was confirmed, and the stability of the flow state was evaluated by measuring the time required for the baseline to stabilize.

[0765] The results are shown in Table 1.

[0766] [Table 1]

[0767]

[0768] Examples 1, 2 and 3 are examples of the present invention. As a result, the flow state was stable, the solubility of the fluorinated polymer in the mobile phase solvent was good, and stable measurement could be achieved.

[0769] Comparative Example 1 is an example in which a fluorinated solvent containing chlorine atoms was used as the mobile phase solvent. The baseline was difficult to stabilize, and stable measurement could not be achieved.

[0770] Industrial Applicability

[0771] According to the method for measuring the molecular weight of a fluorinated polymer of the present invention, the stability of the liquid flow state and the solubility of the sample fluorinated polymer in the mobile phase solvent can be combined to achieve stable measurement. The method for measuring the molecular weight of the present invention is applicable to a wide range of fluorinated polymers.

Claims

1. A method for determining the molecular weight of a fluorinated polymer, which is a method for determining the molecular weight of a fluorinated polymer by size exclusion chromatography, wherein: The method comprises the steps of dissolving the fluorine-containing polymer in a mobile phase solvent to obtain a solution which is passed into a separation carrier, The mobile phase solvent contains a fluorinated solvent, The fluorine-containing solvent does not contain chlorine atoms, The boiling point of the fluorine-containing solvent is 58° C. or higher.

2. The method for determining the molecular weight of a fluorinated polymer according to claim 1, wherein: The measurement temperature is 25°C to 40°C.

3. The method for determining the molecular weight of a fluorinated polymer according to claim 1 or 2, wherein: The fluorine-containing solvent includes at least one selected from the group consisting of fluorine-containing ethers, fluorine-containing alcohols and fluorocarbons.

4. The method for measuring the molecular weight of a fluorinated polymer according to any one of claims 1 to 3, characterized in that: The volume ratio of the chlorine-containing solvent in the mobile phase solvent is 50 volume % or less.

5. The method for measuring the molecular weight of a fluorinated polymer according to any one of claims 1 to 4, characterized in that: The boiling point of the fluorine-containing solvent is 120° C. or lower.

6. The method for measuring the molecular weight of a fluorinated polymer according to any one of claims 1 to 5, characterized in that: The fluorine-containing polymer is a fluorinated polyether group-containing compound, a fluorine-containing carbon compound or a fluorine-containing vinyl polymer.

7. The method for determining the molecular weight of a fluorinated polymer according to claim 6, wherein: The fluorinated polyether group-containing compound is a compound represented by formula (A1), (A2), (B1), (B2), (C1), (C2), (D1), (D2), (E1) or (E2), (Rf-PFPE) β′ -X 3 -Q β …(B1) Q β -X 3 -PFPE-X 3 -Q β …(B2) (Rf-PFPE) γ′ -X 4 -(siR a1 k1 R b1 11 R c1 m1 R d1 n1 ) γ …(C1) (R d1 n1 R c1 m1 R b1 l1 R a1 k1 Si) γ -X 4 -PFPE-X 4 -(SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 ) γ …(C2) (Rf-PFPE) δ′ -X 6 -(CR a2 k2 R b2 12 R c2 m2 R d2 n2 ) δ …(D1) (R d2 n2 R c2 m2 R b2 12 R a2 k2 C) δ -X 6 -PFPE-X 6 -(CR a2 k2 R b2 12 R c2 m2 R d2 n2 ) δ …(D2) (Rf-PFPE) ε′ -X 8 -R 5 0 ε …(E1) R 50 ε -X 8 -PFPE-X 8 -R 50 ε …(E2) In formulas (A1) and (A2), Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; PFPE are each independently a divalent fluorinated polyether group; Q each independently represents -SiR 1 n R 2 3-n or -YA, R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, R 2 Each independently represents a hydroxyl group or a hydrolyzable group, n in each (-SiR 1 n R 2 3-n ) are independently an integer from 0 to 3, Y each independently represents a single bond, -O-, -CO-, -O-CO-, -CO-O-, -NR 3 -CO-, -CO-NR 3 - or a divalent hydrocarbon group having 1 to 22 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, A represents independently -CR 4 =CH2 or -C≡CH, R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, R 11 each independently represents a hydrogen atom or a halogen atom, R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, X 1 Each independently represents a single bond or a di- to decavalent organic group, X 2 Each independently represents a single bond or a divalent organic group, t are each independently an integer of 2 to 10, α is an integer of 1 to 9 independently. α' is an integer from 1 to 9, At least one Q is -SiR 1 n R 2 3－n In the case of, in formula (A1) or (A2) there is at least one R 2 ; In formulas (B1) and (B2), X 3 Each independently represents a single bond or a di- to decavalent organic group, β is an integer of 1 to 9 independently. β' is an integer from 1 to 9, At least one Q is -SiR 1 n R 2 3－n In the case of, in formula (B1) or (B2) there is at least one R 2 , Rf, PFPE, Q, R 1 and R 2 has the same meaning as above; In formulas (C1) and (C2), X 4 Each independently represents a single bond or a di- to decavalent organic group, γ is an integer of 1 to 9 independently. γ' is an integer from 1 to 9, R a1 Each independently represents -Z-SiR 31 p1 R 32 q1 R 33 r1 R 34 s1 , Z each independently represents an oxygen atom or a divalent organic group, R 31 R a ', R a The meaning of R a same, R 32 Represents -X independently 5 -Q, X 5 Each independently represents a single bond or a divalent organic group, R 33 Each independently represents a hydroxyl group or a hydrolyzable group, R 34 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, In each -Z-SiR 31 p1 R 32 q1 R 33 r1 R 34 s1 middle, p1, q1, r1 and s1 are each independently an integer from 0 to 3, The sum of p1, q1, r1 and s1 is 3, R a1 In the formula, the maximum number of Si atoms connected in a straight chain via -Z- groups is 5. R b1 Indicates -X 5 -Q, R c1 Each independently represents a hydroxyl group or a hydrolyzable group, R d1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, In each -SiR a1 k1 R b1 l1 R c1 m1 R d1 n1 middle, k1, l1, m1 and n1 are each independently an integer of 0 to 3, The sum of k1, l1, m1 and n1 is 3, Rf, PFPE and Q have the same meanings as above. In formula (C1) and (C2), there is at least one -Q group; In formulas (D1) and (D2), X 6 Each independently represents a single bond or a di- to decavalent organic group, δ are each independently an integer of 1 to 9, δ' is an integer from 1 to 9, R a2 Represents -Z independently 2 -CR 41 p2 R 42 q2 R 43 r2 R 44 s2 , Z 2 each independently represents an oxygen atom or a divalent organic group, R 41 R a2 ', R a2 The meaning of ' is the same as R a2 same, R 42 Represents -X independently 7 -Q, X 7 Each independently represents a single bond or a divalent organic group, R 43 Each independently represents a hydroxyl group or a hydrolyzable group, R 44 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, In each -Z 2 -CR 41 p2 R 42 q2 R 43 r2 R 44 s2 middle, p2, q2, r2 and s2 are each independently an integer from 0 to 3, The sum of p2, q2, r2 and s2 is 3, R a2 In, via -Z 2 The maximum number of carbon atoms connected in a straight chain is 5. R b2 Represents -X independently 7 -Q, R c2 Each independently represents a hydroxyl group or a hydrolyzable group, R d2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, In each -CR a2 k2 R b2 l2 R c2 m2 R d2 n2 middle, k2, l2, m2 and n2 are each independently an integer of 0 to 3, The sum of k2, l2, m2 and n2 is 3, In-(CR a2 k2 R b2 12 R c2 m2 R d2 n2 ) δ There is at least one Q in Rf, PFPE and Q have the same meanings as above; In formulas (E1) and (E2), X 8 Each independently represents a single bond or a di- to decavalent organic group, ε is an integer of 1 to 9 independently. ε′ is an integer from 1 to 9, R 50 Represents -OR independently 51 、-SR 51 、-NR 51 2. -COOR 51 、-SO3R 51 or -(Si 52 2O) n3 -SiR 52 3. R 51 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, R 52 each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, n3 are each independently an integer from 0 to 100; Rf and PFPE have the same meanings as above.

8. The method for determining the molecular weight of a fluorinated polymer according to claim 6, wherein: The fluorocarbon-containing compound is a compound represented by formula (F1) or (F2), (R 61 -Rf′) φ′ -X 9 -Q φ …(F1) Q φ -X 9 -Rf′-X 9 -Q φ …(F2) In formulas (F1) and (F2), X 9 Each independently represents a single bond or a di- to decavalent organic group, φ are each independently an integer from 1 to 9, φ′ is an integer from 1 to 9, R 61 each independently represents a fluorine atom, -CHF2 or -CF3, Rf' each independently represents a perfluoroalkylene group having 1 to 30 carbon atoms, Q each independently represents -SiR 1 n R 2 3-n or -YA, R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, R 2 Each independently represents a hydroxyl group or a hydrolyzable group, n in each (-SiR 1 n R 2 3-n ) are independently an integer from 0 to 3, Y each independently represents a single bond, -O-, -CO-, -O-CO-, -CO-O-, -NR 3 -CO-, -CO-NR 3 - or a divalent hydrocarbon group having 1 to 22 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, A represents independently -CR 4 =CH2 or -C≡CH, R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, At least one Q is -SiR 1 n R 2 3－n In the case of, in formula (F1) or formula (F2), there is at least one R 2 .

9. The method for determining the molecular weight of a fluorinated polymer according to claim 6, wherein: The fluorinated vinyl polymer is a polymer having one or more of the units represented by formula (G1), (G2) or (G3), In formulas (G1), (G2), and (G3), R a3 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, or a fluorinated alkyl group having 1 to 22 carbon atoms, R b3 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, or a fluorinated alkyl group having 1 to 22 carbon atoms, R c3 represents an alkyl group having 1 to 22 carbon atoms, an alicyclic hydrocarbon group having 3 to 22 carbon atoms, an aromatic hydrocarbon group having 6 to 22 carbon atoms, or a group having 4 to 22 carbon atoms in which an alicyclic hydrocarbon group or an aromatic hydrocarbon group is bonded to an alkylene group, wherein -CH2- contained in these groups may be replaced by an oxygen atom, and hydrogen atoms contained in these groups may be replaced by fluorine atoms, Y 2 Represents -O-, -CO-, -O-CO-, -CO-O-, -NR 6 -CO- or -CO-NR 6 - R 6 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, Y 3 represents a single bond or an oxygen atom, R d3 represents an alkyl group having 1 to 22 carbon atoms, wherein -CH2- contained in the alkyl group may be replaced by an oxygen atom, and the hydrogen atom contained in the alkyl group may be replaced by a fluorine atom, R e3 represents an alkylene group having 3 to 22 carbon atoms, wherein -CH2- contained in the alkylene group may be replaced by an oxygen atom, and wherein a hydrogen atom contained in the alkylene group may be replaced by a fluorine atom, X 10 It represents a single bond, an alkylene group having 1 to 22 carbon atoms, or a fluorinated alkylene group having 1 to 22 carbon atoms.

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