Method for producing olefin-modified fluorine-containing compound, and composition containing said compound

Abstract

This method for producing an olefin-modified fluorine-containing compound involves reacting, in the presence of a radical initiator, a compound represented by formula (1A) or a compound represented by formula (1B), and a compound represented by formula (2). In the formulae, the symbols are as described in the specification. R1A-CFY1-X1 ...(1A) X1-CFY1-R1B-CFY1-X1 ...(1B) R2 3Si-(CH2)n1-CR4=CR5R6 ...(2)

Description

Method for producing olefin-modified fluorine-containing compound and composition containing said compound

[0001] The present disclosure relates to methods for producing olefin-modified fluorine-containing compounds and compositions containing the compounds.

[0002] It is known that fluorine-containing compounds having fluorine atoms in the molecule can contribute to the formation of a layer having physical properties such as water repellency and oil repellency (hereinafter, sometimes referred to as a "surface treatment layer") (for example, Patent Document 1). Such fluorine-containing compounds are used in many applications. Various studies have been conducted on the synthesis of fluorine-containing compounds.

[0003] Japanese Patent Application Laid-Open No. 2021-80448

[0004] An object of the present disclosure is to provide a new method for producing a fluorine-containing compound having an olefin structure (hereinafter, sometimes referred to as an "olefin-modified fluorine-containing compound"), and a composition containing the compound.

[0005] The present disclosure provides the following [1] to

[11] . [1] A method for producing an olefin-modified fluorine-containing compound, which comprises reacting a compound represented by formula (1A) or a compound represented by formula (1B) with a compound represented by formula (2) in the presence of a radical initiator. １Ａ -CFY １ -X １ ...(1A) [wherein: R １Ａ is a monovalent organic group; Y １ is a hydrogen atom or a halogen atom; X １ is a halogen atom other than a fluorine atom.] X １ -CFY １ -R １Ｂ -CFY １ -X １ ...(1B) [In the formula: R １Ｂ is a divalent organic group; Y １ are each independently a hydrogen atom or a halogen atom; １ are each independently a halogen atom other than a fluorine atom. ２ ３Si-(CH ２ ) ｎ１ -CR ４ =CR ５ R ６ ...(2) [In the formula: R ２ are each independently R ２１ ３ is a monovalent group containing Si—; R ２１ is independently in each occurrence a hydrogen atom or C １－１２ is an alkyl group; １－１２ The alkyl group may be substituted with a halogen atom; n1 is an integer of 1 to 10; R ４ , R ５ and R ６ are each independently a hydrogen atom or C １－１０ is an alkyl group.] [2] The Y １ [3] The method according to [1], wherein X is a fluorine atom. １ [4] The manufacturing method according to [1] or [2], wherein R is a bromine atom or an iodine atom. １Ａ is Rf １ -R Ｆ１ -(O) ｎ２１ -; Rf １ is a C optionally substituted with one or more fluorine atoms １－１６ is an alkyl group; R Ｆ１ is represented by the formula: -(OC ６ F １２ ) ａ１ - (OC ５ F １０ ) ｂ１ - (OC ４ F ８ ) ｃ１ - (OC ３ R Ｆａ ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１a1, b1, c1, d1, e1 and f1 each independently represent an integer of 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is 1 or more, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1 or f1 is arbitrary in the formula; R Ｆａ is independently a hydrogen atom, a fluorine atom, or a chlorine atom in each occurrence; and n21 is 0 or 1. [5] The method for producing a compound according to any one of [1] to [3], １Ｂ is -(Rf ２ ) ｎ２３ -R Ｆ１ -(O) ｎ２２ -; Rf ２ is a divalent organic group; R Ｆ１ is represented by the formula: -(OC ６ F １２ ) ａ１ - (OC ５ F １０ ) ｂ１ - (OC ４ F ８ ) ｃ１ - (OC ３ R Ｆａ ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ a1, b1, c1, d1, e1 and f1 each independently represent an integer of 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is 1 or more, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1 or f1 is arbitrary in the formula; R Ｆａ is independently a hydrogen atom, a fluorine atom, or a chlorine atom in each occurrence; n22 is 0 or 1; and n23 is 0 or 1. [6] The method for producing a compound according to any one of [1] to [4], wherein R ２ are each independently R ２１ ３ Si—; ２１each independently represents a C optionally substituted by a halogen atom; １－４ is an alkyl group; １－４ The method according to any one of [1] to [5], wherein the alkyl group is linear or branched. [7] The R ２ are each independently (CH ３ ) ３ [8] The method according to any one of [1] to [7], wherein a purification treatment is carried out after the reaction of a compound represented by formula (1A) or a compound represented by formula (1B) with a compound represented by formula (2). [9] The method according to any one of [1] to [8], wherein the olefin-modified fluorine-containing compound is a compound represented by formula (3A) or a compound represented by formula (3B). R １Ａ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H...(3A) [In the formula: R １Ａ , Y １ , n1, R ４ , R ５ and R ６ are the same as those described in claim 1.] H(CH ２ ) ｎ１－１ -CH=CR ４ -CR ５ R ６ -CFY １ -R １Ｂ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H...(3B) [In the formula: R １Ｂ , Y １ , n1, R ４ , R ５ and R ６are the same as those described in claim 1.]

[10] A composition comprising at least one of an olefin-modified fluorine-containing compound represented by formula (3A) and an olefin-modified fluorine-containing compound represented by formula (3B), and tin in an amount of 1 ppm or less relative to the total amount of the olefin-modified fluorine-containing compound represented by formula (3A) and the olefin-modified fluorine-containing compound represented by formula (3B). R １Ａ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H...(3A) [In the formula: R １Ａ is a monovalent organic group; Y １ is a hydrogen atom or a halogen atom; n1 is an integer of 1 to 10; R ４ , R ５ and R ６ is independently in each occurrence a hydrogen atom or C １－１０ is an alkyl group. ２ ) ｎ１－１ -CH=CR ４ -CR ５ R ６ -CFY １ -R １Ｂ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H...(3B) [In the formula: R １Ｂ is a divalent organic group; Y １ are each independently a hydrogen atom or a halogen atom; n1 is each independently an integer of 1 to 10; R ４ , R ５ and R ６ is independently in each occurrence a hydrogen atom or C １－１０

[11] The composition according to

[10] , wherein the tin is 1 ppb or less based on the total amount of the olefin-modified fluorine-containing compound represented by formula (3A) and the olefin-modified fluorine-containing compound represented by formula (3B).

[0006] According to the present disclosure, a new method for producing an olefin-modified fluorine-containing compound and a composition containing the compound can be provided.

[0007] As used herein, the term "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. As used herein, the term "divalent organic group" is not particularly limited, but examples include divalent groups in which one hydrogen atom has been further removed from a hydrocarbon group.

[0008] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, in which one hydrogen atom has been removed from the molecule. Such hydrocarbon groups are not particularly limited, but include hydrocarbon groups having 1 to 20 carbon atoms, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups, which may be substituted with one or more substituents. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures.

[0009] As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but examples thereof include a halogen atom; a C １－６ Alkyl group, C ２－６ Alkenyl group, C ２－６ Alkynyl group, C ３－１０ Cycloalkyl group, C ３－１０ Unsaturated cycloalkyl groups, 5- to 10-membered heterocyclyl groups, 5- to 10-membered unsaturated heterocyclyl groups, C ６－１０ The alkyl group may include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0010] In this specification, alkyl groups and phenyl groups may be unsubstituted or substituted unless otherwise specified. Substituents for such groups are not particularly limited, but include, for example, halogen atoms, C １－６ Alkyl group, C ２－６ Alkenyl group and C ２－６ alkynyl groups.

[0011] Hereinafter, a method for producing an olefin-modified fluorine-containing compound, which is one embodiment of the present disclosure, will be described.

[0012] (Production Method) The production method of the olefin-modified fluorine-containing compound of the present disclosure includes the following step (I): [Step (I)] A compound represented by formula (1A) or a compound represented by formula (1B): R １Ａ -CFY １ -X １ ... (1A) X １ -CFY １ -R １Ｂ -CFY １ -X １ ...(1B) and a compound represented by formula (2): R ２ ３ Si-(CH ２ ) ｎ１ -CR ４ =CR ５ R ６ ...(2) in the presence of a radical initiator.

[0013] By the above steps, an olefin-modified fluorine-containing compound represented by formula (3A) or a composition containing an olefin-modified fluorine-containing compound represented by formula (3B) can be obtained. １Ａ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H...(3A) H(CH ２ ) ｎ１－１ -CH=CR ４ -CR ５ R ６ -CFY １ -R１Ｂ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H (3B) Hereinafter, the olefin-modified fluorine-containing compound refers to an olefin-modified fluorine-containing compound represented by formula (3A) or an olefin-modified fluorine-containing compound represented by formula (3B).

[0014] By using the above production method, the selectivity of the olefin-modified fluorine-containing compound among the compounds produced is improved. ２ ３ Si- and X １ By reaction with -CFY １ In the above production method, -CFY radicals are generated. １ It is believed that the rate of radical generation can be appropriately controlled, and as a result, the selectivity of the olefin-modified fluorine-containing compound to be produced is thought to be improved.

[0015] Each formula will be described below.

[0016] (Formula (1A)) R １Ａ -CFY １ -X １ ... (1A)

[0017] X １ is a halogen atom other than a fluorine atom, preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a bromine atom or an iodine atom. １ is a bromine atom. １ is an iodine atom.

[0018] Y １ is a hydrogen atom or a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom.

[0019] R １Ａ is a monovalent organic group.

[0020] In one embodiment, R １Ａ is Rf １-R Ｆ１ -(O) ｎ２１ It is expressed as -.

[0021] Rf １ is a C optionally substituted with one or more fluorine atoms １－１６ It is an alkyl group. １－１６ The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－６ Alkyl groups, especially straight or branched C １－３ alkyl group, more preferably a straight-chain C １－６ Alkyl groups, especially C １－３ It is an alkyl group.

[0022] The above Rf １ is preferably a C substituted by one or more fluorine atoms １－１６ alkyl group, more preferably C １－１６ It is a perfluoroalkyl group. １－１６ The perfluoroalkyl group may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－６ Perfluoroalkyl groups, especially straight-chain or branched-chain C １－３ perfluoroalkyl groups, more preferably linear C １－６ Perfluoroalkyl groups, especially C １－３ It is a perfluoroalkyl group.

[0023] In one embodiment, Rf １ is a C optionally substituted with one or more fluorine atoms １－６ It is an alkyl group. １－６ The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－３ In one embodiment, the C １－６ The alkyl group is preferably a straight chain C １－６ Alkyl groups, especially C １－３ Rf is an alkyl group. １ In one aspect, ３ -; in another embodiment, CF ３ CF ２ -; and in yet another embodiment, CF３ CF ２ CF ２ - is.

[0024] In the above embodiment, Rf １ is preferably a C substituted by one or more fluorine atoms １－６ alkyl group, more preferably C １－６ In this embodiment, the C １－６ The perfluoroalkyl group may be linear or branched, and is preferably a linear C １－６ Perfluoroalkyl groups, especially C １－３ It is a perfluoroalkyl group.

[0025] R Ｆ１ is represented by the formula: -(OC ｊ R ｃ ２ｊ ) ｊ１ - (OC ｈ R ｃ ２ｈ－２ ) ｈ１ - is a group represented by the formula: -OC ｊ R ｃ ２ｊ Each - is independently linear or branched; ｈ R ｃ ２ｈ－２ Each - is independently a structure containing a ring structure. ｃ are each independently a hydrogen atom, a chlorine atom, or a fluorine atom, provided that R Ｆ１ At least one R ｃ is a fluorine atom. Each j is independently an integer of 1 to 6, each h is independently an integer of 1 to 7, j1 is an integer of 0 or more, h1 is an integer of 0 or more, and the sum of j1 and h1 is 1 or more. The repeating units enclosed in parentheses with j1 or h1 may be present in any order in the formula.

[0026] In one embodiment, R Ｆ１ is represented by the formula: -(OC ６ F １２ ) ａ１ - (OC ５ F １０ ) ｂ１- (OC ４ F ８ ) ｃ１ - (OC ３ R Ｆａ ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ a1, b1, c1, d1, e1 and f1 are each independently an integer of 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is 1 or more, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1 or f1 is arbitrary in the formula. Ｆ１ By having the above, it is possible to form a surface treatment layer having water repellency, oil repellency, chemical resistance, friction durability, etc. Ｆ１ The left side is Rf １ , and the right side is - (O) ｎ２１ - and bond to each other.

[0027] R Ｆａ is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom.

[0028] R Ｆａ is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0029] Preferably, a1, b1, c1, d1, e1 and f1 may each independently be an integer of 0 to 100.

[0030] The sum of a1, b1, c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a1, b1, c1, d1, e1, and f1 is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0031] R Ｆ１ In the formula (I), these repeating units may be linear or branched, or may contain a ring structure.

[0032] Examples of the linear or branched repeating unit include the following structures: ６ F １２ )- is -(OCF ２ CF ２ CF ２ CF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ CF ２ CF ２ CF ２ ) -, -(OCF ２ CF (CF ３ )CF ２ CF ２ CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )CF ２ CF ２ ) -, -(OCF ２ CF ２ CF ２ CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF ２ CF ２ CF (CF ３ ))-, etc. ５ F １０ )- is -(OCF ２ CF ２ CF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ CF ２ CF ２ ) -, -(OCF ２ CF (CF ３ )CF ２ CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF２ CF (CF ３ ))-, etc. ４ F ８ )- is -(OCF ２ CF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ CF ２ ) -, -(OCF ２ CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )) -, -(OC(CF ３ ) ２ CF ２ ) -, -(OCF ２ C (CF ３ ) ２ )-,-(OCF(CF ３ )CF(CF ３ ))-,-(OCF(C ２ F ５ )CF ２ )-and-(OCF ２ CF (C ２ F ５ ))-. ３ F ６ ) - (i.e., in the above formula, R Ｆａ is a fluorine atom) is -(OCF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ )-and-(OCF ２ CF (CF ３ ))-. ２ F ４ )- is -(OCF ２ CF ２ )-and-(OCF(CF ３ ))-.

[0033] The ring structure may be a three-, four-, five-, or six-membered ring as shown below. [In the formula, * indicates the bonding position.]

[0034] In one embodiment, the repeating unit is linear.

[0035] In one embodiment, the repeating unit comprises a branched chain.

[0036] In one embodiment, the repeat unit comprises a ring structure.

[0037] In one embodiment, R Ｆ１ is independently a group represented by any one of the following formulas (f1) to (f6) in each occurrence: —(OC ３ F ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ - (f1) [wherein d1 is an integer of 1 to 200, and e1 is 0 or 1, preferably 1.]; - (OC ４ F ８ ) ｃ１ - (OC ３ F ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - (f2) [wherein c1 and d1 each independently represent an integer of 0 or more and 30 or less, e1 and f1 each independently represent an integer of 1 or more and 200 or less, the sum of c1, d1, e1, and f1 is 2 or more, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript c1, d1, e1, or f1 is arbitrary in the formula.]; - (R ７１ -R ７２ ) ｇ１ - (f3) [wherein, R ７１ is OCF ２ or O.C. ２ F ４ and R ７２ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２or a combination of two or three groups independently selected from these groups, and g1 is an integer of 2 to 100. ]; -(R ７１ -R ７２ ) ｇ１ -R ｒ - (R ７２’ -R ７１’ ) ｇ１’ - (f4) [wherein, R ７１ is OCF ２ or O.C. ２ F ４ and R ７２ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups; ７１’ is OCF ２ or O.C. ２ F ４ and R ７２’ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups, g1 is an integer from 2 to 100, g1' is an integer from 2 to 100, R ｒ teeth, (wherein * indicates the bond position). ]; -(OC ６ F １２ ) ａ１ - (OC ５ F １０ ) ｂ１ - (OC ４ F ８ ) ｃ１ - (OC３ F ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - (f5) [In the formula, e1 is an integer of 1 or more and 200 or less, a1, b1, c1, d1 and f1 are each independently an integer of 0 or more and 200 or less, the sum of a1, b1, c1, d1, e1 and f1 is at least 1, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1 or f1 is arbitrary in the formula.] - (OC ６ F １２ ) ａ１ - (OC ５ F １０ ) ｂ１ - (OC ４ F ８ ) ｃ１ - (OC ３ F ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - (f6) [In the formula, f1 is an integer of 1 or more and 200 or less, a1, b1, c1, d1, and e1 are each independently an integer of 0 or more and 200 or less, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula.]

[0038] In the above formula (f1), d1 is preferably an integer of 5 to 200, more preferably 10 to 100, and even more preferably 15 to 50, for example, an integer of 25 to 35. ３ F ６ ) is preferably (OCF ２ CF ２ CF ２ ) or (OCF(CF ３ )CF ２ ), and more preferably, a group represented by (OCF ２ CF ２ CF ２(OC) in the above formula (f1). ２ F ４ ) is preferably (OCF ２ CF ２ ) or (OCF(CF ３ )), and more preferably, a group represented by (OCF ２ CF ２ ) is a group represented by the formula:

[0039] In the formula (f2), e1 and f1 are each independently an integer of preferably 5 or more and 200 or less, more preferably 10 to 200. The sum of c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the formula (f2) is preferably -(OCF ２ CF ２ CF ２ CF ２ ) ｃ１ -(OCF ２ CF ２ CF ２ ) ｄ１ -(OCF ２ CF ２ ) ｅ１ -(OCF ２ ) ｆ１ In another embodiment, formula (f2) is a group represented by -(OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ It may be a group represented by -.

[0040] In the above formula (f3), R ７１ is preferably OC ２ F ４ In the above (f3), R ７２ is preferably OC ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８ or a combination of two or three groups independently selected from these groups, more preferably OC ３ F６ and O.C. ４ F ８ is a group selected from ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８ The combination of two or three groups independently selected from the group consisting of, but not limited to, —OC ２ F ４ O.C. ３ F ６ -, -OC ２ F ４ O.C. ４ F ８ -, -OC ３ F ６ O.C. ２ F ４ -, -OC ３ F ６ O.C. ３ F ６ -, -OC ３ F ６ O.C. ４ F ８ -, -OC ４ F ８ O.C. ４ F ８ -, -OC ４ F ８ O.C. ３ F ６ -, -OC ４ F ８ O.C. ２ F ４ -, -OC ２ F ４ O.C. ２ F ４ O.C. ３ F ６ -, -OC ２ F ４ O.C. ２ F ４ O.C. ４ F ８ -, -OC ２ F ４ O.C. ３ F ６ O.C. ２ F ４ -, -OC ２ F ４ O.C. ３ F ６O.C. ３ F ６ -, -OC ２ F ４ O.C. ４ F ８ O.C. ２ F ４ -, -OC ３ F ６ O.C. ２ F ４ O.C. ２ F ４ -, -OC ３ F ６ O.C. ２ F ４ O.C. ３ F ６ -, -OC ３ F ６ O.C. ３ F ６ O.C. ２ F ４ -, and -OC ４ F ８ O.C. ２ F ４ O.C. ２ F ４ In the formula (f3), g1 is preferably an integer of 3 or more, more preferably an integer of 5 or more. The g1 is preferably an integer of 50 or less. In the formula (f3), OC ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ may be either a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC ２ F ４ -OC ３ F ６ ) ｇ１ -or- (OC ２ F ４ -OC ４ F ８ ) ｇ１ - is.

[0041] In the above formula (f4), R ７１ , R ７２and g1 have the same meanings as those described in the above formula (f3) and have the same embodiments. ７１’ , R ７２’ and g1′ are R ７１ , R ７２ and g1 and have the same meaning and aspects. ｒ is preferably [wherein * indicates the bonding position], and more preferably [wherein * indicates the bonding position.]

[0042] In the above formula (f5), e1 is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less. The sum of a1, b1, c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0043] In the above formula (f5), R Ｆ１ The repeating unit at the terminal portion is -(OCF ２ CF ２ OCF ２ CF ２ CF ２ )- may also be used.

[0044] In the above formula (f6), f1 is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less. The sum of a1, b1, c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0045] In one embodiment, the R Ｆ１ is a group represented by the above formula (f1).

[0046] In one embodiment, the R Ｆ１ is a group represented by the above formula (f2).

[0047] In one embodiment, the R Ｆ１ is a group represented by the above formula (f3) or (f4).

[0048] In one embodiment, the R Ｆ１ is a group represented by the above formula (f3).

[0049] In one embodiment, the R Ｆ１ is a group represented by the above formula (f4).

[0050] In one embodiment, the R Ｆ１ is a group represented by the above formula (f5).

[0051] In one embodiment, the R Ｆ１ is a group represented by the above formula (f6).

[0052] In one embodiment, the R Ｆ１ is a group represented by the above formula (f1), (f2), (f5) or (f6).

[0053] In one embodiment, the R Ｆ１ is a group represented by the above formula (f1), (f2), or (f6).

[0054] The above R Ｆ１ In the formula, the ratio of e1 to f1 (hereinafter referred to as the "e / f ratio") is, for example, 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, more preferably 0.2 to 2, even more preferably 0.2 or more and 1.5 or less, still more preferably 0.2 or more and less than 0.9, and particularly preferably 0.2 or more and 0.85 or less. When the e / f ratio is within the above range, the stability of the obtained fluorine-containing compound is improved. Here, f1 is an integer of 1 or more.

[0055] In one embodiment, R Ｆ１ In the formula, the e / f ratio is preferably 1.0 or more, for example, 1.1 or more, or may be 1.3 or more. Ｆ１ In the formula, the e / f ratio is preferably 10.0 or less, 9.0 or less, more preferably 5.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less. Ｆ１ In the formula, the e / f ratio is, for example, 1.0 to 10.0, specifically 1.0 to 5.0, more specifically 1.0 to 2.0, and even more specifically 1.0 to 1.5.

[0056] In one embodiment, R Ｆ１ In the formula, the e / f ratio may be in the range of 1.0 to 1.2.

[0057] In one correspondence, RＦ１ In the above formula, the e / f ratio may be less than 0.9, for example, 0.8 or less, or 0.7 or less. Ｆ１ In the formula, the e / f ratio is preferably 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more. Ｆ１ In the formula, the e / f ratio is, for example, 0.2 or more and less than 0.9, specifically 0.4 or more and 0.8 or less, and more specifically 0.5 or more and 0.7 or less.

[0058] In one embodiment, d1 is preferably an integer of 1 or greater, more preferably 3 or greater, and even more preferably 6 or greater, and may be 200 or less, 120 or less, 60 or less, or 54 or less. In this embodiment, d1 may be 1 to 200, 3 to 120, 3 to 60, or 6 to 60.

[0059] In one embodiment, R Ｆ１ is -(OC ３ F ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ - (f1) [wherein d1 is an integer of 3 to 60, preferably an integer of 6 to 54; e1 is 1; OC ３ F ６ and O.C. ２ F ４ is a linear group.

[0060] In one embodiment, R Ｆ１ is -(OC ３ F ６ ) ｄ１ - (OC ２ F ４ ) ｅ１ - (f1) [wherein d1 is an integer of 3 to 120, preferably an integer of 6 to 60; e1 is 1; each OC ３ F ６ and O.C. ２ F ４has a branched chain.] For example, in formula (f1), the repeating unit is -OCF(CF ３ )CF ２ It is expressed as -.

[0061] The above R Ｆ１ The number average molecular weight of the portion is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. Ｆ１ The number average molecular weight of １９ The value is measured by F-NMR.

[0062] In another embodiment, R Ｆ１ The number average molecular weight of the moiety may be from 500 to 30,000, preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from 2,000 to 10,000, for example from 3,000 to 6,000.

[0063] In another embodiment, R Ｆ１ The number average molecular weight of the moiety can be from 4,000 to 30,000, preferably from 5,000 to 10,000, and more preferably from 6,000 to 10,000.

[0064] n21 is 0 or 1. In one embodiment, n21 is 0. In one embodiment, n21 is 1.

[0065] (Formula (1B)) １ -CFY １ -R １Ｂ -CFY １ -X １ ...(1B)

[0066] X １ are each independently a halogen atom other than a fluorine atom, preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a bromine atom or an iodine atom. １ is a bromine atom. １ is an iodine atom.

[0067] Y １are each independently a hydrogen atom or a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom.

[0068] R １Ｂ is a divalent organic group.

[0069] In one embodiment, R １Ｂ is -(Rf ２ ) ｎ２３ -R Ｆ１ -(O) ｎ２２ It is expressed as -.

[0070] R Ｆ１ is as described above.

[0071] Rf ２ is a divalent organic group.

[0072] The above Rf ２ is preferably a C optionally substituted by one or more fluorine atoms. １－６ It is an alkylene group.

[0073] The C optionally substituted with one or more fluorine atoms １－６ "C" in the alkylene group １－６ The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－３ alkylene groups, more preferably linear C １－３ It is an alkylene group.

[0074] The above Rf ２ is preferably a C substituted by one or more fluorine atoms １－６ is an alkylene group, more preferably C １－６ A perfluoroalkylene group, more preferably C １－３ It is a perfluoroalkylene group.

[0075] Above C １－６ The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－３ A perfluoroalkylene group, more preferably a linear C １－３Perfluoroalkylene groups, specifically —CF ２ -, -CF ２ CF ２ - or -CF ２ CF ２ CF ２ - is.

[0076] n22 is 0 or 1. In one embodiment, n22 is 0. In one embodiment, n22 is 1.

[0077] n23 is 0 or 1. In one embodiment, n23 is 0. In one embodiment, n23 is 1.

[0078] (Formula (2)) R ２ ３ Si-(CH ２ ) ｎ１ -CR ４ =CR ５ R ６ ...(2)

[0079] R ２ are each independently R ２１ ３ It is a monovalent group containing Si—.

[0080] In one embodiment, the R ２ is R ２１ ３ It is a group having Si— and a divalent organic group.

[0081] The above R ２ are preferably each independently R ２１ ３ It is Si-.

[0082] R ２１ are each independently a hydrogen atom or C １－１２ It is an alkyl group. １－１２ The alkyl group may be substituted with a halogen atom. １－１２ The alkyl groups are each independently linear or branched.

[0083] The above R ２１ are preferably each independently a C optionally substituted by a halogen atom. １－４ It is an alkyl group.１－４ The alkyl groups are each independently linear or branched. １－４ The alkyl group is linear. １－４ The alkyl group is branched.

[0084] The above R ２１ More preferably, each independently represents C １－４ It is an alkyl group.

[0085] The above R ２１ is more preferably CH ３ In this case, R ２ is (CH ３ ) ３ It is represented by Si-.

[0086] n1 is an integer of 1 to 10, preferably an integer of 1 to 3.

[0087] In one embodiment, n1 is 1. In this case, the terminal of the olefin-modified fluorine-containing compound represented by formula (3A) or the olefin-modified fluorine-containing compound represented by formula (3B) formed is -CR ４ =CH ２ In this production method, the olefin-modified fluorine-containing compound represented by formula (3A) or the olefin-modified fluorine-containing compound represented by formula (3B) having the above-mentioned terminal group is particularly well formed. ４ =CH ２ This is thought to be because there is little steric hindrance and the reaction proceeds smoothly. When surface treatment is carried out using a surface treatment agent containing the above compound, the adhesion to the substrate can be particularly good.

[0088] R ４ , R ５ , and R ６ is independently in each occurrence a hydrogen atom or C １－１０ It is an alkyl group.

[0089] The above R ４ is preferably a hydrogen atom or C １－６ is an alkyl group, more preferably a hydrogen atom or CH ３ In one embodiment, R ４is a hydrogen atom. ４ is CH ３ It is the base.

[0090] The above R ５ is preferably a hydrogen atom or C １－６ is an alkyl group, more preferably a hydrogen atom or CH ３ It is a group, preferably a hydrogen atom.

[0091] The above R ６ is preferably a hydrogen atom or C １－６ is an alkyl group, more preferably a hydrogen atom or CH ３ It is a group, preferably a hydrogen atom.

[0092] In one embodiment, R ５ , or R ６ Either one of them is CH ３ group, and the other is a hydrogen atom.

[0093] In one embodiment, R ５ , and R ６ is a hydrogen atom. In this case, the reactivity of the compound represented by formula (1A) or the compound represented by formula (1B) with the compound represented by formula (2) can be particularly good. The mixing ratio of the compound represented by formula (1A) and the compound represented by formula (1B) is not particularly limited, and they can be mixed at any ratio. The mixing ratio of the compound represented by formula (1A) and the compound represented by formula (1B) can be adjusted according to the content of the compound represented by formula (2).

[0094] In one embodiment, a compound represented by formula (1A) can be used.

[0095] In one embodiment, a compound represented by formula (1B) can be used.

[0096] In one embodiment, the compound represented by formula (1A) and the compound represented by formula (2) are mixed in a molar ratio ranging from 1:1 to 1:10. The compound represented by formula (1A) and the compound represented by formula (2) are preferably mixed in a molar ratio ranging from 1:1 to 1:8, more preferably from 1:1 to 1:6, and even more preferably from 1:2 to 1:6. By mixing at such a molar ratio, the reaction can proceed particularly well.

[0097] In one embodiment, the compound represented by formula (1B) and the compound represented by formula (2) are mixed in a molar ratio ranging from 1:2 to 1:20. The compound represented by formula (1B) and the compound represented by formula (2) are preferably mixed in a molar ratio ranging from 1:2 to 1:16, more preferably from 1:2 to 1:12, and even more preferably from 1:4 to 1:12. By mixing at such a molar ratio, the reaction can proceed particularly well.

[0098] (Formula (3A)) R １Ａ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H... (3A)

[0099] R １Ａ , Y １ , n1, R ４ , R ５ , and R ６ is as described in formula (1A) or formula (2).

[0100] (Formula (3B)) H(CH ２ ) ｎ１－１ -CH=CR ４ -CR ５ R ６ -CFY １ -R １Ｂ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H... (3B)

[0101] R １Ｂ , Y １ , n1, R ４ , R ５ , and R ６ is as described in formula (1B) or formula (2).

[0102] As described above, the compound represented by formula (3A) or the compound represented by formula (3B) (i.e., the olefin-modified fluorine-containing compound) has an olefin. When the olefin-modified fluorine-containing compound is contained in a surface treatment agent, the olefin can provide good adhesion to a substrate. The olefin-modified fluorine-containing compound can also be effectively used as a raw material for synthesizing other compounds.

[0103] (Radical Initiator) As the radical initiator, any radical initiator that can promote the reaction in step (I) can be used, and examples thereof include azo compounds, dihalogens, and organic peroxides.

[0104] Examples of azo compounds include azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), 1-[(1-cyano-1-methylethyl)azo]formamide, 4,4'-azobis(4-cyanovaleric acid), dimethyl-1,1'-azobis(1-cyclohexanecarboxylate), 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), etc. Azo compounds are preferably used because of their good solubility.

[0105] The dihalogen may include chlorine molecules.

[0106] Examples of organic peroxides include di-tert-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, di-(3-methylbenzoyl) peroxide, benzoyl(3-methylbenzoyl) peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)-2-methylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, and 2,2-di(t-butylperoxy)butane. , t-butylcumyl peroxide, di-t-hexyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, and the like.

[0107] In one embodiment, the compound represented by formula (1A) and the radical initiator are mixed in a molar ratio of preferably 1:0.005 to 1:0.2, more preferably 1:0.01 to 1:0.1.

[0108] In one embodiment, the compound represented by formula (1B) and the radical initiator are mixed in a molar ratio of preferably 1:0.01 to 1:0.4, more preferably 1:0.02 to 1:0.2.

[0109] (Solvent) The reaction in step (I) may be carried out in a solvent.

[0110] The solvent is preferably one that can dissolve the compound represented by formula (1A) or the compound represented by formula (1B) and the compound represented by formula (2). The solvent may be used alone or in combination of two or more.

[0111] The solvent is, for example, a fluorine-based solvent or a non-fluorine-based solvent.

[0112] A fluorine-based solvent is a solvent containing one or more fluorine atoms. Examples of fluorine-based solvents include compounds in which at least one hydrogen atom of a hydrocarbon is substituted with a fluorine atom, such as hydrofluorocarbons, hydrochlorofluorocarbons, and perfluorocarbons; hydrofluoroethers, etc. Here, the term "hydrocarbon" refers to a compound containing only carbon atoms and hydrogen atoms.

[0113] Examples of hydrofluorocarbons include bis(trifluoromethyl)benzene, specifically 1,3-bis(trifluoromethyl)benzene (m-XHF), 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, C ６ F １３ CH ２ CH ３ (for example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Zeon Corporation), and the like.

[0114] Examples of hydrochlorofluorocarbons include HCFC-225 (for example, Asahiklin AK-225 manufactured by AGC Inc.) and HFO-1233zd(Z) (for example, Cerefin 1233Z manufactured by Central Glass Co., Ltd.).

[0115] Examples of perfluorocarbons include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and perfluorobenzene.

[0116] Examples of hydrofluoroethers include perfluoropropyl methyl ether (C ３ F ７ OCH ３ ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C ４ F ９ OCH ３ ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C４ F ９ O.C. ２ H ５ ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C ２ F ５ CF (OCH ３ ) C ３ F ７ ) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) and other alkyl perfluoroalkyl ethers (the perfluoroalkyl and alkyl groups may be linear or branched); CF ３ CH ２ OCF ２ CHF ２ (For example, Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.)

[0117] Of the fluorine-based solvents listed above, m-XHF, HFE7100, HFE7200, HFE7300, AC-6000, perfluorohexane, and perfluorobenzene are preferred.

[0118] Examples of non-fluorine-based solvents include S atom-containing solvents, amide-based solvents, ether-based solvents, halogen-containing solvents, and hydrocarbon-based solvents.

[0119] Examples of S atom-containing solvents include dimethyl sulfoxide, sulfolane, dimethyl sulfide, and carbon disulfide. Examples of amide solvents include N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, and hexamethylphosphoric triamide. Examples of ether solvents include diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, ethylene glycol, monoglyme, and diglyme. Examples of halogen-containing solvents include dichloromethane and chloroform. Examples of hydrocarbon solvents include pentane, hexane, heptane, benzene, and toluene.

[0120] The solvent is preferably at least one selected from the group consisting of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,3-bis(trifluoromethyl)benzene, diglyme, and dimethyl sulfoxide, and more preferably at least one selected from the group consisting of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,3-bis(trifluoromethyl)benzene, and dimethyl sulfoxide. By using such a solvent, the compound represented by formula (1A) or the compound represented by formula (1B) and the compound represented by formula (2) can be dissolved. Furthermore, by using such a solvent, the reactivity of the compound represented by formula (1A) or the compound represented by formula (1B) with the compound represented by formula (2) can be improved. Furthermore, by using such a solvent, the water content in the composition can be reduced.

[0121] Although not particularly limited, the solvent may be contained in an amount of, for example, 1 to 200 mass %, more specifically, 50 to 150 mass %, based on the total amount of the compound represented by formula (1A), the compound represented by formula (1B), and the compound represented by formula (2). When only one of the compound represented by formula (1A) and the compound represented by formula (1B) is present, the mass of the compound present is used as the mass of the compound represented by formula (1A) or the compound represented by formula (1B).

[0122] The reaction temperature in step (I) is not particularly limited, and may be, for example, 0 to 200°C, 10 to 180°C, or 20 to 160°C.

[0123] In the method for producing an olefin-modified fluorine-containing compound of the present disclosure, a purification treatment may be carried out after step (I).

[0124] The purification treatment may include, for example, a separation treatment.

[0125] The separation treatment facilitates extraction of a composition containing the target compound (i.e., at least one selected from the group consisting of the compound represented by formula (3A) and the compound represented by formula (3B). The separation treatment includes, for example, a step of adding at least one of water and an organic solvent to the composition obtained in step (I), and a step of separating the obtained water or organic solvent layer.

[0126] The organic solvents may be used alone or in combination of two or more thereof, such as acetone, pentane, hexane, heptane, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, perfluorohexane, m-XHF, HFE7100, HFE7200, HFE7300, AC-6000, perfluorobenzene, and HCFC-225.

[0127] The amount of the organic solvent is not particularly limited. In one embodiment, the organic solvent is added in a volume ratio of 1.0 to 2.0 with respect to the solvent used in step (I).

[0128] In one embodiment, the organic solvent used has a low water content. By using such an organic solvent, the water content of the composition obtained in step (I) is reduced. The water content of the organic solvent is preferably 5,000 ppm or less, more preferably 1,000 ppm or less, even more preferably 500 ppm or less, and particularly preferably 100 ppm or less, by mass.

[0129] In one embodiment, after the liquid separation treatment, a dehydrating agent may be added to the layer containing the organic solvent to perform dehydration treatment. The layer containing the organic solvent contains an olefin-modified fluorine compound. The dehydrating agent is not particularly limited. In one embodiment, the dehydrating agent may be molecular sieve, aluminum oxide, calcium chloride, calcium oxide, calcium sulfate, magnesium oxide, magnesium perchlorate, magnesium sulfate, calcium carbonate, silica gel, sodium sulfate, or a mixture thereof.

[0130] Before or after the separation treatment, volatile components may be distilled off.

[0131] (Composition) In one embodiment, the compound represented by formula (3A) is contained in the composition at a molar ratio of 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 0.95 or more, relative to the solid content of the composition. For example, the compound represented by formula (3A) may be contained at a molar ratio of 0.98 or more, 0.99 or more, or even substantially 1, relative to the solid content of the composition.

[0132] In one embodiment, the compound represented by formula (3B) is contained in the composition at a molar ratio of 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 0.95 or more, relative to the solid content of the composition. For example, the compound represented by formula (3B) may be contained in an amount of 0.98 or more, 0.99 or more, or substantially 1, relative to the solid content of the composition.

[0133] In one embodiment, the compound represented by formula (3A) and the compound represented by formula (3B) are contained in a total amount, in terms of molar ratio relative to the solid content of the composition, of 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 0.95 or more. For example, the compound may be contained in a molar ratio relative to the solid content of the composition of 0.98 or more, 0.99 or more, or even substantially 1.

[0134] In this specification, the above-mentioned "substantially 1" means that the solid content contains only the compound represented by formula (3A), only the compound represented by formula (3B), or both the compound represented by formula (3A) and the compound represented by formula (3B), or even if other compounds are contained, １９ This means that the amount contained is so large that it is not possible to calculate the content by F NMR.

[0135] The solid content refers to, for example, the composition obtained by concentrating the composition using an evaporator or the like and then drying the concentrated composition.

[0136] In one embodiment, the composition may contain, for example, the compound represented by formula (3A) in a molar ratio of 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more relative to the composition. For example, the compound represented by formula (3A) may be contained in a molar ratio of 0.98 or more, 0.99 or more, or substantially 1 relative to the composition.

[0137] In one embodiment, the composition may contain, for example, the compound represented by formula (3B) in a molar ratio of 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more relative to the composition. For example, the compound represented by formula (3B) may be contained in a molar ratio of 0.98 or more, 0.99 or more, or substantially 1 relative to the composition.

[0138] In one embodiment, the composition may contain, for example, the compound represented by formula (3A) and the compound represented by formula (3B) in a total amount, in terms of molar ratio relative to the composition, of 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more. For example, the compound may be contained in a molar ratio relative to the composition of 0.98 or more, 0.99 or more, or substantially 1.

[0139] In the present disclosure, no compound containing a metal atom is added in the reaction. Therefore, a step of removing the compound containing a metal atom from the composition using, for example, silica gel or the like is not particularly necessary. Therefore, in the present disclosure, the composition can be easily purified. Furthermore, in the present disclosure, the time required for purification can be shortened. It is preferable that the composition does not contain a compound containing a metal. By not including a compound containing a metal, the reaction after step (I) can proceed smoothly. For example, the metal can be inhibited from acting as a catalyst. Furthermore, by not including a compound containing a metal, a decrease in stability during storage of the composition can be suppressed. Furthermore, a surface treatment layer can be successfully formed from the composition. The durability of the formed surface treatment layer is maintained.

[0140] Examples of the metal atom include tin, palladium, copper, nickel, platinum, and silver, specifically tin.

[0141] The content of the metal atom (e.g., tin) is preferably 1 ppm or less, particularly preferably 1 ppb or less, based on mass of the olefin-modified fluorine-containing compound. The content of the metal atom can be measured using an ICP (Inductively Coupled Plasma) emission spectrophotometer. In this specification, the olefin-modified fluorine-containing compound is at least one selected from the group consisting of compounds represented by formula (3A) and compounds represented by formula (3B).

[0142] In one embodiment, the composition of the present disclosure contains an olefin-modified fluorine-containing compound and is essentially free of metal atoms (e.g., tin). Here, "essentially free" means that the metal atoms are in a range that cannot be measured using an ICP optical emission spectrometer, for example, 1 ppb or less relative to the olefin-modified fluorine-containing compound.

[0143] The composition may further contain other components. １Ａ -CFY １ -X １Ａ , R １Ａ -CFY １ -H, R １Ａ -(CFY １ ) ２ -R １Ａ , solvents, etc. Each symbol has the same meaning as above. Examples of the solvent include the solvents described above.

[0144] The composition of the present disclosure can be used as an additive such as a surface treatment agent, a raw material for grease, a sealant, a monomer for resin, etc.

[0145] The composition of the present disclosure may further contain additives such as a non-reactive fluoropolyether group-containing compound (e.g., a compound called "fluorine-containing oil") or a (non-reactive) silicone compound that can be understood as silicone oil (e.g., a compound called "silicone oil"), a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, a sol-gel, a hydrocarbon-based polymer, a fluorine-containing polymer, a radical scavenger, an inorganic porous material, a dehydrating agent, or a dehalogenating compound.

[0146] The fluorine-containing oil is not particularly limited, but examples thereof include compounds represented by the following general formula (4) (perfluoro(poly)ether compounds): ５ - (OC ４ F ８ ) ａ’ - (OC ３ F ６ ) ｂ’ - (OC ２ F ４ ) ｃ’ -(OCF ２ ) ｄ’ -Rf ６ ...(4) In the formula, Rf ５ is an alkyl group having 1 to 16 carbon atoms (preferably C １―１６ Rf represents a perfluoroalkyl group ６ is an alkyl group having 1 to 16 carbon atoms (preferably C １－１６ Rf represents a fluorine atom or a hydrogen atom; ５ and Rf ６ More preferably, each independently represents C １－３It is a perfluoroalkyl group. a', b', c' and d' respectively represent the number of four types of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, and the sum of a', b', c' and d' is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of the repeating units enclosed in parentheses with the subscript a', b', c' or d' is arbitrary in the formula. Of these repeating units, -(OC ４ F ８ )- is -(OCF ２ CF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ CF ２ ) -, -(OCF ２ CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )) -, -(OC(CF ３ ) ２ CF ２ ) -, -(OCF ２ C (CF ３ ) ２ )-,-(OCF(CF ３ )CF(CF ３ ))-,-(OCF(C ２ F ５ )CF ２ )- and (OCF ２ CF (C ２ F ５ ))-, but preferably -(OCF ２ CF ２ CF ２ CF ２ )-. -(OC ３ F ６ )- is -(OCF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ )- and (OCF ２ CF (CF ３))-, and preferably -(OCF ２ CF ２ CF ２ )-. -(OC ２ F ４ )- is -(OCF ２ CF ２ )- and (OCF(CF ３ ))-, but preferably -(OCF ２ CF ２ )-.

[0147] Examples of the perfluoro(poly)ether compound represented by the general formula (4) include compounds represented by the following general formulas (4a) and (4b) (which may be one type or a mixture of two or more types): ５ -(OCF ２ CF ２ CF ２ ) ｂ” -Rf ６ ...(4a) Rf ５ -(OCF ２ CF ２ CF ２ CF ２ ) ａ” -(OCF ２ CF ２ CF ２ ) ｂ” -(OCF ２ CF ２ ) ｃ” -(OCF ２ ) ｄ” -Rf ６ ...(4b) In these formulas, Rf ５ and Rf ６ is as defined above; in formula (4a), b" is an integer of 1 or more and 100 or less; in formula (4b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The order of occurrence of each repeating unit enclosed in parentheses with the subscripts a", b", c", and d" is arbitrary in the formula.

[0148] From another viewpoint, the fluorine-containing oil is a compound represented by the general formula Rf ３ -F (wherein, Rf３ is C ５－１６ The compound may be a compound represented by the formula (I) below, which is a perfluoroalkyl group. Also, it may be a chlorotrifluoroethylene oligomer.

[0149] The fluorine-containing oil may have a number average molecular weight of 500 to 10,000. The molecular weight of the fluorine-containing oil can be measured using gel permeation chromatography.

[0150] The fluorinated oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the composition of the present disclosure. In one embodiment, the composition of the present disclosure is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means that the composition does not contain any fluorinated oil, or may contain a very small amount of fluorinated oil.

[0151] The fluorine-containing oil contributes to improving the surface slip properties of the layer formed from the composition of the present disclosure.

[0152] In one embodiment, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the olefin-modified fluorine-containing compound. By setting the average molecular weight in this manner, better friction durability and surface slipperiness can be obtained. This embodiment is particularly advantageous when the surface treatment layer is formed by vacuum deposition.

[0153] In one embodiment, the average molecular weight of the fluorinated oil may be smaller than the average molecular weight of the olefin-modified fluorinated compound. By adjusting the average molecular weight in this manner, the composition of the present disclosure can form a cured product having high friction durability and high surface slippage while suppressing a decrease in the transparency of the cured product formed using the composition.

[0154] The silicone oil may be, for example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds. The linear silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, or the like. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0155] In the composition of the present disclosure, such silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass of the above-mentioned fluorinated polyether group-containing compounds of the present disclosure (the total of these when two or more types are used; the same applies hereinafter).

[0156] The silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

[0157] Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), and the like.

[0158] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0159] The present disclosure will be explained in more detail below through examples, but is not limited to these examples.

[0160] Quantitative analysis of tin in each compound was performed using an inductively coupled plasma (ICP) optical emission spectrometer (ICP-OES). The carrier gas flow rate during plasma introduction was 12 L / min, and during nebulizer introduction it was 0.7 L / min. ICP-OES: Agilent 5900. Measurement wavelength: Sn 188.925 nm.

[0161] Example 1: Under an argon atmosphere, CF ３ CF ２ CF ２ O (CF ２ CF ２ CF ２ O) ｎ CF ２ CF ２ 0.51 g of HCl (n=29, weight average molecular weight (Mw) 5,100), 0.4 mL of 1,3-bis(trifluoromethyl)benzene, 2.4 mg of azobisisobutyronitrile (AIBN), and 0.53 mmol of 1,1,1,3,3,3-hexamethyl-2-(2-propen-1-yl)-2-(trimethylsilyl)trisilane were introduced. This reaction solution was stirred at 90°C for 3 hours and then cooled to room temperature. The weight average molecular weight was １９ Determined by F NMR.

[0162] Acetone and perfluorohexane were added to the resulting reaction solution, and the mixture was separated. After distilling off the volatile matter, the resulting composition was １９ The composition was analyzed using F NMR. The compound (A) was contained in an amount of 100 parts by mass relative to 100 parts by mass of the composition. Compound (A): NMR analysis results of compound (A): 1 H NMR (D2O, C6F6): δ 2.63 (td, J = 17.42, 6.96 Hz, 2H), 5.11 (d, J = 7.28 Hz, 1H), 5.14 (s, 1H), 5.56 − 5.72 (m, 1H); 19 F NMR (D2O, C6F6; δ -163): δ -80.57 (t, J = 7.57 Hz, 3F), -81.10 - -81.70 (m, 4nF), -82.25 (m, 2F), -82.70 - -82.80 (m, 2F), -85.67 (t, J = 13.41 Hz, 2F), -86.12 (s, 2F), -87.53 - -87.54 (m, 2F), -116.74 (t, J = 11.29 Hz, 2F), -127.70 - -128.15 (m, 2nF), -128.68 (s, 2F).

[0163] Comparative Example 1 A reaction was carried out under the same conditions as in Example 1, except that 0.32 mmol of allyltributyltin was used instead of 1,1,1,3,3,3-hexamethyl-2-(2-propen-1-yl)-2-(trimethylsilyl)trisilane.

[0164] Acetone and perfluorohexane were added to the obtained reaction solution, and the mixture was separated. After the volatile matter was distilled off, the obtained composition was purified using a silica gel column. The volatile matter of the obtained distillate was distilled off under reduced pressure, and the obtained composition was １９ The composition was analyzed using F NMR. The compound (A) was contained in an amount of 97 parts by mass per 100 parts by mass of the composition. Quantitative analysis of tin was carried out using ICP-OES. The tin content was 40 ppm relative to the compound (A).

[0165] Example 2 A reaction was carried out under the same conditions as in Example 1, except that 1,1,1,3,3,3-hexamethyl-2-(2-methyl-2-propen-1-yl)-2-(trimethylsilyl)trisilane was used instead of 1,1,1,3,3,3-hexamethyl-2-(2-propen-1-yl)-2-(trimethylsilyl)trisilane.

[0166] Acetone and perfluorohexane were added to the resulting reaction solution, and the mixture was separated. After distilling off the volatile matter, the resulting composition was １９ The composition was analyzed using F NMR. The compound (B) was contained in an amount of 84 parts by mass relative to 100 parts by mass of the composition. Compound (B): NMR analysis results of compound (B): 1 H NMR (D2O, C6F6): δ 1.65 (s, 3H), 2.55 (t, J = 18.44 Hz, 1H), 4.69 (s, 1H), 4.82 (t, J = 1.40 Hz, 1H); 19F NMR (D2O, C6F6; δ -163): δ -80.58 (t, J = 7.57 Hz, 3F), -81.74 - -81.99 (m, 4nF), -82.27 - -82.28 (m, 2F), -82.76 - -82.85 (m, 2F), -86.15 (s, 2F), -86.38 (t, J = 13.41 Hz, 2F), -87.10 - -87.20 (m, 2F), -115.74 (t, J = 18.48 Hz, 2F), -127.70 - -128.10 (m, 2nF), -128.73 (s, 2F)

[0167] As described above, the selectivity of the olefin-modified fluorine-containing compound formed in Example 1 was improved compared to Comparative Example 1. In Comparative Example 1, the reaction between tributyltin radicals and iodine radicals proceeded quickly, resulting in the formation of CF ３ CF ２ CF ２ O (CF ２ CF ２ CF ２ O) ｎ CF ２ CF ２ It is believed that in Comparative Example 1, side reactions caused by these radicals were more likely to proceed, resulting in a lower selectivity for the olefin-modified fluorine-containing compound.

[0168] According to the present disclosure, a new method for producing an olefin-modified fluorine-containing compound can be obtained, and the selectivity of the olefin-modified fluorine-containing compound can be improved.

Claims

1. A method for producing an olefin-modified fluorine-containing compound, comprising reacting a compound represented by formula (1A) or a compound represented by formula (1B) with a compound represented by formula (2) in the presence of a radical initiator. R １Ａ -CFY １ -X １ ・・・(1A) [In the formula: R １Ａ is represented by Rf 1 -R F1 -(O) n21 -; Rf 1 is a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; R F1 is represented by the following formula (f1), (f2), or (f4) to (f6): -(OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (f1) [In formula (f1): d1 is an integer from 1 to 200; e1 is 1. -(OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f2) [In formula (f2): c1 and d1 each independently represent an integer of 0 to 30; e1 and f1 each independently represent an integer of 1 or more and 200 or less; The sum of c1, d1, e1, and f1 is 2 or more; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c1, d1, e1, or f1 is arbitrary in the formula. -(R 71 -R 72) g1 -R r -(R 72' -R 71') g1' - (f4) [In formula (f4): R 71 is OCF 2 or OC 2 F 4 ; R 72 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of two or three groups independently selected from these groups; R 71′ is OCF 2 or OC 2 F 4 ; R 72′ is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of two or three groups independently selected from these groups; g1 is an integer from 2 to 100; g1' is an integer from 2 to 100; Rr is 【Chemistry 1】 (In the formula, * indicates the bond position.) . . . - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f5) [In formula (f5): e1 is an integer of 1 or more and 200 or less; a1, b1, c1, d1, and f1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 5 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f6) [In formula (f6): f1 is an integer of 1 or more and 200 or less; a1, b1, c1, d1, and e1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 5 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. is a group represented by any one of the following formulas: n21 is 0 or 1; Y １ is a hydrogen atom or a halogen atom; X １ is a halogen atom other than a fluorine atom. X １ -CFY １ -R １Ｂ -CFY １ -X １ ・・・(1B) [In the formula: R １Ｂ is represented by -(Rf 2 ) n23 -R F1 -(O) n22 -; Rf 2 is a divalent organic group; R F1 is represented by the formula (f1), (f2), or (f4) to (f6): -(OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (f1) [In formula (f1): d1 is an integer from 1 to 200; e1 is 1. -(OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f2) [In formula (f2): c1 and d1 each independently represent an integer of 0 to 30; e1 and f1 each independently represent an integer of 1 or more and 200 or less; The sum of c1, d1, e1, and f1 is 2 or more; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c1, d1, e1, or f1 is arbitrary in the formula. -(R 71 -R 72) g1 -R r -(R 72' -R 71') g1' - (f4) [In formula (f4): R 71 is OCF 2 or OC 2 F 4 ; R 72 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of two or three groups independently selected from these groups; R 71′ is OCF 2 or OC 2 F 4 ; R 72′ is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of two or three groups independently selected from these groups; g1 is an integer from 2 to 100; g1' is an integer from 2 to 100; Rr is 【Chemistry 2】 (In the formula, * indicates the bond position.) . . . - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f5) [In formula (f5): e1 is an integer of 1 or more and 200 or less; a1, b1, c1, d1, and f1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 5 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f6) [In formula (f6): f1 is an integer of 1 or more and 200 or less; a1, b1, c1, d1, and e1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 5 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. is a group represented by any one of the following formulas: n22 is 0 or 1; n23 is 0 or 1; Y １ are each independently a hydrogen atom or a halogen atom; X １ are each independently a halogen atom other than a fluorine atom. R ２ ３ Si-(CH ２ ) ｎ１ -CR ４ =CR ５ R ６ ・・・(2) [In the formula: R ２ are each independently R ２１ ３ is a monovalent group containing Si-; R ２１ is independently at each occurrence a hydrogen atom or C １－１２ is an alkyl group; Said C １－１２ The alkyl group may be substituted with a halogen atom; n1 is an integer from 1 to 10; R ４ , R ５ and R ６ are each independently a hydrogen atom or C １－１０ is an alkyl group.

2. The Y １ The method according to claim 1 , wherein is a fluorine atom.

3. The X １ The method according to claim 1 or 2, wherein is a bromine atom or an iodine atom.

4. The R ２ are each independently R ２１ ３ Si-; The R ２１ each independently represents C optionally substituted by a halogen atom; １－４ is an alkyl group; Said C １－４ The alkyl group is linear or branched. The method according to claim 1 or 2.

5. The R ２ Each independently represents (CH ３ ) ３ The method of claim 4, wherein the compound is Si-.

6. The method according to claim 1 or 2, further comprising the step of carrying out a purification treatment after the reaction of the compound represented by formula (1A) or the compound represented by formula (1B) with the compound represented by formula (2).

7. The method according to claim 1 or 2, wherein the olefin-modified fluorine-containing compound is a compound represented by formula (3A) or a compound represented by formula (3B). R １Ａ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H ・・・(3A) [In the formula: R １Ａ , Y １ , n1, R ４ , R ５ and R ６ are the same as those described in claim 1. H(CH ２ ) ｎ１－１ -CH=CR ４ -CR ５ R ６ -CFY １ -R １Ｂ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H ・・・(3B) [In the formula: R １Ｂ , Y １ , n1, R ４ , R ５ and R ６ are the same as those described in claim 1.

8. A composition comprising at least one of an olefin-modified fluorine-containing compound represented by formula (3A) and an olefin-modified fluorine-containing compound represented by formula (3B), and tin in an amount of 1 ppm or less based on the total amount of the olefin-modified fluorine-containing compound represented by formula (3A) and the olefin-modified fluorine-containing compound represented by formula (3B). R １Ａ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H ・・・(3A) [In the formula: R １Ａ is represented by Rf 1 -R F1 -(O) n21 -; Rf 1 is a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; R F1 is represented by the following formula (f1), (f2), or (f4) to (f6): -(OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (f1) [In formula (f1): d1 is an integer from 1 to 200; e1 is 1; -(OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f2) [In formula (f2): c1 and d1 each independently represent an integer of 0 to 30; e1 and f1 each independently represent an integer of 1 or more and 200 or less; The sum of c1, d1, e1, and f1 is 2 or more; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c1, d1, e1, or f1 is arbitrary in the formula. -(R 71 -R 72) g1 -R r -(R 72' -R 71') g1' - (f4) [In formula (f4): R 71 is OCF 2 or OC 2 F 4 ; R 72 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of two or three groups independently selected from these groups; R 71′ is OCF 2 or OC 2 F 4 ; R 72′ is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of two or three groups independently selected from these groups; g1 is an integer from 2 to 100; g1' is an integer from 2 to 100; Rr is 【Chemistry 3】 (In the formula, * indicates the bond position.) . . . - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f5) [In formula (f5): e1 is an integer of 1 or more and 200 or less; a1, b1, c1, d1, and f1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 5 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f6) [In formula (f6): f1 is an integer of 1 or more and 200 or less; a1, b1, c1, d1, and e1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 5 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. is a group represented by any one of the following formulas: n21 is 0 or 1; Y １ is a hydrogen atom or a halogen atom; n1 is an integer from 1 to 10; R ４ , R ５ and R ６ is independently at each occurrence a hydrogen atom or C １－１０ is an alkyl group. H(CH ２ ) ｎ１－１ -CH=CR ４ -CR ５ R ６ -CFY １ -R １Ｂ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H ・・・(3B) [In the formula: R １Ｂ is represented by -(Rf 2 ) n23 -R F1 -(O) n22 -; Rf 2 is a divalent organic group; R F1 is represented by the formula (f1), (f2), or (f4) to (f6): -(OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (f1) [In formula (f1): d1 is an integer from 1 to 200; e1 is 1. -(OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f2) [In formula (f2): c1 and d1 each independently represent an integer of 0 to 30; e1 and f1 each independently represent an integer of 1 or more and 200 or less; The sum of c1, d1, e1, and f1 is 2 or more; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c1, d1, e1, or f1 is arbitrary in the formula. -(R 71 -R 72) g1 -R r -(R 72' -R 71') g1' - (f4) [In formula (f4): R 71 is OCF 2 or OC 2 F 4 ; R 72 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of two or three groups independently selected from these groups; R 71′ is OCF 2 or OC 2 F 4 ; R 72′ is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of two or three groups independently selected from these groups; g1 is an integer from 2 to 100; g1' is an integer from 2 to 100; Rr is 【Chemistry 4】 (In the formula, * indicates the bond position.) . . . - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f5) [In formula (f5): e1 is an integer of 1 or more and 200 or less; a1, b1, c1, d1, and f1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 5 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - (f6) [In formula (f6): f1 is an integer of 1 or more and 200 or less; a1, b1, c1, d1, and e1 are each independently an integer of 0 to 200, and the sum of a1, b1, c1, d1, e1, and f1 is 5 or more; The order of occurrence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula. is a group represented by any one of the following formulas: n22 is 0 or 1; n23 is 0 or 1; Y １ are each independently a hydrogen atom or a halogen atom; Each n1 is independently an integer from 1 to 10; R ４ , R ５ and R ６ is independently at each occurrence a hydrogen atom or C １－１０ is an alkyl group.

9. The composition according to claim 8, wherein the tin content is 1 ppb or less based on the total amount of the olefin-modified fluorine-containing compound represented by formula (3A) and the olefin-modified fluorine-containing compound represented by formula (3B).

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