WO2018180561A1 - Fluorinated ether composition and method for producing same - Google Patents

Fluorinated ether composition and method for producing same Download PDF

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Publication number
WO2018180561A1
WO2018180561A1 PCT/JP2018/010306 JP2018010306W WO2018180561A1 WO 2018180561 A1 WO2018180561 A1 WO 2018180561A1 JP 2018010306 W JP2018010306 W JP 2018010306W WO 2018180561 A1 WO2018180561 A1 WO 2018180561A1
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compound
group
transition metal
same
fluorine
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PCT/JP2018/010306
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French (fr)
Japanese (ja)
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清貴 高尾
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Ａｇｃ株式会社
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Priority to JP2019509261A priority Critical patent/JP6977767B2/en
Priority to CN201880017367.0A priority patent/CN110392711B/en
Publication of WO2018180561A1 publication Critical patent/WO2018180561A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a fluorine-containing ether composition and a method for producing the same.
  • the fluorine-containing compound exhibits high lubricity, water / oil repellency, etc.
  • it is used as a surface treatment agent or the like.
  • lubricity, water and oil repellency, etc. are imparted, and the dirt on the surface of the base material can be easily wiped off, thereby improving the dirt removability.
  • fluorine-containing compounds fluorine-containing ether compounds having a poly (oxyperfluoroalkylene) chain in which an ether bond (—O—) is present in the middle of the perfluoroalkyl chain are excellent in the removal of dirt such as fats and oils.
  • fluorine-containing ether compound has a performance (fingerprint stain removal property) that can easily remove fingerprints attached to the surface by wiping off, for example, as a surface treatment agent for a member constituting a touch surface of a touch panel. It is used.
  • a hydrolyzable silyl group is introduced at the end of the fluorine-containing ether compound, What is necessary is just to chemically bond an ether compound and a base material.
  • the hydrolyzable silyl group is hydrolyzed to form a silanol group, and the silanol group is bonded to the surface of the substrate.
  • a hydrolyzable silyl group As a method of introducing a hydrolyzable silyl group into the terminal of the fluorine-containing ether compound, a 2-propenyl group (—CH 2 CH ⁇ CH 2 , commonly used name: allyl group) is introduced into the terminal of the molecule of the raw material compound, A method in which a hydrosilane compound is reacted with a compound into which a 2-propenyl group has been introduced and hydrosilylated is preferably used. The hydrosilylation reaction is performed, for example, in the presence of a trace amount of a transition metal compound (Patent Documents 1 to 4).
  • the surface layer formed by coating the surface of the base material with a fluorine-containing ether compound having a hydrolyzable silyl group at the end, obtained by hydrosilylation by the methods described in Patent Documents 1 to 4, has durability. Not always enough. Since a touch panel or the like is repeatedly rubbed with a finger, the surface layer formed on the surface of the base material is required to have durability capable of maintaining performance for a long period of time. In particular, in a touch panel for outdoor use (digital signage such as a vending machine or a guide board), an in-vehicle touch panel, etc., high durability is required for the surface layer. In addition, a substrate provided with a surface layer is required to have high transparency.
  • An object of the present invention is to provide a fluorine-containing ether composition and a method for producing the fluorine-containing ether composition capable of forming a surface layer having excellent durability without impairing the transparency of the substrate.
  • the present invention can provide a fluorine-containing ether composition and a method for producing a fluorine-containing ether compound having the following configurations [1] to [13].
  • a fluorine-containing ether composition comprising a compound (A) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (I), and a transition metal compound,
  • a fluorine-containing ether composition wherein a mass ratio of the transition metal compound to the compound (A) is 300 to 4,000 ppm in terms of transition metal.
  • L is a hydroxyl group or a hydrolysable group
  • R is a hydrogen atom or a monovalent hydrocarbon group
  • n is an integer from 0 to 2, when n is 0 or 1, (3-n) L's may be the same or different; When n is 2, n R may be the same or different.
  • the alkylene groups may all be the same or different, R fe is the poly (oxyperfluoroalkylene) chain, Z 1 is a (a + b) -valent linking group, a is an integer of 1 or more, b is an integer of 1 or more, When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different, When b is 2 or more, b [-SiR n L 3-n ] may be the same or different.
  • the poly ( oxyperfluoroalkylene ) chain is ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ , ⁇ (CF 2 O) m11 (CF 2 CF 2 CF 2 O) m12 ⁇ , ⁇ (CF 2 O) m11 (CF 2 CF 2 CF 2 O) m12 ⁇ or (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) m15 (where m11 is an integer of 1 or more) M12 is an integer of 1 or more, (m11 + m12) is an integer of 2 to 200, and m15 is an integer of 1 to 100), or a fluorine-containing ether composition according to [1] or [2] .
  • L is a hydroxyl group or a hydrolysable group
  • R is a hydrogen atom or a monovalent hydrocarbon group
  • n is an integer from 0 to 2, when n is 0 or 1, (3-n) L's may be the same or different; When n is 2, n R may be the same or different.
  • R f1 is a perfluoroalkyl group
  • Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups.
  • the alkylene groups may all be the same or different, R fe is the poly (oxyperfluoroalkylene) chain, Z 1X is a (a + b) -valent linking group, and has —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n , a is an integer of 1 or more, b is an integer of 1 or more, When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different, When b is 2 or more, b [-SiR n L 3-n ] may be the same or different. [13] The method for producing a fluorinated ether composition according to any one of [10] to [12], wherein the transition metal compound is a platinum compound.
  • a surface layer having excellent durability can be formed without impairing the transparency of the substrate.
  • a fluorine-containing ether composition capable of forming a surface layer having excellent durability can be produced without impairing the transparency of the substrate.
  • a compound represented by the formula (1) is referred to as a compound (1).
  • the meanings of the following terms in this specification are as follows.
  • the “hydrolyzable silyl group” means a group that can form a silanol group (Si—OH) by a hydrolysis reaction.
  • L in the formula (I) is a hydrolyzable group
  • —SiR n L 3-n is a hydrolyzable silyl group.
  • the chemical formula of the oxyperfluoroalkylene group is expressed by describing the oxygen atom on the right side of the perfluoroalkylene group.
  • the fluorine-containing ether composition of the present invention contains the following compound (A) and a transition metal compound.
  • the composition does not contain a liquid medium.
  • the composition may contain a liquid medium having an impurity amount.
  • the present composition may contain other components as long as the effects of the present invention are not impaired.
  • other fluorine-containing ether compounds other than the compound (A) described later impurities other than the compound (A), transition metal compounds and other fluorine-containing ether compounds, hydrolysis of hydrolyzable silyl groups and Well-known additives, such as an acid catalyst and a basic catalyst which accelerate a condensation reaction, are mentioned.
  • impurities other than the compound (A), the transition metal compound and other fluorine-containing ether compounds include compounds unavoidable in the production of the compound (A) and other fluorine-containing ether compounds.
  • Compound (A) has a poly (oxyperfluoroalkylene) chain and a group (I). -SiR n L 3-n (I) However, L is a hydroxyl group or a hydrolysable group, R is a hydrogen atom or a monovalent hydrocarbon group, n is an integer from 0 to 2, when n is 0 or 1, (3-n) L's may be the same or different; When n is 2, n R may be the same or different.
  • Compound (A) may further have a group (II).
  • R f1 is a perfluoroalkyl group
  • Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups. All of the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may be the same or different.
  • Examples of the poly (oxyperfluoroalkylene) chain include those represented by the following formula (a).
  • (R f2 O) m1 (a) Where R f2 is a perfluoroalkylene group, m1 is an integer from 2 to 200, (R f2 O) m1 may be composed of two or more types of R f2 O having different carbon numbers. In that case, two or more types of R f2 O may be arranged in any of random, alternating, and block. Particularly, in the case of (CF 2 O) and PFE chain having and other (R f2 O), preferably disposed randomly and (CF 2 O) and the other (R f2 O).
  • the number of carbon atoms of R f2 is preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 4 from the viewpoint of further excellent friction resistance and fingerprint removability of the surface layer.
  • One to two is particularly preferred, and a perfluoroalkylene group having 3 to 4 carbon atoms is particularly preferred from the viewpoint of further improving the friction resistance of the surface layer.
  • R f2 may be branched or linear, and is preferably linear because the surface layer is further excellent in friction resistance and lubricity.
  • M1 is an integer of 2 to 200, preferably an integer of 5 to 150, particularly preferably an integer of 10 to 80. If m1 is not less than the lower limit of the above range, the water and oil repellency of the surface layer is excellent. If m1 is not more than the upper limit of the above range, the surface layer has excellent friction resistance. That is, when the number average molecular weight of the compound (A) is too large, the number of groups (I) present per unit molecular weight is reduced, and the friction resistance is lowered.
  • Specific embodiments of the PFE chain include the following (a-1) to (a-8).
  • m01 is an integer of 2 to 200
  • m11 is an integer of 1 or more
  • m12 is an integer of 1 or more
  • m01 and (m11 + m12) are each an integer of 2 to 200, preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 80.
  • the ratio of m11 to m12 (m11 / m12) is preferably 99/1 to 30/70, particularly preferably 90/10 to 40/60.
  • m13 and m14 are each an integer of 2 to 200.
  • m15 is an integer of 1 to 100, preferably an integer of 3 to 75, and particularly preferably an integer of 5 to 40.
  • (a-2) to (a-4) and (a-8) are preferable, and (a-2) is particularly preferable.
  • L is a hydroxyl group or a hydrolyzable group.
  • the hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, when L is a hydrolyzable group, Si—L of the group (I) becomes a silanol group (Si—OH) by the hydrolysis reaction.
  • the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (—NCO) and the like.
  • the number of carbon atoms of the alkoxy group is preferably 1 to 4.
  • the acyl group preferably has 2 to 5 carbon atoms.
  • As the halogen atom a chlorine atom is particularly preferable.
  • L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of ease of production of the compound (A).
  • L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of little outgassing during coating and excellent storage stability of the compound (A), and when long-term storage stability of the compound (A) is required.
  • Is particularly preferably an ethoxy group, and a methoxy group is particularly preferred when the reaction time after coating is short.
  • R is a hydrogen atom or a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group include a saturated hydrocarbon group such as an alkyl group and a cycloalkyl group, an alkenyl group, and an allyl group, and a saturated hydrocarbon group is preferable.
  • the number of carbon atoms of the monovalent saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint that the compound (A) can be easily produced.
  • n is preferably 0 or 1, particularly preferably 0.
  • the adhesion to the substrate becomes stronger and the durability of the surface layer is further improved.
  • n is 0 or 1
  • (3-n) L may be the same or different.
  • a part of L may be a hydrolyzable group and the remaining L may be a hydroxyl group.
  • Si (OCH 3 ) 3 As the group (I), Si (OCH 3 ) 3 , SiCH 3 (OCH 3 ) 2 , Si (OCH 2 CH 3 ) 3 , SiCl 3 , Si (OCOCH 3 ) 3 , and Si (NCO) 3 are preferable. From the viewpoint of ease of handling in industrial production, Si (OCH 3 ) 3 is particularly preferable.
  • R f1 is a perfluoroalkyl group.
  • the number of carbon atoms of the perfluoroalkyl group in R f1 is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3 in view of further excellent lubricity and durability of the surface layer.
  • the perfluoroalkyl group may be branched or linear, and is preferably linear. Examples of the linear perfluoroalkyl group include CF 3 —, CF 3 CF 2 —, CF 3 CF 2 CF 2 — and the like.
  • Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 (preferably 2 to 4) of the oxyfluoroalkylene group. .
  • the polyoxyfluoroalkylene group the plurality of oxyfluoroalkylene groups are usually bonded in series.
  • the compound (A) is less likely to aggregate in the coating liquid, and the compound (A) is less likely to aggregate in the course of drying after being applied to the surface of the substrate, so that the appearance of the surface layer is further improved.
  • the number of carbon atoms in the oxyfluoroalkylene group is preferably 1 to 6, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 2 or 3.
  • the number of hydrogen atoms in the oxyfluoroalkylene group is 1 or more, preferably 2 or more, particularly preferably 3 or more, from the viewpoint of excellent appearance of the surface layer.
  • the number of hydrogen atoms in the oxyfluoroalkylene group is preferably (Q carbon number) ⁇ 2 or less, particularly preferably (Q carbon number) or less, from the viewpoint of further excellent water and oil repellency of the surface layer.
  • the oxyfluoroalkylene group may be branched or linear, and is preferably linear because the lubricity of the surface layer is further improved. In the polyoxyfluoroalkylene group, 2 to 5 oxyfluoroalkylene groups may all be the same or different.
  • Q is a single bond or —CHFCF 2 OCH 2 CF 2 O—, —CF 2 CHFCF 2 OCH 2 CF 2 O—, —CF 2 CF from the viewpoint of ease of production of the compound (A).
  • the compound (A) may have one PFE chain or two or more PFE chains. One to three is preferable from the viewpoint of ease of production and handling. When the compound (A) has two or more PFE chains, each PFE chain may be the same or different.
  • the group (I) possessed by the compound (A) may be one or two or more. Two or more are preferable and three or more are particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the bond with the substrate. 10 or less is preferable, 5 or less is more preferable, and 4 or less is particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the density of molecules bonded to the substrate. Accordingly, the group (I) possessed by the compound (A) is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 3 to 4. When the compound (A) has two or more groups (I), each group (I) may be the same or different. In terms of ease of production of the compound (A), it is preferred that all are the same group.
  • the group (II) is bonded to one end of the PFE chain. That is, the compound (A) preferably further has a group (II) bonded to one end of the PFE chain. Thereby, the lubricity of the surface layer is further improved.
  • the number average molecular weight (Mn) of the compound (A) is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and particularly preferably 4,000 to 12,000. If the number average molecular weight of the compound (A) is not less than the lower limit of the above range, the lubricity of the surface layer is further improved. When the number average molecular weight of the compound (A) is at least the lower limit of the above range, the durability of the surface layer is further improved.
  • the number average molecular weight (Mn) is measured by the measuring method described in the examples described later.
  • the compound (A) is not particularly limited as long as it has a PFE chain and a group (I).
  • it can be appropriately selected from known fluorine-containing ether compounds described in the following documents. JP 2013-91047 A, JP 2014-80473 A, International Publication No. 2013/042732, International Publication No. 2013/042733, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, International Publication No. 2014/175124, International Publication No. 2015/0887902, Japanese Unexamined Patent Publication No. 2013-227279, Japanese Unexamined Patent Publication No. 2013-241369, Japanese Unexamined Patent Publication No. 2013-2013. No.
  • the compound (A) may be a single compound composed of one kind of compound (A) or a mixture composed of two or more kinds of compounds (A).
  • fluorine-containing ether compounds that are the same compound group except that they have a distribution in the number of repeating oxyperfluoroalkylene groups in the poly (oxyperfluoroalkylene) chain are regarded as a single compound.
  • the same group of compounds, except for the distribution in m11 and m12 includes a fluorine-containing ether compound that is a single compound. To do.
  • a fluorine-containing ether compound represented by the following formula (A1) (hereinafter also referred to as compound (A1)) can be mentioned.
  • R f1 , Q, L, R and n are as defined above
  • R fe is a PFE chain
  • Z 1 is a (a + b) -valent linking group
  • a is an integer of 1 or more
  • b is an integer of 1 or more
  • a [R f1 -OQR fe- ] may be the same or different
  • b [-SiR n L 3-n ] may be the same or different.
  • R f1 is the same as R f1 in the group (II), preferable embodiments thereof are also the same.
  • a R f1 is preferably the same in number of carbon atoms, and from the viewpoint of ease of production, the same group, that is, the same number of carbon atoms and the same chemical structure. Is preferred.
  • the group having the same carbon number and the same chemical structure means that, for example, when a is 2, two R f1 are CF 3 CF 2 CF 2 — (the two R f1 (It is not a combination of CF 3 CF 2 CF 2 — and CF 3 CF (CF 3 ) —, which have the same carbon number but different chemical structures.)
  • Q is the same as Q in the group (II), and preferred embodiments are also the same.
  • the PFE chain of R fe is the same as described above, and the preferred embodiment is also the same.
  • L is the same as L in the group (I), and preferred embodiments are also the same.
  • R is the same as R in the group (I), and preferred embodiments are also the same.
  • n is the same as n in the group (I), and preferred embodiments are also the same.
  • Preferred values for a are the same as the preferred number of PFE chains that compound (A) has. That is, each a is preferably an integer of 1 to 3.
  • the preferable value of b is the same as the preferable number of groups (I) that the compound (A) has.
  • b is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and particularly preferably an integer of 3 to 4.
  • a + b) is preferably 2 to 13, more preferably 3 to 8, and particularly preferably 4 to 7.
  • a [R f1 -OQR fe- ] are preferably the same, and when b is 2 or more, b [-SiR n L 3-n ] Are preferably the same.
  • Z 1 is, for example, a (a + b) -valent substituted or unsubstituted hydrocarbon group, a group or atom other than a hydrocarbon group at the carbon-carbon atom or / and terminal of the substituted or unsubstituted hydrocarbon group.
  • Examples thereof include (a + b) -valent groups and (a + b) -valent organopolysiloxane groups.
  • Examples of the unsubstituted hydrocarbon group include a linear or branched saturated hydrocarbon group, an aromatic hydrocarbon cyclic group (for example, (a + b) hydrogen atoms from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring).
  • a group excluding an atom a group composed of a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, an alkyl group bonded to the aromatic hydrocarbon cyclic group as a substituent)
  • groups having an arylene group such as a phenylene group between and / or at the terminal of the saturated hydrocarbon group), and a group formed of a combination of two or more aromatic hydrocarbon cyclic groups.
  • a linear or branched saturated hydrocarbon group is preferable.
  • the number of carbon atoms of the unsubstituted hydrocarbon group is preferably 20 or less.
  • the substituted hydrocarbon group is a group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with a substituent.
  • the substituent include a hydroxyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an amino group, a nitro group, a cyano group, and an aminocarbonyl group.
  • Examples of the group or atom other than the hydrocarbon group between the carbon-carbon atoms and / or the terminal of the hydrocarbon group include an etheric oxygen atom (—O—), a thioetheric sulfur atom (—S—), a nitrogen atom ( —N ⁇ ), silicon atom (> Si ⁇ ), carbon atom (> C ⁇ ), —N (R 15 ) —, —C (O) N (R 15 ) —, —OC (O) N (R 15 )-, -Si (R 16 ) (R 17 )-, organopolysiloxane groups, -C (O)-, -C (O) -O-, -C (O) -S- and the like.
  • R 15 is a hydrogen atom, an alkyl group or a phenyl group
  • R 16 to R 17 are each independently an alkyl group or a phenyl group.
  • the alkyl group preferably has 1 to 6 carbon atoms.
  • the organopolysiloxane group may be linear, branched, or cyclic.
  • ⁇ Preferred Form of Compound (A1)> As the compound (A1), at least one selected from the group consisting of the following compound (A11), compound (A12) and compound (A13) is used because the surface layer is further excellent in friction resistance and fingerprint stain removability. preferable.
  • Compound (A11) The compound (A11) is represented by the following formula (A11).
  • R f1 , Q, R fe , R, L and n are as defined above,
  • Q 32 represents a fluoroalkylene group having 1 to 20 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 to 20 carbon atoms (however, one end is bonded to the etheric oxygen atom).
  • R 33 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, p1 is 0 or 1, R 34 is a single bond, an alkylene group having 1 to 6 carbon atoms, and an etheric oxygen at the terminal of the alkylene group (provided that the terminal is bonded to C [—R 35 —SiR n L 3-n ] 3 ).
  • a group having an etheric oxygen atom between carbon-carbon atoms of Three [—R 35 —SiR n L 3-n ] may be the same or different.
  • a is 1, b is 3, and Z 1 is —Q 32 — [C (O) N (R 33 )] p1 —R 34 —C [—R 35 —] 3
  • the number of (CF 2 O) in R fe is preferably 4 or more, and the number of (CF 2 O) in Q 32 is preferably 0 to 3.
  • the three [—R 35 —SiR n L 3-n ] are preferably the same.
  • the fluoroalkylene group having 1 to 20 carbon atoms is preferably a perfluoroalkylene group or a fluoroalkylene group containing one or more hydrogen atoms.
  • the fluoroalkylene group is preferably linear from the viewpoint of friction resistance and lubricity of the surface layer.
  • Examples of the group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms include the group (ii) described later.
  • Q 32 includes a perfluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 1 to 20 carbon atoms containing one or more hydrogen atoms, and a fluoro having 2 to 20 carbon atoms containing one or more hydrogen atoms.
  • a group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group is preferred.
  • Q 32 is typically a C 1 perfluoroalkylene group. If p1 is 1, the Q 32, include the following groups. (I) a perfluoroalkylene group. (Ii) a fluoroalkylene group having R F CH 2 O (wherein R F is a C 1-6 perfluoroalkylene group) on the side bonded to R fe and containing one or more hydrogen atoms A group having (on the side bonded to C (O) N (R 33 )) (which may have an etheric oxygen atom between carbon-carbon atoms).
  • R 34 represents a single bond, —CH 2 O—, —CH 2 OCH 2 —, —CH 2 OCH 2 CH 2 O— from the viewpoint of ease of production of the compound (A11). And a group selected from the group consisting of —CH 2 OCH 2 CH 2 OCH 2 — (wherein the left side is bonded to Q 32 ) is preferable.
  • R 34 is preferably a group selected from the group consisting of a single bond, —CH 2 —, and —CH 2 CH 2 — from the viewpoint of easy production of the compound (A11).
  • R 35 represents —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 OCH 2 CH 2 CH 2 —, —OCH 2 CH from the viewpoint of ease of production of the compound (A11).
  • a group selected from the group consisting of 2 CH 2 — (where the right side is bonded to Si) is preferred.
  • R 35 those having no etheric oxygen atom are particularly preferred from the viewpoint of excellent light resistance of the surface layer.
  • the water and oil repellent layers are required to have light resistance.
  • Three R 35 in the compound (A11) may be the same or different.
  • Examples of the compound (A11) include compounds of the following formula.
  • the compound is preferable because it is easy to produce industrially, is easy to handle, and is excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity and appearance of the surface layer.
  • W in these formulas is R f1 —OQRfe —.
  • a preferred form of W is a combination of the preferred R f1 , Q and R fe described above.
  • a preferred range of Q 32 are as described above.
  • Compound (A12) The compound (A12) is represented by the following formula (A12).
  • R 42 is a C 1-6 perfluoroalkylene group
  • R 43 represents a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or —NH— at the terminal of the alkylene group (excluding the terminal bonded to N), A group having an etheric oxygen atom or —NH— between carbon and carbon atoms of an alkylene group of 2 to 6 or an alkylene group having 2 to 6 carbon atoms (excluding the terminal on the side bonded to N) And a group having an etheric oxygen atom or —NH— between carbon-carbon atoms, R 44 is an
  • the compound (A12) is a compound in which a is 1, b is 2, and Z 1 is —R 42 —R 43 —N [—R 44 —] 2 in the above formula (A1).
  • R 42 is preferably a linear perfluoroalkylene group. If R 42 is a linear perfluoroalkylene group, abrasion resistance and lubricity of the surface layer is further excellent. R 42 is typically a C 1 perfluoroalkylene group when R fe is ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ .
  • R 43 represents —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 OCH 2 CH 2 — and — from the viewpoint of ease of production of the compound (A12).
  • R 43 has a high polarity and does not have an ester bond with insufficient chemical resistance and light resistance, and therefore is excellent in the initial water repellency, chemical resistance and light resistance of the surface layer.
  • R 44 —CH 2 CH 2 CH 2 — and —CH 2 CH 2 OCH 2 CH 2 CH 2 — (provided that the right side is bonded to Si from the viewpoint of easy production of the compound (A12)). ) Is preferred. Since R 44 has high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, it is excellent in the initial water repellency, chemical resistance and light resistance of the surface layer. R 44 is particularly preferably one having no etheric oxygen atom from the viewpoint of excellent light resistance of the surface layer.
  • Two R 44 in the compound (A12) may be the same or different. The two R 44 are preferably the same, and the two [—R 44 —SiR n L 3-n ] are preferably the same.
  • Examples of the compound (A12) include compounds of the following formula.
  • the compound is preferred because it is easy to produce industrially, is easy to handle, and is further excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity, chemical resistance and light resistance.
  • W in these formulas is R f1 —OQRfe —.
  • a preferred form of W is a combination of the preferred R f1 , Q and R fe described above.
  • a preferred range for R 42 is as described above.
  • Compound (A13) is represented by the following formula (A13). [R f1 -OQR fe -R 51 -R 52 -O-] e Z 3 [-O-R 53 -SiR n L 3-n ] f (A13)
  • R 51 is a C 1-6 perfluoroalkylene group
  • R 52 is an alkylene group having 1 to 6 carbon atoms
  • Z 3 is an (e + f) -valent hydrocarbon group, or a group having 2 or more carbon atoms and an (e + f) -valent group having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group
  • R 53 is an alkylene group having 1 to 20 carbon atoms
  • e is an integer greater than or equal to 1
  • f is an integer of 1 or more
  • (E + f) is 3 or more
  • e is preferably an integer of 1 to 3.
  • f is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and particularly preferably an integer of 3 to 4. Further, when e is 2 or more, it is preferable that e [R f1 -OQR fe -R 51 -R 52 -O-] are the same, and when f is 2 or more, f [[ —O—R 53 —SiR n L 3-n ] are preferably the same.
  • R 51 is —CF 2 — when, for example, R fe is ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ .
  • R 51 is preferably linear. If R51 is a straight-chain compound (A13), a surface layer having better friction resistance and lubricity can be formed.
  • R 52 is preferably an alkylene group having 1 to 4 carbon atoms, particularly preferably —CH 2 —, from the viewpoint of easy production of the compound (A13).
  • the R f1 —O—Q—R fe —R 51 — group has the following features: water / oil repellency, durability, fingerprint stain removability, lubricity, and further appearance of the surface layer; and production of compound (A13) From the viewpoint of easy handling, the group (R f -1) and the group (R f -2) are preferable.
  • R f11 is a linear perfluoroalkyl group with 1 to 20 carbon atoms
  • m21 and m22 are each an integer of 1 or more
  • m21 + m22 is an integer of 2 ⁇ 200, m21 amino CF
  • the bonding order of 2 O and m22 CF 2 CF 2 O is not limited.
  • Z 3 examples include a residue obtained by removing a hydroxyl group from a polyhydric alcohol having (e + f) hydroxyl groups.
  • Specific examples of Z 3 include groups represented by the following formula.
  • Z 3 is preferably a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a primary hydroxyl group from the viewpoint of excellent hydroxyl reactivity. From the viewpoint of availability of raw materials, Z (3), (Z-2) and the group (Z-3) are particularly preferred.
  • R 4 is an alkyl group, and is preferably a methyl group or an ethyl group.
  • R 53 is preferably an alkylene group having 3 to 14 carbon atoms from the viewpoint of easy production of the compound (A13). Furthermore, a by-product in which part or all of the allyl group (—CH 2 CH ⁇ CH 2 ) is isomerized to the inner olefin (—CH ⁇ CHCH 3 ) during hydrosilylation in the production of the compound (A13) described later is obtained.
  • An alkylene group having 4 to 10 carbon atoms is particularly preferred because it is difficult to form.
  • Examples of the compound (A13) include compounds represented by the following formula. These compounds are preferable because they are easy to produce industrially, are easy to handle, and are excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity and appearance of the surface layer.
  • W in these formulas is R f1 —OQRfe —.
  • a preferred form of W is a combination of the preferred R f1 , Q and R fe described above.
  • a preferred form of R 51 is as described above.
  • Transition metal compounds include catalysts in hydrosilylation reactions described later, hydrolysis reactions of hydrolyzable silyl groups into silanol groups, and dehydration condensation reactions between the silanol groups and hydroxyl groups on the surface of the substrate (substrate-OH). The thing which acts as is mentioned.
  • Examples of the transition metal compound having such an action include compounds containing a group 8-10 transition metal.
  • Examples of the compound containing a Group 8-10 transition metal include ruthenium (Ru) compounds, iron (Fe) compounds, rhodium (Rh) compounds, cobalt (Co) compounds, platinum (Pt) compounds, nickel (Ni) compounds, Examples thereof include palladium (Pd) compounds.
  • a platinum compound is particularly preferable because it exhibits a high catalytic action for the hydrolysis reaction and dehydration condensation reaction.
  • Groups 8 to 10 are group numbers according to the revised IUPAC inorganic chemical nomenclature (1989).
  • platinum compound examples include platinum alone, platinum / divinyltetramethyldisiloxane complex, platinum / tetramethyltetravinylcyclotetrasiloxane complex, chloroplatinic acid, and platinum oxide. Of these, platinum / divinyltetramethyldisiloxane complexes and platinum / tetramethyltetravinylcyclotetrasiloxane complexes are preferred.
  • This composition may consist of a compound (A) and a transition metal compound, and may further contain other fluorine-containing ether compounds other than a compound (A).
  • fluorine-containing ether compounds include fluorine-containing ether compounds having a poly (oxyperfluoroalkylene) chain and having no group (I) (hereinafter also referred to as compound (C)).
  • the poly (oxyperfluoroalkylene) chain may be a PFE chain.
  • Examples of the compound (C) include the compound (C1).
  • a 31 and A 32 are each independently a perfluoroalkyl group having 1 to 20 carbon atoms;
  • Q 51 is a single bond having 1 to 6 carbon atoms that does not have a branched structure containing one or more hydrogen atoms.
  • An etheric oxygen atom at the terminal of a fluoroalkylene group having 1 to 6 carbon atoms not having a branched structure containing one or more hydrogen atoms (excluding the terminal on the side bonded to A 31 —O)
  • Q 52 represents a fluoroalkylene group having 1 to 20 carbon atoms which does not have a branched structure containing one or more hydrogen atoms, or one or more hydrogen atoms.
  • a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms not having a branched structure (provided that the oxygen number is 10 or less);
  • R F3 is a branched structure M30 is an integer of 2 to 200;
  • (R F3 O) m30 is composed of two or more types of R F3 O having different carbon numbers. at best; p3, if Q 51 is a single bond is 0, if Q 51 is other than a single bond is 1.
  • compound (C1) one produced by a known production method may be used, or a commercially available product may be used.
  • commercial products of compound (C1) in which Q 51 is a single bond and p3 is 0 include FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, FOMBLIN (registered trademark) Z (above, Solvaiso Lexis), Krytox (registered trademark) (manufactured by DuPont), and Demnam (registered trademark) (manufactured by Daikin Industries).
  • composition of this composition In the present composition, the mass ratio of the transition metal compound to the compound (A) is 300 to 4,000 ppm in terms of transition metal. If the mass ratio of the transition metal compound is within the above range, the durability of the surface layer can be improved without impairing the transparency of the substrate.
  • the mass ratio of the transition metal compound to the compound (A) is preferably 400 to 2,000 ppm, particularly preferably 500 to 1,000 ppm, in terms of transition metal.
  • the total amount of the compound (A) and the transition metal compound is preferably 0.1% by mass or more, more preferably 5% by mass or more, and further preferably 30% by mass or more with respect to the total mass of the present composition.
  • An upper limit is not specifically limited, 100 mass% may be sufficient.
  • the compound (AX) may be produced as follows.
  • the method for producing a fluorinated ether composition of the first embodiment includes a compound (B) shown below and a compound represented by the following formula (S) (hereinafter referred to as compound (S)).
  • a transition metal compound hereinafter also referred to as a hydrosilylation reaction
  • the amount of the transition metal compound used is 300 to 4,000 ppm in terms of transition metal as the mass ratio of the transition metal compound to the compound (B).
  • the hydrosilylation reaction may be performed in the presence or absence of a solvent.
  • the resulting fluorine-containing ether composition contains a compound (AH) produced by the reaction and a transition metal compound, and the mass ratio of the transition metal compound to the compound (AH) is 300 to 4,000 ppm in terms of transition metal. It is a composition.
  • HSiR n L 3-n (S) L is a hydroxyl group or a hydrolysable group, R is a hydrogen atom or a monovalent hydrocarbon group, n is an integer from 0 to 2, when n is 0 or 1, (3-n) L's may be the same or different; When n is 2, n R may be the same or different.
  • Compound (B) has a poly (oxyperfluoroalkylene) chain and a group (III).
  • -CH CH 2 (III)
  • the poly (oxyperfluoroalkylene) chain of the compound (B) is the same as the poly (oxyperfluoroalkylene) chain of the product compound (AX).
  • the poly (oxyperfluoroalkylene) chain that the compound (AX) has is the same as the PFE chain that the compound (A) has.
  • the group (III) possessed by the compound (B) may be one or two or more. Two or more are preferable and three or more are particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the bond with the substrate. 10 or less is preferable, 5 or less is more preferable, and 4 or less is particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the density of molecules bonded to the substrate. Accordingly, the group (III) of the compound (B) is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 3 to 4.
  • the group (III) possessed by the compound (B) reacts with the compound (S) described later (hydrosilylation reaction), whereby the group (IX) possessed by the compound (AX) described later is obtained.
  • a preferred embodiment of compound (B) is compound (B1). [R f1 —OQR fe —] a Y 1 [—CH ⁇ CH 2 ] b (B1)
  • R f1 , Q, R fe , a and b are as defined above
  • Y 1 is a (a + b) -valent linking group
  • a [R f1 -OQR fe- ] may be the same or different.
  • R f1 is the same as R f1 in the group (II), preferable embodiments thereof are also the same.
  • a R f1 is preferably the same in number of carbon atoms, and from the viewpoint of ease of production, the same group, that is, the same number of carbon atoms and the same chemical structure. Is preferred.
  • the group having the same carbon number and the same chemical structure means that, for example, when a is 2, two R f1 are CF 3 CF 2 CF 2 — (the two R f1 (It is not a combination of CF 3 CF 2 CF 2 — and CF 3 CF (CF 3 ) —, which have the same carbon number but different chemical structures.)
  • Q is the same as Q in the group (II), and preferred embodiments are also the same.
  • the poly (oxyperfluoroalkylene) chain of R fe is the same as described above, and the preferred embodiment is also the same.
  • Preferred values for a are the same as the preferred number of PFE chains that compound (A) has. That is, each a is preferably an integer of 1 to 3.
  • the preferable value of b is the same as the preferable number of groups (I) that the compound (A) has. That is, b is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and particularly preferably an integer of 3 to 4.
  • Y 1 is, for example, a (a + b) -valent substituted or unsubstituted hydrocarbon group, a group or atom other than a hydrocarbon group at the carbon-carbon atom or / and terminal of the substituted or unsubstituted hydrocarbon group.
  • Examples thereof include (a + b) -valent groups and (a + b) -valent organopolysiloxane groups.
  • Examples of the unsubstituted hydrocarbon group include a linear or branched saturated hydrocarbon group, an aromatic hydrocarbon cyclic group (for example, (a + b) hydrogen atoms from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring).
  • a group excluding an atom a group composed of a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, an alkyl group bonded to the aromatic hydrocarbon cyclic group as a substituent)
  • groups having an arylene group such as a phenylene group between and / or at the terminal of the saturated hydrocarbon group), and a group formed of a combination of two or more aromatic hydrocarbon cyclic groups.
  • a linear or branched saturated hydrocarbon group is preferable.
  • the number of carbon atoms of the unsubstituted hydrocarbon group is preferably 20 or less.
  • the substituted hydrocarbon group is a group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with a substituent.
  • the substituent include a hydroxyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an amino group, a nitro group, a cyano group, and an aminocarbonyl group.
  • Examples of the group or atom other than the hydrocarbon group between the carbon-carbon atoms and / or the terminal of the hydrocarbon group include an etheric oxygen atom (—O—), a thioetheric sulfur atom (—S—), a nitrogen atom ( —N ⁇ ), silicon atom (> Si ⁇ ), carbon atom (> C ⁇ ), —N (R 15 ) —, —C (O) N (R 15 ) —, —OC (O) N (R 15 )-, -Si (R 16 ) (R 17 )-, organopolysiloxane groups, -C (O)-, -C (O) -O-, -C (O) -S- and the like.
  • R 15 is a hydrogen atom, an alkyl group or a phenyl group
  • R 16 to R 17 are each independently an alkyl group or a phenyl group.
  • the alkyl group preferably has 1 to 6 carbon atoms.
  • the organopolysiloxane group may be linear, branched, or cyclic.
  • the compound (S) is a compound represented by the following formula (S). HSiR n L 3-n (S) However, L is a hydroxyl group or a hydrolysable group, R is a hydrogen atom or a monovalent hydrocarbon group, n is an integer from 0 to 2, when n is 0 or 1, (3-n) L's may be the same or different; When n is 2, n R may be the same or different.
  • R, L and n in the formula (S) are the same as R, L and n in the group (I).
  • HSi (OCH 3 ) 3 As the compound (S), HSi (OCH 3 ) 3 , HSiCH 3 (OCH 3 ) 2 , HSi (OCH 2 CH 3 ) 3 , HSiCl 3 , HSi (OCOCH 3 ) 3 and HSi (NCO) 3 are preferable.
  • HSi (OCH 3 ) 3 is particularly preferable from the viewpoint of easy handling in industrial production.
  • Transition metal compounds examples include those exemplified above.
  • the organic solvent may be a fluorinated organic solvent or a non-fluorinated organic solvent, or both solvents may be used.
  • the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
  • the fluorinated alkane a compound having 4 to 8 carbon atoms is preferable.
  • Examples of commercially available products include C 6 F 13 H (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC-2000), C 6 F 13 C 2 H 5 (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC-6000). ), C 2 F 5 CHFCHFCF 3 (manufactured by Chemers, Bertrell (registered trademark) XF) and the like.
  • Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorobenzene, bis ( ⁇ trifluoromethyl) benzene, and the like.
  • fluoroalkyl ether a compound having 4 to 12 carbon atoms is preferable.
  • examples of commercially available products include CF 3 CH 2 OCF 2 CF 2 H (Asahi Glass Co., Ltd., Asahiklin (registered trademark) AE-3000), C 4 F 9 OCH 3 (3M Co., Novec (registered trademark) 7100).
  • C 4 F 9 OC 2 H 5 manufactured by 3M, Novec (registered trademark) 7200
  • C 6 F 13 OCH 3 manufactured by 3M, Novec (registered trademark) 7300
  • fluorinated alkylamine examples include perfluoropolypropylamine and perfluoropolybutylamine.
  • fluoroalcohol examples include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
  • the fluorine-based organic solvent is at least one fluorine-containing compound selected from the group consisting of a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether in terms of compatibility between the compound (B) and the compound (S). It is preferable to use an organic solvent.
  • non-fluorine organic solvent a compound consisting only of hydrogen and carbon atoms, a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferred, hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, esters System organic solvents.
  • hydrocarbon-based organic solvent include hexane, heptane, and hexane hexane.
  • ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • ether-based organic solvents include diethyl ether, terahydrofuran, and teraethylene glycol dimethyl ether.
  • ester organic solvent include ethyl acetate and butyl acetate.
  • a hydrocarbon organic solvent is particularly preferable from the viewpoint of compatibility of the compound (B) and the compound (S).
  • the amount of the solvent used is preferably 0.1 to 10,000 parts by mass, particularly preferably 1 to 1,000 parts by mass with respect to 100 parts by mass of the compound (B).
  • amount of the solvent used is within the above range, there is an effect of sufficiently compatibilizing the compound (B) and the compound (S), and the reaction conditions can be moderated.
  • the hydrosilylation reaction between the compound (B) and the compound (S) in the presence of the transition metal compound is, for example, a resin container such as a polyolefin or a fluorine-containing resin, a glass container, a metal container such as SUS, or the like.
  • a lining container coated with a fluororesin is used.
  • the reaction temperature is preferably 0 to 100 ° C., particularly preferably 20 to 50 ° C., from the viewpoint that the reaction proceeds sufficiently and the formation of by-products is suppressed.
  • the reaction time is preferably 1 to 100 hours, particularly preferably 2 to 20 hours.
  • the reaction pressure is preferably ⁇ 0.01 to 1 MPaG, particularly preferably 0 to 0.1 MPaG.
  • “G” in “MPaG” indicates a gauge pressure.
  • a transition metal compound is used in a hydrosilylation reaction in a mass ratio of 300 to 4,000 ppm in terms of transition metal relative to the compound (B).
  • the amount of the transition metal compound used is preferably 400 to 2,000 ppm, particularly preferably 500 to 1,000 ppm, in terms of transition metal.
  • the amount of the transition metal compound used here is the amount relative to the compound (B), but the amount of the transition metal compound used is approximately equal to the ratio of the transition metal compound to the product compound (AX).
  • L is a halogen atom (for example, HSiCl 3 or the like) as the compound (S)
  • an ortho ester such as methyl orthoformate may be used in combination.
  • the compound in which the halogen atom of L is substituted with an alkoxy group is introduced into the compound (B).
  • reaction solution may be concentrated after the reaction to remove the solvent.
  • a transition metal compound is not added to the compound (AX) produced, but a transition metal compound is added to the compound (AX) produced as necessary. May be.
  • the addition amount of the transition metal compound is preferably such that the mass ratio of the transition metal compound to the compound (AX) is 300 to 4,000 ppm in terms of transition metal. An amount of 2,000 ppm is more preferable, and an amount of 500 to 1,000 ppm is particularly preferable.
  • Compound (AX) has a poly (oxyperfluoroalkylene) chain and a group (IX). —CH 2 CH 2 —SiR n L 3-n (IX)
  • L is a hydroxyl group or a hydrolysable group
  • R is a hydrogen atom or a monovalent hydrocarbon group
  • n is an integer from 0 to 2, when n is 0 or 1, (3-n) L's may be the same or different; When n is 2, n R may be the same or different.
  • the poly (oxyperfluoroalkylene) chain of the compound (AX) is the same as the PFE chain of the compound (A).
  • the fluorine-containing ether compounds described in International Publication No. 2014/163004, International Publication No. 2013/121984, and Japanese Patent Application Laid-Open No. 2015-199906, and the following compound (AX1) are preferable.
  • a preferred embodiment of compound (AX) is compound (AX1). [R f1 -OQR fe- ] a Z 1X [-SiR n L 3-n ] b (AX1)
  • R f1 , Q, R fe , L, R, n, a and b are as defined above
  • Z 1X is a (a + b) -valent linking group, and has —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n
  • a [R f1 -OQR fe- ] may be the same or different
  • b [-SiR n L 3-n ] may be the same or different.
  • Z 1X examples include a group having —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n in Z 1 of the formula (A1). That is, the compound (AX1) is the compound (A1) in which Z 1 has —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n .
  • Examples of the method for producing compound (A11) include the following methods (1) to (6).
  • examples of the method for producing compound (A11) include the following methods (11) to (16).
  • Method (1) Commercially available compound (10) is used as starting material. HO—CH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (10) However, (R F1 O) x is a poly (oxyperfluoroalkylene) chain, and x is an integer of 1 or more.
  • compound (10) is reacted with R f1 —O—CF ⁇ CF 2 to obtain a mixture of compound (11), compound (3A) and unreacted compound (10).
  • Compound (11) is isolated from the mixture, and compound (12) is obtained by esterification reaction of compound (11) and CF 3 CF 2 CF 2 OCF (CF 3 ) C (O) F.
  • the esterification reaction may be a reaction between the compound (11) and another acid fluoride, acid chloride, acid bromide, acid anhydride or the like.
  • a compound (13) is obtained by substituting the fluorine atom for the hydrogen atom of the compound (12) using fluorine gas.
  • the fluorination step can be performed, for example, according to the method described in International Publication No. 2000/56694.
  • Compound (14) is obtained by reacting compound (13) with an alcohol (methanol, ethanol, 1-propanol, 2-propanol, etc., hereinafter referred to as R 10 OH, R 10 is an alkyl group).
  • Compound (15) is obtained by subjecting compound (14) to hydrogen reduction using a reducing agent (sodium borohydride, lithium aluminum hydride, etc.).
  • a reducing agent sodium borohydride, lithium aluminum hydride, etc.
  • Method (2) The compound (11) obtained in method (1) is used as starting material.
  • R f1 O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (11)
  • Compound (16B) is obtained by reacting compound (11) with CF 3 SO 2 Cl in the presence of a basic compound.
  • R f1 O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OSO 2 CF 3 (16B)
  • the compound (17B) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal with respect to the compound (17B) and, if necessary, a solvent, to give a compound ( 1B) is obtained.
  • Compound (16C) is obtained by reacting compound (15C) with CF 3 SO 2 Cl in the presence of a basic compound.
  • the compound (17D) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (17D).
  • Method (5) The compound (11) obtained in method (1) is used as starting material.
  • R f1 O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (11)
  • the compound (17E) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17E) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1E) is obtained.
  • the compound (17F) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17F) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1F).
  • Method (11) The compound (14) obtained in method (1) is used as a starting material.
  • the compound (17G) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17G) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1G) is obtained.
  • Method (12) The compound (11) obtained in method (1) is used as starting material.
  • R f1 O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (11)
  • the compound (17H) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (17H).
  • R f1 O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —C (O) NH—R 34 —C [CH 2 CH 2 CH 2 —SiR n L 3-n ] 3. .. (1H)
  • the compound (17I) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17I) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1I) is obtained.
  • Compound (17) is obtained by reacting compound (11) with compound (30) obtained in method (14) in the presence of a basic compound.
  • R f1 O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R 34 —C (CH 2 CH ⁇ CH 2 3 ... (17K)
  • the compound (17L) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17L) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1L).
  • the compound (40) is reacted with R f1 —O—CF ⁇ CF 2 to obtain a mixture of the compound (41), the compound (3A ′) and the unreacted compound (40).
  • Compound (41) is isolated from the mixture, and compound (42) is obtained by esterification reaction of compound (41) and CF 3 CF 2 CF 2 OCF (CF 3 ) COF.
  • the esterification reaction may be a reaction between the compound (41) and another acid fluoride, acid chloride, acid bromide, acid anhydride or the like.
  • R f1 O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OCOCF (CF 3 ) OCF 2 CF 2 CF 3 (42)
  • a compound (43) is obtained by substituting the fluorine atom for the hydrogen atom of the compound (42) using fluorine gas.
  • the fluorination step can be performed, for example, according to the method described in International Publication No. 2000/56694.
  • Compound (44) is obtained by reacting compound (43) with alcohol (methanol, ethanol, 1-propanol, 2-propanol, etc., hereinafter referred to as ROH, R is an alkyl group).
  • ROH methanol, ethanol, 1-propanol, 2-propanol, etc., hereinafter referred to as ROH, R is an alkyl group).
  • the compound (44) represented by the following formula (45) is obtained by hydrogen reduction of the compound (44) using a reducing agent (sodium borohydride, lithium aluminum hydride, etc.).
  • a reducing agent sodium borohydride, lithium aluminum hydride, etc.
  • Compound (47) is obtained by reacting compound (46) with HN (CH 2 CH ⁇ CH 2 ) 2 in the presence of a basic compound.
  • the compound (47) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (47). 4A) is obtained.
  • Method (22) The compound (41) obtained in method (21) is used as starting material.
  • R f1 O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (41)
  • Compound (47B) is obtained by reacting compound (46B) with HN (CH 2 CH ⁇ CH 2 ) 2 in the presence of a basic compound.
  • the compound (47B) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (47B).
  • the compound (4B) represented by (4B) is obtained.
  • Compound (16C) is obtained by reacting compound (45C) with CF 3 SO 2 Cl in the presence of a basic compound.
  • compound (46C) is reacted with HN (CH 2 CH ⁇ CH 2 ) 2 to obtain compound (47C) represented by the following formula (47C).
  • the compound (47C) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (47C).
  • the compound (4C) represented by (4C) is obtained.
  • “Production Method of Compound (A13)” As a manufacturing method of a compound (A13), the following method is mentioned, for example.
  • the compound (2) and the compound (3) are reacted to obtain a crude product.
  • the crude product contains a plurality of types of compounds (4) having different ratios of e and f.
  • the compound (4) in which the ratio of e to f is a desired ratio is separated from the crude product by a known means (column purification or the like).
  • Compound (5) is obtained by reacting compound (4) with trifluoromethanesulfonic anhydride in the presence of a base such as 2,6-lutidine.
  • a base such as 2,6-lutidine.
  • Compound (7) is obtained by reacting compound (5) with compound (6) in the presence of a base.
  • [-O-R 54 -CH CH 2 ] f (7)
  • Examples of the compound (2) in which e + f is 3 include glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol and the like.
  • Examples of the compound (2) in which e + f is 4 include diglycerin, pentaerythritol, ditrimethylolpropane, and the like.
  • Examples of the compound (2) in which e + f is 6 include dipentaerythritol, sorbitol, mannitol, dulcitol and the like.
  • Examples of the compound (3) include allyl bromide and 5-bromo-1-pentene.
  • Compound (6) can be produced, for example, by the method described in International Publication No. 2013/121984, International Publication No. 2014/163004, International Publication No. 2015/088792.
  • Examples of the compound (S) include trimethoxysilane, triethoxysilane, methyldimethoxysilane, and trichlor
  • the compound (2), the compound (3), the compound (6) and the compound (8) are appropriately selected, and the desired compound is selected by appropriately selecting the ratio of e to f in the compound (4) and carrying out each reaction. (A13) can be manufactured.
  • the method for producing a fluorinated ether composition according to the second embodiment is characterized in that the compound (B) and the compound (S) are mixed in a mass ratio of the transition metal compound to the compound (B). Is produced in the presence of a transition metal compound having a transition metal equivalent of 1 ppm or more and less than 300 ppm to produce a compound (AX), and the mass ratio of the transition metal compound to the compound (AX) is then a transition metal.
  • a transition metal compound is added to the reaction product so as to be 300 to 4,000 ppm in terms of conversion.
  • the hydrosilylation reaction may be performed in the presence or absence of a solvent.
  • the resulting fluorine-containing ether composition contains a compound (AH) produced by the reaction and a transition metal compound, and the mass ratio of the transition metal compound to the compound (AH) is 300 to 4,000 ppm in terms of transition metal. It is a composition.
  • the amount of the transition metal compound used in the hydrosilylation reaction is 300 to 4,000 ppm in terms of transition metal in the first embodiment, whereas it is 1 ppm or more and less than 300 ppm in the second embodiment, and In contrast to the generated compound (AX), in the first embodiment, it is not necessary to add a transition metal compound, whereas in the second embodiment, the second embodiment is the same except that a specific amount of the transition metal compound is added.
  • the first embodiment and the second embodiment are the same.
  • the durability of the surface layer is maintained without impairing the transparency of the substrate. Can be improved.
  • the amount of the transition metal compound added to the produced compound (AX) is preferably such that the mass ratio of the transition metal compound to the compound (AX) is 400 to 2,000 ppm in terms of transition metal, and 500 to 1,000 ppm. Is particularly preferred.
  • the transition metal compound used for the hydrosilylation reaction and the transition metal compound added to the generated compound (AX) may be the same type or different types. The same type is preferred.
  • the fluorine-containing ether composition of the present invention may be dissolved or dispersed in a liquid medium and used as a coating liquid. That is, the coating liquid contains the present composition and a liquid medium.
  • an organic solvent is preferable.
  • the organic solvent include a solvent used in the hydrosilylation reaction.
  • the solvent and the liquid medium contained in the coating liquid during the hydrosilylation reaction may be the same type or different types.
  • the content of the present composition is preferably 0.001 to 30% by mass, particularly preferably 0.1 to 20% by mass, based on the total mass of the coating liquid.
  • the content of the liquid medium is preferably 70 to 99.999% by mass, particularly preferably 80 to 99.9% by mass, based on the total mass of the coating liquid.
  • the solid concentration of the coating solution is preferably 0.001 to 10% by mass, particularly preferably 0.01 to 1% by mass, based on the total mass of the coating solution.
  • the solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120 ° C.
  • the concentration of the present composition can be calculated from the solid content concentration and the charged amounts of the present composition and solvent.
  • the article has a surface layer formed from the composition on the surface of the substrate.
  • the thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the surface layer is not less than the lower limit of the above range, the effect of the surface treatment can be sufficiently obtained. If the thickness of the surface layer is not more than the upper limit of the above range, the utilization efficiency is high.
  • the thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by an X-ray reflectivity method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G). It can be calculated.
  • the base material is a main body part of various articles (such as an optical lens, a touch panel, a display, and an optical recording medium) that require friction resistance and fingerprint stain removability, or a member constituting the surface of the article.
  • the substrate is not particularly limited as long as it is required to impart lubricity and water / oil repellency.
  • Examples of the material for the surface of the substrate include metal, resin, glass, sapphire, ceramic, stone, and a composite material thereof.
  • the glass may be chemically strengthened.
  • a base film such as a SiO 2 film may be formed on the surface of the substrate.
  • an optical lens, a substrate for touch panel, a substrate for display, and a substrate for optical recording medium are suitable, and a substrate for touch panel is particularly suitable.
  • the base material for touch panels has translucency. “Having translucency” means that a normal incidence visible light transmittance in accordance with JIS R3106: 1998 (ISO 9050: 1990) is 25% or more.
  • a material for the surface of the substrate in the optical lens, touch panel, display, and optical recording medium glass and transparent resin are preferable.
  • the article can be manufactured, for example, by the following method.
  • the present composition can be used as it is in a dry coating method.
  • This composition is suitable for forming a surface layer having excellent adhesion by a dry coating method.
  • Examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method.
  • the vacuum deposition method is particularly preferable from the viewpoint of suppressing the decomposition of the compound (A) and the simplicity of the apparatus.
  • the temperature during vacuum deposition is preferably 20 to 300 ° C, particularly preferably 30 to 200 ° C.
  • the pressure during vacuum deposition is preferably 1 ⁇ 10 ⁇ 1 Pa or less, particularly preferably 1 ⁇ 10 ⁇ 2 Pa or less.
  • Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, ink jet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. Examples thereof include a coating method.
  • an operation for promoting the reaction between the compound (A) and the substrate may be performed as necessary.
  • the operation include heating, humidification, and light irradiation.
  • hydrolysis reaction of hydrolyzable silyl groups to silanol groups reaction of hydroxyl groups on the substrate surface with silanol groups, silanols, Reactions such as formation of siloxane bonds by group condensation reactions can be promoted.
  • compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific methods include, for example, a method of pouring a solvent over the surface layer and a method of wiping with a cloth soaked with a solvent.
  • the present composition and the coating liquid containing the present composition contain the compound (A) and a specific amount of the transition metal compound, a surface layer having excellent durability can be formed. That is, by forming a surface layer on the surface of the substrate using the present composition or a coating liquid containing the present composition, excellent properties such as initial water and oil repellency are imparted, and Even if it is repeatedly rubbed, it is possible to obtain excellent durability in which the characteristics are not easily lowered. The reason is considered as follows.
  • the present composition contains 300 ppm or more of a transition metal compound in terms of transition metal with respect to the compound (A), the hydrolysis reaction of the hydrolyzable silyl group in the compound (A) to a silanol group, and the silanol
  • base material—OH base material
  • the number of chemical bonds (base material—O—Si) between the hydroxyl group and the silanol group on the surface of the base material increases.
  • An increase in the number of chemical bonds between the hydroxyl groups and silanol groups on the surface of the substrate is considered to contribute to the improvement of durability.
  • the surface layer formed from this composition is less likely to deteriorate the water and oil repellency even if the surface is repeatedly rubbed, so that it can easily remove fingerprint stains on the surface of the substrate (removal of fingerprint stains).
  • this inventor discovered that a base material will color when the mass ratio of a transition metal compound exceeds 4,000 ppm in conversion of a transition metal with respect to a compound (A). Therefore, the mass ratio of the transition metal compound to the compound (A) is set to 4,000 ppm or less in terms of transition metal.
  • the mass ratio of the transition metal compound to the compound (A) is small, specifically, when it is 10 ppm or less in terms of transition metal, the durability of the surface layer is inferior, but the fluorine-containing ether composition containing the compound (A) There is a tendency for the storage stability of to increase. Therefore, when the storage stability of the composition is more important than the durability of the surface layer, the mass ratio of the transition metal compound to the compound (A) is preferably 10 ppm or less in terms of transition metal.
  • the amount of the transition metal compound used is 0. It may be 1 to 10 ppm.
  • the hydrosilylation reaction is performed using a transition metal compound in excess of 10 ppm in terms of transition metal, the transition metal compound is removed by performing post-treatment such as activated carbon treatment and molecular distillation after the reaction, and the compound (A ) May be adjusted to 10 ppm or less in terms of transition metal.
  • the water contained in the activated carbon to be used is brought into the compound (AX), it may take time to remove the water. Therefore, a method in which a hydrosilylation reaction is performed using 0.1 to 10 ppm of a transition metal compound in terms of transition metal is preferable.
  • the number average molecular weight of the fluorinated ether compound was calculated by determining the number (average value) of oxyperfluoroalkylene groups based on the terminal groups by 1 H-NMR and 19 F-NMR.
  • the terminal group is, for example, group (I) or group (II).
  • a reciprocating traverse tester manufactured by KE NTE was used in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), a steel wool bonster (# 0000) was loaded at a rate of 0.5 kg / cm 2 , and the speed : Reciprocating at 320 cm / min.
  • the water contact angle was measured every 500 reciprocations, and the upper limit number of times that the water contact angle of 100 ° or more was maintained (the number of maintenance times of the contact angle of 100 ° or more) was determined. As the number of times increases, the surface layer is less likely to be damaged by friction, and the durability is excellent.
  • Example 1 The compound (51) was obtained according to the method described in Example 1-2 of International Publication No. 2014/163004. CF 3 CF 2 CF 2 —O—CHFCF 2 OCH 2 CF 2 O — ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ —CF 2 —CH 2 —O—CH 2 CH ⁇ CH 2. ⁇ (51) Average value of unit number m11: 21, Average value of unit number m12: 20, Number average molecular weight of compound (51): 4,200.
  • the substrate was surface-treated by the following wet coating method to obtain the article of Example 1. Chemically tempered glass was used as the substrate. The obtained article was evaluated for durability and coloring of the substrate. The results are shown in Table 1.
  • ⁇ Wet coating method> The obtained composition was mixed with C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200) as a liquid medium to prepare a coating solution having a solid content concentration of 20%.
  • the substrate was dipped in the coating solution, and after standing for 30 minutes, the substrate was pulled up (dip coating method).
  • the coating film was dried at 200 ° C. for 30 minutes and washed with dichloropentafluoropropane (Asahi Glass Co., Ltd., AK-225) to obtain an article having a surface layer on the surface of the substrate.
  • Example 2 In the hydrosilylation reaction, the amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) used was 1.50625 g (based on compound (51)). Except that the amount of platinum used was changed to equivalent to 1,205 ppm, a composition of compound (52-1) and compound (52-2) and platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. Further, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 1,000 ppm. An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
  • Example 3 In the hydrosilylation reaction, a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) was used in an amount of 3.0125 g (based on compound (51)). Except that the amount of platinum used was changed to equivalent to 2,410 ppm, a composition of compound (52-1) and compound (52-2) with platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. Further, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 2,000 ppm. An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
  • Example 4 The compound (14I-1) was obtained according to the method described in Example 6 of WO2013 / 121984. CF 3 -O- (CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) x3 (CF 2 CF 2 O) -CF 2 CF 2 CF 2 -C (O) OCH 3 ⁇ (14I- 1) Average value of number of units ⁇ 3: 13, number average molecular weight of compound (14I-1): 4,700.
  • the mass ratio of platinum to the compound (63) corresponding to the compound (A) was 2,000 ppm.
  • m11: m12 47: 53 and m11 + m12 ⁇ 43.
  • Example 6 In the hydrosilylation reaction, the amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) used was 7.53125 g (based on compound (51)). Except that the amount of platinum used was changed to 6,025 ppm), a composition of compound (52-1) and compound (52-2) and platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. In addition, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 5,000 ppm. An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
  • Example 7 In the hydrosilylation reaction, the amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) used was 0.150625 g (based on compound (51)). Except that the amount of platinum used was changed to 120.5 ppm, a composition of compound (52-1) and compound (52-2) and platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. Further, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 100 ppm. An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
  • Example 8 In the hydrosilylation reaction, the amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) used was 0.00753125 g (based on compound (51)). Except that the amount of platinum used was changed to 6.025 ppm, a composition of compound (52-1) and compound (52-2) and platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. Further, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 5 ppm. An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
  • compositions of Examples 1 to 5 in which the mass ratio of platinum to the compound (A) is 300 to 4,000 ppm are compared with the compositions of Examples 7 and 8 in which the mass ratio of platinum to the compound (A) is 100 ppm or less.
  • a surface layer having excellent durability could be formed.
  • the compositions of Examples 1 to 5 are surface layers excellent in durability without hindering the transparency of the substrate as compared with the composition of Example 6 in which the mass ratio of platinum to the compound (A) is 5,000 ppm. could be formed.
  • the composition of Example 8 was stored at 60 ° C. and 90% RH for 2 months, no turbidity, separation, precipitation, or solidification occurred, and transparency was maintained and storage stability was maintained. It was excellent.
  • the composition and the coating liquid containing the composition can be used for various applications that are required to impart water and oil repellency.
  • display input devices such as touch panels; surface protective coatings made of transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members, antifouling coatings for kitchens; water and moisture repellent coatings for electronic devices, heat exchangers, batteries, etc.
  • More specific examples of use include a front protective plate of a display, an antireflection plate, a polarizing plate, an antiglare plate, or an antireflection coating on the surface thereof, a touch panel of a device such as a mobile phone or a portable information terminal.

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Abstract

Provided are: a fluorinated ether composition which can be formed into a surface layer having excellent durability without deteriorating the transparency of a base; and a method for producing a fluorinated ether composition. A fluorinated ether composition containing a compound (A) having a poly(oxyperfluoroalkylene) chain and a group represented by formula (I) and a transition metal compound, wherein the ratio of the mass of the transition metal compound to the mass of the compound (A) is 300 to 4,000 ppm in terms of a transition metal content. (I) -SiRnL3-n; wherein L represents a hydroxyl group or a hydrolysable group, R represents a hydrogen atom or a monovalent hydrocarbon group, and n represents an integer of 0 to 2.

Description

含フッ素エーテル組成物およびその製造方法Fluorine-containing ether composition and method for producing the same
　本発明は、含フッ素エーテル組成物およびその製造方法に関する。 The present invention relates to a fluorine-containing ether composition and a method for producing the same.
　含フッ素化合物は、高い潤滑性、撥水撥油性等を示すことから、表面処理剤等に用いられる。たとえば表面処理剤として基材の表面に塗布し表面層を形成すると、潤滑性、撥水撥油性等が付与され、基材の表面の汚れを拭き取りやすくなり、汚れの除去性が向上する。含フッ素化合物の中でも、ペルフルオロアルキル鎖の途中にエーテル結合（－Ｏ－）が存在するポリ（オキシペルフルオロアルキレン）鎖を有する含フッ素エーテル化合物は、油脂等の汚れの除去性に優れる。
　このような含フッ素エーテル化合物は、拭き取りによって表面に付着した指紋を容易に除去できる性能（指紋汚れ除去性）を有するため、たとえば、タッチパネルの、指で触れる面を構成する部材の表面処理剤に用いられている。 Since the fluorine-containing compound exhibits high lubricity, water / oil repellency, etc., it is used as a surface treatment agent or the like. For example, when the surface layer is applied as a surface treatment agent to form a surface layer, lubricity, water and oil repellency, etc. are imparted, and the dirt on the surface of the base material can be easily wiped off, thereby improving the dirt removability. Among fluorine-containing compounds, fluorine-containing ether compounds having a poly (oxyperfluoroalkylene) chain in which an ether bond (—O—) is present in the middle of the perfluoroalkyl chain are excellent in the removal of dirt such as fats and oils.
Since such a fluorine-containing ether compound has a performance (fingerprint stain removal property) that can easily remove fingerprints attached to the surface by wiping off, for example, as a surface treatment agent for a member constituting a touch surface of a touch panel. It is used.
　ガラスや金属等の基材の表面に形成される表面層に指紋汚れ除去性等の性能を付与するためには、たとえば、含フッ素エーテル化合物の末端に加水分解性シリル基を導入し、含フッ素エーテル化合物と基材とを化学結合させればよい。加水分解性シリル基を有する含フッ素エーテル化合物の被膜は、加水分解性シリル基が加水分解してシラノール基を形成し、該シラノール基が基材の表面に結合する。 In order to impart performance such as fingerprint stain removability to the surface layer formed on the surface of a substrate such as glass or metal, for example, a hydrolyzable silyl group is introduced at the end of the fluorine-containing ether compound, What is necessary is just to chemically bond an ether compound and a base material. In the coating of the fluorine-containing ether compound having a hydrolyzable silyl group, the hydrolyzable silyl group is hydrolyzed to form a silanol group, and the silanol group is bonded to the surface of the substrate.
　含フッ素エーテル化合物の末端に加水分解性シリル基を導入する方法としては、原料化合物の分子の末端に２－プロペニル基（－ＣＨ２ＣＨ＝ＣＨ２、慣用名：アリル基）を導入し、次いで、２－プロペニル基が導入された化合物にヒドロシラン化合物を反応させて、ヒドロシリル化する方法が好適に用いられる。ヒドロシリル化反応は、たとえば、微量の遷移金属化合物の存在下で行われる（特許文献１～４）。 As a method of introducing a hydrolyzable silyl group into the terminal of the fluorine-containing ether compound, a 2-propenyl group (—CH 2 CH═CH 2 , commonly used name: allyl group) is introduced into the terminal of the molecule of the raw material compound, A method in which a hydrosilane compound is reacted with a compound into which a 2-propenyl group has been introduced and hydrosilylated is preferably used. The hydrosilylation reaction is performed, for example, in the presence of a trace amount of a transition metal compound (Patent Documents 1 to 4).
国際公開第２０１４／１６３００４号International Publication No. 2014/163004 国際公開第２０１４／０６９５９２号International Publication No. 2014/069592 特開２０１５－１９９９０６号公報JP 2015-199906 A 国際公開第２０１５／０８７９０３号International Publication No. 2015/087903
　しかし、特許文献１～４に記載の方法によりヒドロシリル化して得られる、末端に加水分解性シリル基を有する含フッ素エーテル化合物を基材の表面にコーティングして形成される表面層は、耐久性が必ずしも充分ではない。
　タッチパネル等は、指で繰り返し摩擦されるため、基材の表面に形成される表面層には、長期間性能を維持できる耐久性が求められる。特に、屋外使用のタッチパネル（自動販売機、案内板等のデジタルサイネージ）、車載タッチパネル等においては、表面層に高い耐久性が求められる。加えて、表面層を設けた基材には、高い透明性が求められる。 However, the surface layer formed by coating the surface of the base material with a fluorine-containing ether compound having a hydrolyzable silyl group at the end, obtained by hydrosilylation by the methods described in Patent Documents 1 to 4, has durability. Not always enough.
Since a touch panel or the like is repeatedly rubbed with a finger, the surface layer formed on the surface of the base material is required to have durability capable of maintaining performance for a long period of time. In particular, in a touch panel for outdoor use (digital signage such as a vending machine or a guide board), an in-vehicle touch panel, etc., high durability is required for the surface layer. In addition, a substrate provided with a surface layer is required to have high transparency.
　本発明は、基材の透明性を損なうことなく、耐久性に優れる表面層を形成できる含フッ素エーテル組成物および含フッ素エーテル組成物の製造方法の提供を目的とする。 An object of the present invention is to provide a fluorine-containing ether composition and a method for producing the fluorine-containing ether composition capable of forming a surface layer having excellent durability without impairing the transparency of the substrate.
　本発明は、以下［１］～［１３］の構成を有する、含フッ素エーテル組成物および含フッ素エーテル化合物の製造方法を提供できる。
　［１］ポリ（オキシペルフルオロアルキレン）鎖および下式（Ｉ）で表される基を有する化合物（Ａ）と、遷移金属化合物とを含む含フッ素エーテル組成物であって、
　前記化合物（Ａ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍであることを特徴とする含フッ素エーテル組成物。
　－ＳｉＲｎＬ３－ｎ　・・・（Ｉ）
　ただし、Ｌは水酸基または加水分解性基であり、
　Ｒは水素原子または１価の炭化水素基であり、
　ｎは０～２の整数であり、
　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。 The present invention can provide a fluorine-containing ether composition and a method for producing a fluorine-containing ether compound having the following configurations [1] to [13].
[1] A fluorine-containing ether composition comprising a compound (A) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (I), and a transition metal compound,
A fluorine-containing ether composition, wherein a mass ratio of the transition metal compound to the compound (A) is 300 to 4,000 ppm in terms of transition metal.
-SiR n L 3-n (I)
However, L is a hydroxyl group or a hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
When n is 2, n R may be the same or different.
　［２］前記化合物（Ａ）が、下式（Ａ１）で表される化合物である、［１］に記載の含フッ素エーテル組成物。
　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］ａＺ１［－ＳｉＲｎＬ３－ｎ］ｂ　・・・（Ａ１）
　ただし、Ｌ、Ｒおよびｎはそれぞれ前記と同義であり、
　Ｒｆ１は、ペルフルオロアルキル基であり、
　Ｑは、単結合、１個以上の水素原子を含むオキシフルオロアルキレン基、または該オキシフルオロアルキレン基の２～５個が結合してなるポリオキシフルオロアルキレン基であり、該基を構成するオキシフルオロアルキレン基は全てが同一であっても異なっていてもよく、
　Ｒｆｅは、前記ポリ（オキシペルフルオロアルキレン）鎖であり、
　Ｚ１は、（ａ＋ｂ）価の連結基であり、
　ａは、１以上の整数であり、
　ｂは、１以上の整数であり、
　ａが２以上のときａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は、同一であっても異なっていてもよく、
　ｂが２以上のときｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。 [2] The fluorine-containing ether composition according to [1], wherein the compound (A) is a compound represented by the following formula (A1).
[R f1 -OQR fe- ] a Z 1 [-SiR n L 3-n ] b (A1)
However, L, R, and n are respectively synonymous with the above,
R f1 is a perfluoroalkyl group;
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups. The alkylene groups may all be the same or different,
R fe is the poly (oxyperfluoroalkylene) chain,
Z 1 is a (a + b) -valent linking group,
a is an integer of 1 or more,
b is an integer of 1 or more,
When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different,
When b is 2 or more, b [-SiR n L 3-n ] may be the same or different.
　［３］前記ポリ（オキシペルフルオロアルキレン）鎖が、｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝、｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１２｝、｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１２｝または（ＣＦ２ＣＦ２Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１５である（ただし、ｍ１１は１以上の整数であり、ｍ１２は１以上の整数であって（ｍ１１＋ｍ１２）は２～２００の整数であり、ｍ１５は１～１００の整数である。）、［１］または［２］に記載の含フッ素エーテル組成物。
　［４］前記ａが１～３の整数であって、ａが２または３の場合ａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は同一であり、前記ｂが２～５の整数であって、ｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一である、［３］に記載の含フッ素エーテル組成物。
　［５］前記化合物（Ａ）の数平均分子量（Ｍｎ）が、２，０００～２０，０００である、［１］～［４］のいずれかに記載の含フッ素エーテル化合物。
　［６］前記遷移金属化合物が、ヒドロシリル化反応の触媒として作用する遷移金属化合物である、［１］～［５］のいずれかに記載の含フッ素エーテル組成物。
　［７］前記遷移金属化合物が白金化合物である、［１］～［６］のいずれかに記載の含フッ素エーテル組成物。
　［８］前記［１］～［７］のいずれかに記載の含フッ素エーテル組成物と、液状媒体とを含むことを特徴とするコーティング液。
　［９］前記［１］～［７］のいずれかに記載の含フッ素エーテル組成物から形成された表面層を有することを特徴とする物品。 [3] The poly ( oxyperfluoroalkylene ) chain is {(CF 2 O) m11 (CF 2 CF 2 O) m12 }, {(CF 2 O) m11 (CF 2 CF 2 CF 2 O) m12 }, { (CF 2 O) m11 (CF 2 CF 2 CF 2 CF 2 O) m12 } or (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) m15 (where m11 is an integer of 1 or more) M12 is an integer of 1 or more, (m11 + m12) is an integer of 2 to 200, and m15 is an integer of 1 to 100), or a fluorine-containing ether composition according to [1] or [2] .
[4] When a is an integer of 1 to 3 and a is 2 or 3, a number of [R f1 —OQR fe —] is the same, and b is an integer of 2 to 5 The b-containing [—SiR n L 3-n ] is the same, and the fluorine-containing ether composition according to [3].
[5] The fluorine-containing ether compound according to any one of [1] to [4], wherein the compound (A) has a number average molecular weight (Mn) of 2,000 to 20,000.
[6] The fluorine-containing ether composition according to any one of [1] to [5], wherein the transition metal compound is a transition metal compound that acts as a catalyst for a hydrosilylation reaction.
[7] The fluorine-containing ether composition according to any one of [1] to [6], wherein the transition metal compound is a platinum compound.
[8] A coating liquid comprising the fluorinated ether composition according to any one of [1] to [7] and a liquid medium.
[9] An article having a surface layer formed from the fluorine-containing ether composition according to any one of [1] to [7].
　［１０］ポリ（オキシペルフルオロアルキレン）鎖および下式（ＩＸ）で表される基を有する化合物（ＡＨ）と、遷移金属化合物とを含み、前記化合物（ＡＨ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍである含フッ素エーテル組成物を製造する方法であって、
　ポリ（オキシペルフルオロアルキレン）鎖および下式（ＩＩＩ）で表される基を有する化合物（Ｂ）と、下式（Ｓ）で表される化合物とを、前記化合物（Ｂ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍである量の前記遷移金属化合物の存在下に反応を行って、前記化合物（ＡＨ）を生成させることを特徴とする含フッ素エーテル組成物の製造方法。
　－ＣＨ＝ＣＨ２　・・・（ＩＩＩ）
　ＨＳｉＲｎＬ３－ｎ　・・・（Ｓ）
　－ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ　・・・（ＩＸ）
　ただし、Ｌは水酸基または加水分解性基であり、
　Ｒは水素原子または１価の炭化水素基であり、
　ｎは０～２の整数であり、
　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。 [10] A compound (AH) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (IX), and a transition metal compound, wherein the mass ratio of the transition metal compound to the compound (AH) is A method for producing a fluorine-containing ether composition having a transition metal equivalent of 300 to 4,000 ppm,
A compound (B) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (III), and a compound represented by the following formula (S) are converted into the transition metal compound for the compound (B): A method for producing a fluorine-containing ether composition, wherein the compound (AH) is produced by reacting in the presence of the transition metal compound in an amount of 300 to 4,000 ppm in terms of transition metal in terms of mass ratio .
-CH = CH 2 (III)
HSiR n L 3-n (S)
—CH 2 CH 2 —SiR n L 3-n (IX)
However, L is a hydroxyl group or a hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
When n is 2, n R may be the same or different.
　［１１］ポリ（オキシペルフルオロアルキレン）鎖および下式（ＩＸ）で表される基を有する化合物（ＡＨ）と、遷移金属化合物とを含み、前記化合物（ＡＨ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍである含フッ素エーテル組成物を製造する方法であって、
　ポリ（オキシペルフルオロアルキレン）鎖および下式（ＩＩＩ）で表される基を有する化合物（Ｂ）と、下式（Ｓ）で表される化合物とを、前記化合物（Ｂ）に対する前記遷移金属化合物の質量割合が遷移金属換算で１ｐｐｍ以上３００ｐｐｍ未満である量の前記遷移金属化合物の存在下に反応を行って前記化合物（ＡＨ）を生成させ、
　次いで、前記化合物（ＡＸ）に対する遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍとなるように、反応生成物に遷移金属化合物を添加することを特徴とする含フッ素エーテル組成物の製造方法。
　－ＣＨ＝ＣＨ２　・・・（ＩＩＩ）
　ＨＳｉＲｎＬ３－ｎ　・・・（Ｓ）
　－ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ　・・・（ＩＸ）
　ただし、Ｌは水酸基または加水分解性基であり、
　Ｒは水素原子または１価の炭化水素基であり、
　ｎは０～２の整数であり、
　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。
　［１２］前記化合物（ＡＸ）が、下式（ＡＸ１）で表される化合物である、［１０］または［１１］に記載の含フッ素エーテル組成物の製造方法。
　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］ａＺ１Ｘ［－ＳｉＲｎＬ３－ｎ］ｂ　・・・（ＡＸ１）
　ただし、Ｌ、Ｒおよびｎはそれぞれ前記と同義であり、
　Ｒｆ１は、ペルフルオロアルキル基であり、
　Ｑは、単結合、１個以上の水素原子を含むオキシフルオロアルキレン基、または該オキシフルオロアルキレン基の２～５個が結合してなるポリオキシフルオロアルキレン基であり、該基を構成するオキシフルオロアルキレン基は全てが同一であっても異なっていてもよく、
　Ｒｆｅは、前記ポリ（オキシペルフルオロアルキレン）鎖であり、
　Ｚ１Ｘは、（ａ＋ｂ）価の連結基であり、－ＳｉＲｎＬ３－ｎとの結合末端に－ＣＨ２ＣＨ２－を有し、
　ａは、１以上の整数であり、
　ｂは、１以上の整数であり、
　ａが２以上のときａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は、同一であっても異なっていてもよく、
　ｂが２以上のときｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。
　［１３］前記遷移金属化合物が白金化合物である、［１０］～［１２］のいずれかに記載の含フッ素エーテル組成物の製造方法。 [11] A compound (AH) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (IX), and a transition metal compound, wherein the mass ratio of the transition metal compound to the compound (AH) is A method for producing a fluorine-containing ether composition having a transition metal equivalent of 300 to 4,000 ppm,
A compound (B) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (III), and a compound represented by the following formula (S) are converted into the transition metal compound for the compound (B): Reaction is performed in the presence of an amount of the transition metal compound having a mass ratio of 1 ppm or more and less than 300 ppm in terms of transition metal to produce the compound (AH),
Next, the transition metal compound is added to the reaction product so that the mass ratio of the transition metal compound to the compound (AX) is 300 to 4,000 ppm in terms of transition metal. Production method.
-CH = CH 2 (III)
HSiR n L 3-n (S)
—CH 2 CH 2 —SiR n L 3-n (IX)
However, L is a hydroxyl group or a hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
When n is 2, n R may be the same or different.
[12] The method for producing a fluorinated ether composition according to [10] or [11], wherein the compound (AX) is a compound represented by the following formula (AX1).
[R f1 -OQR fe- ] a Z 1X [-SiR n L 3-n ] b (AX1)
However, L, R, and n are respectively synonymous with the above,
R f1 is a perfluoroalkyl group;
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups. The alkylene groups may all be the same or different,
R fe is the poly (oxyperfluoroalkylene) chain,
Z 1X is a (a + b) -valent linking group, and has —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n ,
a is an integer of 1 or more,
b is an integer of 1 or more,
When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different,
When b is 2 or more, b [-SiR n L 3-n ] may be the same or different.
[13] The method for producing a fluorinated ether composition according to any one of [10] to [12], wherein the transition metal compound is a platinum compound.
　本発明の含フッ素エーテル組成物によれば、基材の透明性を損なうことなく、耐久性に優れる表面層を形成できる。
　本発明の含フッ素エーテル組成物の製造方法によれば、基材の透明性を損なうことなく、耐久性に優れる表面層を形成できる含フッ素エーテル組成物を製造できる。 According to the fluorine-containing ether composition of the present invention, a surface layer having excellent durability can be formed without impairing the transparency of the substrate.
According to the method for producing a fluorine-containing ether composition of the present invention, a fluorine-containing ether composition capable of forming a surface layer having excellent durability can be produced without impairing the transparency of the substrate.
　本明細書において、式（１）で表される化合物を化合物（１）と記す。他の式で表される化合物も同様に記す。
　本明細書における以下の用語の意味は、以下の通りである。
　「加水分解性シリル基」とは、加水分解反応することによってシラノール基（Ｓｉ－ＯＨ）を形成し得る基を意味する。たとえば、式（Ｉ）中のＬが加水分解性基であり、－ＳｉＲｎＬ３－ｎが加水分解性シリル基である。
　オキシペルフルオロアルキレン基の化学式は、その酸素原子をペルフルオロアルキレン基の右側に記載して表すものとする。
　「表面層」とは、基材の表面に形成される層を意味する。
　コーティング液を塗布して「乾燥する」とは、コーティング液を基材に塗布して該基材上にコーティング液の塗膜を形成した後、該塗膜から液状媒体を蒸発除去することをいう。 In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
The meanings of the following terms in this specification are as follows.
The “hydrolyzable silyl group” means a group that can form a silanol group (Si—OH) by a hydrolysis reaction. For example, L in the formula (I) is a hydrolyzable group, and —SiR n L 3-n is a hydrolyzable silyl group.
The chemical formula of the oxyperfluoroalkylene group is expressed by describing the oxygen atom on the right side of the perfluoroalkylene group.
“Surface layer” means a layer formed on the surface of a substrate.
“Drying” by applying a coating solution refers to applying a coating solution to a substrate to form a coating film of the coating solution on the substrate, and then evaporating and removing the liquid medium from the coating film. .
〔含フッ素エーテル組成物〕
　本発明の含フッ素エーテル組成物（以下、本組成物とも記す。）は、以下に示す化合物（Ａ）と、遷移金属化合物とを含む。本組成物は、液状媒体を含まない。ただし、本組成物が不純物量の液状媒体を含むことは差し支えない。本組成物は、本発明の効果を損なわない範囲で、その他の成分を含んでいてもよい。その他の成分としては、後述する化合物（Ａ）以外の他の含フッ素エーテル化合物や、化合物（Ａ）、遷移金属化合物および他の含フッ素エーテル化合物以外の不純物、加水分解性シリル基の加水分解と縮合反応を促進する酸触媒や塩基性触媒等の公知の添加剤が挙げられる。化合物（Ａ）、遷移金属化合物および他の含フッ素エーテル化合物以外の不純物としては、化合物（Ａ）および他の含フッ素エーテル化合物の製造上不可避の化合物等が挙げられる。 [Fluorine-containing ether composition]
The fluorine-containing ether composition of the present invention (hereinafter also referred to as the present composition) contains the following compound (A) and a transition metal compound. The composition does not contain a liquid medium. However, the composition may contain a liquid medium having an impurity amount. The present composition may contain other components as long as the effects of the present invention are not impaired. As other components, other fluorine-containing ether compounds other than the compound (A) described later, impurities other than the compound (A), transition metal compounds and other fluorine-containing ether compounds, hydrolysis of hydrolyzable silyl groups and Well-known additives, such as an acid catalyst and a basic catalyst which accelerate a condensation reaction, are mentioned. Examples of impurities other than the compound (A), the transition metal compound and other fluorine-containing ether compounds include compounds unavoidable in the production of the compound (A) and other fluorine-containing ether compounds.
（化合物（Ａ））
　化合物（Ａ）は、ポリ（オキシペルフルオロアルキレン）鎖および基（Ｉ）を有する。
　－ＳｉＲｎＬ３－ｎ　・・・（Ｉ）
　ただし、Ｌは水酸基または加水分解性基であり、
　Ｒは水素原子または１価の炭化水素基であり、
　ｎは０～２の整数であり、
　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。 (Compound (A))
Compound (A) has a poly (oxyperfluoroalkylene) chain and a group (I).
-SiR n L 3-n (I)
However, L is a hydroxyl group or a hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
When n is 2, n R may be the same or different.
　化合物（Ａ）は、基（ＩＩ）をさらに有することができる。
　Ｒｆ１－Ｏ－Ｑ－　・・・（ＩＩ）
　ただし、Ｒｆ１は、ペルフルオロアルキル基であり、
　Ｑは、単結合、１個以上の水素原子を含むオキシフルオロアルキレン基、または該オキシフルオロアルキレン基の２～５個が結合してなるポリオキシフルオロアルキレン基である。該ポリオキシフルオロアルキレン基を構成するオキシフルオロアルキレン基は全てが同一であっても異なっていてもよい。 Compound (A) may further have a group (II).
R f1 -OQ- (II)
However, R f1 is a perfluoroalkyl group,
Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups. All of the oxyfluoroalkylene groups constituting the polyoxyfluoroalkylene group may be the same or different.
　＜ポリ（オキシペルフルオロアルキレン）鎖＞
　ポリ（オキシペルフルオロアルキレン）鎖（以下、化合物（Ａ）中のポリ（オキシペルフルオロアルキレン）鎖を、ＰＦＥ鎖とも記す。）としては、下式（ａ）で表されるものが挙げられる。
　（Ｒｆ２Ｏ）ｍ１　・・・（ａ）
　ただし、Ｒｆ２はペルフルオロアルキレン基であり、
　ｍ１は２～２００の整数であり、
　（Ｒｆ２Ｏ）ｍ１は炭素数の異なる２種以上のＲｆ２Ｏからなるものであってもよい。その場合、２種以上のＲｆ２Ｏは、ランダム、交互、ブロックのいずれに配置されてもよい。特に、（ＣＦ２Ｏ）と他の（Ｒｆ２Ｏ）とを有するＰＦＥ鎖の場合は、（ＣＦ２Ｏ）と他の（Ｒｆ２Ｏ）とはランダムに配置されていることが好ましい。 <Poly (oxyperfluoroalkylene) chain>
Examples of the poly (oxyperfluoroalkylene) chain (hereinafter, the poly (oxyperfluoroalkylene) chain in the compound (A) is also referred to as a PFE chain) include those represented by the following formula (a).
(R f2 O) m1 (a)
Where R f2 is a perfluoroalkylene group,
m1 is an integer from 2 to 200,
(R f2 O) m1 may be composed of two or more types of R f2 O having different carbon numbers. In that case, two or more types of R f2 O may be arranged in any of random, alternating, and block. Particularly, in the case of (CF 2 O) and PFE chain having and other (R f2 O), preferably disposed randomly and (CF 2 O) and the other (R f2 O).
　Ｒｆ２の炭素数は、表面層の耐摩擦性および指紋除去性にさらに優れる点から、１～６個が好ましく、１～４個がより好ましく、表面層の潤滑性にさらに優れる点からは、１～２個が特に好ましく、表面層の耐摩擦性にさらに優れる点からは、炭素数３～４個のペルフルオロアルキレン基が特に好ましい。
　Ｒｆ２は、分岐状でも直鎖状でもよく、表面層の耐摩擦性および潤滑性がさらに優れる点から、直鎖状が好ましい。 The number of carbon atoms of R f2 is preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 4 from the viewpoint of further excellent friction resistance and fingerprint removability of the surface layer. One to two is particularly preferred, and a perfluoroalkylene group having 3 to 4 carbon atoms is particularly preferred from the viewpoint of further improving the friction resistance of the surface layer.
R f2 may be branched or linear, and is preferably linear because the surface layer is further excellent in friction resistance and lubricity.
　ｍ１は、２～２００の整数であり、５～１５０の整数が好ましく、１０～８０の整数が特に好ましい。ｍ１が前記範囲の下限値以上であれば、表面層の撥水撥油性に優れる。ｍ１が前記範囲の上限値以下であれば、表面層の耐摩擦性に優れる。すなわち、化合物（Ａ）の数平均分子量が大きすぎると、単位分子量あたりに存在する基（Ｉ）の数が減少し、耐摩擦性が低下する。 M1 is an integer of 2 to 200, preferably an integer of 5 to 150, particularly preferably an integer of 10 to 80. If m1 is not less than the lower limit of the above range, the water and oil repellency of the surface layer is excellent. If m1 is not more than the upper limit of the above range, the surface layer has excellent friction resistance. That is, when the number average molecular weight of the compound (A) is too large, the number of groups (I) present per unit molecular weight is reduced, and the friction resistance is lowered.
　ＰＦＥ鎖の具体的な態様として、以下の（ａ－１）～（ａ－８）等が挙げられる。
　（ＣＦ２Ｏ）ｍ０１　・・・（ａ－１）
　｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝ 　・・・（ａ－２）
　｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１２｝ 　・・・（ａ－３）
　｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１２｝ 　・・・（ａ－４）
　｛（ＣＦ２Ｏ）ｍ１１（ＣＦ（ＣＦ３）ＣＦ２Ｏ）ｍ１２｝ 　・・・（ａ－５）
　（ＣＦ２ＣＦ２Ｏ）ｍ１３　・・・（ａ－６）
　（ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１４ 　・・・（ａ－７）
　（ＣＦ２ＣＦ２Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１５ 　・・・（ａ－８）
　ただし、ｍ０１は２～２００の整数であり、ｍ１１は１以上の整数であり、ｍ１２は１以上の整数であり、（ｍ１１＋ｍ１２）は２～２００の整数である。
　ｍ０１、（ｍ１１＋ｍ１２）はそれぞれ２～２００の整数であり、５～１５０の整数が好ましく、１０～８０の整数が特に好ましい。
　ｍ１１とｍ１２との比（ｍ１１／ｍ１２）は、９９／１～３０／７０が好ましく、９０／１０～４０／６０が特に好ましい。
　ｍ１３およびｍ１４はそれぞれ２～２００の整数である。ｍ１５は１～１００の整数であり、３～７５の整数が好ましく、５～４０の整数が特に好ましい。
　上記のなかでも、（ａ－２）～（ａ－４）、（ａ－８）が好ましく、（ａ－２）が特に好ましい。 Specific embodiments of the PFE chain include the following (a-1) to (a-8).
(CF 2 O) m01 (a-1)
{(CF 2 O) m11 (CF 2 CF 2 O) m12 } (a-2)
{(CF 2 O) m11 (CF 2 CF 2 CF 2 O) m12 } (a-3)
{(CF 2 O) m11 (CF 2 CF 2 CF 2 CF 2 O) m12 } (a-4)
{(CF 2 O) m11 (CF (CF 3 ) CF 2 O) m12 } (a-5)
(CF 2 CF 2 O) m13 (a-6)
(CF 2 CF 2 CF 2 O) m14 (a-7)
(CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) m15 (a-8)
However, m01 is an integer of 2 to 200, m11 is an integer of 1 or more, m12 is an integer of 1 or more, and (m11 + m12) is an integer of 2 to 200.
m01 and (m11 + m12) are each an integer of 2 to 200, preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 80.
The ratio of m11 to m12 (m11 / m12) is preferably 99/1 to 30/70, particularly preferably 90/10 to 40/60.
m13 and m14 are each an integer of 2 to 200. m15 is an integer of 1 to 100, preferably an integer of 3 to 75, and particularly preferably an integer of 5 to 40.
Among the above, (a-2) to (a-4) and (a-8) are preferable, and (a-2) is particularly preferable.
　＜基（Ｉ）＞
　基（Ｉ）において、Ｌは、水酸基または加水分解性基である。
　加水分解性基は、加水分解反応によって水酸基となる基である。すなわち、Ｌが加水分解性基である場合、基（Ｉ）のＳｉ－Ｌは、加水分解反応によってシラノール基（Ｓｉ－ＯＨ）となる。
　加水分解性基としては、アルコキシ基、ハロゲン原子、アシル基、イソシアナート基（－ＮＣＯ）等が挙げられる。アルコキシ基の炭素数は、１～４が好ましい。アシル基の炭素数は、２～５が好ましい。ハロゲン原子としては、塩素原子が特に好ましい。 <Group (I)>
In group (I), L is a hydroxyl group or a hydrolyzable group.
The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, when L is a hydrolyzable group, Si—L of the group (I) becomes a silanol group (Si—OH) by the hydrolysis reaction.
Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (—NCO) and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 4. The acyl group preferably has 2 to 5 carbon atoms. As the halogen atom, a chlorine atom is particularly preferable.
　Ｌは、化合物（Ａ）の製造のしやすさの点から、炭素数１～４のアルコキシ基またはハロゲン原子であることが好ましい。Ｌとしては、塗布時のアウトガスが少なく、化合物（Ａ）の保存安定性に優れる点から、炭素数１～４のアルコキシ基が好ましく、化合物（Ａ）の長期の保存安定性が必要な場合にはエトキシ基が特に好ましく、塗布後の反応時間を短時間とする場合にはメトキシ基が特に好ましい。 L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of ease of production of the compound (A). L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of little outgassing during coating and excellent storage stability of the compound (A), and when long-term storage stability of the compound (A) is required. Is particularly preferably an ethoxy group, and a methoxy group is particularly preferred when the reaction time after coating is short.
　Ｒは水素原子または１価の炭化水素基である。
　１価の炭化水素基としては、アルキル基、シクロアルキル基等の飽和炭化水素基、アルケニル基、アリル基等が挙げられ、飽和炭化水素基が好ましい。
　１価の飽和炭化水素基の炭素数は、化合物（Ａ）が製造しやすい点で、１～６が好ましく、１～３がより好ましく、１～２が特に好ましい。 R is a hydrogen atom or a monovalent hydrocarbon group.
Examples of the monovalent hydrocarbon group include a saturated hydrocarbon group such as an alkyl group and a cycloalkyl group, an alkenyl group, and an allyl group, and a saturated hydrocarbon group is preferable.
The number of carbon atoms of the monovalent saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint that the compound (A) can be easily produced.
　ｎは、０または１が好ましく、０が特に好ましい。１個の基（Ｉ）にＬが複数存在することによって、基材との接着性がより強固になり、表面層の耐久性がさらに優れる。
　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよい。たとえば一部のＬが加水分解性基で、残りのＬが水酸基であってもよい。 n is preferably 0 or 1, particularly preferably 0. By the presence of a plurality of L in one group (I), the adhesion to the substrate becomes stronger and the durability of the surface layer is further improved.
When n is 0 or 1, (3-n) L may be the same or different. For example, a part of L may be a hydrolyzable group and the remaining L may be a hydroxyl group.
　基（Ｉ）としては、Ｓｉ（ＯＣＨ３）３、ＳｉＣＨ３（ＯＣＨ３）２、Ｓｉ（ＯＣＨ２ＣＨ３）３、ＳｉＣｌ３、Ｓｉ（ＯＣＯＣＨ３）３、およびＳｉ（ＮＣＯ）３が好ましい。工業的な製造における取扱いやすさの点から、Ｓｉ（ＯＣＨ３）３が特に好ましい。 As the group (I), Si (OCH 3 ) 3 , SiCH 3 (OCH 3 ) 2 , Si (OCH 2 CH 3 ) 3 , SiCl 3 , Si (OCOCH 3 ) 3 , and Si (NCO) 3 are preferable. From the viewpoint of ease of handling in industrial production, Si (OCH 3 ) 3 is particularly preferable.
　＜基（ＩＩ）＞
　基（ＩＩ）において、Ｒｆ１はペルフルオロアルキル基である。
　Ｒｆ１におけるペルフルオロアルキル基の炭素数は、表面層の潤滑性および耐久性がさらに優れる点から、１～２０が好ましく、１～１０がより好ましく、１～６がさらに好ましく、１～３が特に好ましい。
　ペルフルオロアルキル基は分岐状でも直鎖状でもよく、直鎖状が好ましい。直鎖状のペルフルオロアルキル基として、たとえばＣＦ３－、ＣＦ３ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２－等が挙げられる。 <Group (II)>
In group (II), R f1 is a perfluoroalkyl group.
The number of carbon atoms of the perfluoroalkyl group in R f1 is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3 in view of further excellent lubricity and durability of the surface layer. preferable.
The perfluoroalkyl group may be branched or linear, and is preferably linear. Examples of the linear perfluoroalkyl group include CF 3 —, CF 3 CF 2 —, CF 3 CF 2 CF 2 — and the like.
　Ｑは、単結合、１個以上の水素原子を含むオキシフルオロアルキレン基、または該オキシフルオロアルキレン基の２～５個（好ましくは２～４個）が結合してなるポリオキシフルオロアルキレン基である。ポリオキシフルオロアルキレン基において複数のオキシフルオロアルキレン基は、通常、直列に結合している。
　Ｑが水素原子を含むオキシフルオロアルキレン基または該オキシフルオロアルキレン基の２～５個が結合してなるポリオキシフルオロアルキレン基であると、化合物（Ａ）の液状媒体への溶解性が高くなる。そのため、コーティング液中で化合物（Ａ）が凝集しにくく、また、基材の表面に塗布した後、乾燥させる途中に化合物（Ａ）が凝集しにくいため、表面層の外観にさらに優れる。
　オキシフルオロアルキレン基の炭素数は、１～６が好ましく、２～６がより好ましく、２～４がさらに好ましく、２または３が特に好ましい。
　オキシフルオロアルキレン基における水素原子の数は、表面層の外観に優れる点から、１個以上であり、２個以上が好ましく、３個以上が特に好ましい。オキシフルオロアルキレン基における水素原子の数は、表面層の撥水撥油性にさらに優れる点から、（Ｑの炭素数）×２個以下が好ましく、（Ｑの炭素数）個以下が特に好ましい。
　オキシフルオロアルキレン基は、分岐状でも直鎖状でもよく、表面層の潤滑性がさらに優れる点から、直鎖状が好ましい。
　ポリオキシフルオロアルキレン基において、２～５個のオキシフルオロアルキレン基は、全てが同一であっても異なっていてよい。
　Ｑは、化合物（Ａ）の製造のしやすさの点から、単結合であるか、または－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－、－ＣＦ２ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－、－ＣＦ２ＣＦ２ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－、－ＣＦ２ＣＦ２ＯＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－、－ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－、－ＣＦ２ＣＨ２ＯＣＨ２ＣＦ２Ｏ－、および－ＣＦ２ＣＦ２ＯＣＦ２ＣＨ２ＯＣＨ２ＣＦ２Ｏ－からなる群から選ばれる基（ただし、左側がＲｆ１－Ｏに結合する。）であることが好ましい。 Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 (preferably 2 to 4) of the oxyfluoroalkylene group. . In the polyoxyfluoroalkylene group, the plurality of oxyfluoroalkylene groups are usually bonded in series.
When Q is an oxyfluoroalkylene group containing a hydrogen atom or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, the solubility of the compound (A) in the liquid medium is increased. Therefore, the compound (A) is less likely to aggregate in the coating liquid, and the compound (A) is less likely to aggregate in the course of drying after being applied to the surface of the substrate, so that the appearance of the surface layer is further improved.
The number of carbon atoms in the oxyfluoroalkylene group is preferably 1 to 6, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 2 or 3.
The number of hydrogen atoms in the oxyfluoroalkylene group is 1 or more, preferably 2 or more, particularly preferably 3 or more, from the viewpoint of excellent appearance of the surface layer. The number of hydrogen atoms in the oxyfluoroalkylene group is preferably (Q carbon number) × 2 or less, particularly preferably (Q carbon number) or less, from the viewpoint of further excellent water and oil repellency of the surface layer.
The oxyfluoroalkylene group may be branched or linear, and is preferably linear because the lubricity of the surface layer is further improved.
In the polyoxyfluoroalkylene group, 2 to 5 oxyfluoroalkylene groups may all be the same or different.
Q is a single bond or —CHFCF 2 OCH 2 CF 2 O—, —CF 2 CHFCF 2 OCH 2 CF 2 O—, —CF 2 CF from the viewpoint of ease of production of the compound (A). 2 CHFCF 2 OCH 2 CF 2 O-, -CF 2 CF 2 OCHFCF 2 OCH 2 CF 2 O-, -CF 2 CF 2 OCF 2 CF 2 OCHFCF 2 OCH 2 CF 2 O-, -CF 2 CH 2 OCH 2 CF A group selected from the group consisting of 2 O— and —CF 2 CF 2 OCF 2 CH 2 OCH 2 CF 2 O— (where the left side is bonded to R f1 —O) is preferable.
　化合物（Ａ）が有するＰＦＥ鎖は１個でもよく２個以上でもよい。製造の容易さと取扱いの容易さの点から、１～３個が好ましい。
　化合物（Ａ）がＰＦＥ鎖を２個以上有する場合、各ＰＦＥ鎖は同一であっても異なっていてもよい。 The compound (A) may have one PFE chain or two or more PFE chains. One to three is preferable from the viewpoint of ease of production and handling.
When the compound (A) has two or more PFE chains, each PFE chain may be the same or different.
　化合物（Ａ）が有する基（Ｉ）は１個でもよく２個以上でもよい。基材との結合が増えることにより表面層の耐久性がより優れる点から、２個以上が好ましく、３個以上が特に好ましい。基材に結合する分子密度を高くすることにより表面層の耐久性がより優れる点から、１０個以下が好ましく、５個以下がより好ましく、４個以下が特に好ましい。
　したがって、化合物（Ａ）が有する基（Ｉ）は１～１０個が好ましく、２～５個がより好ましく、３～４個が特に好ましい。
　化合物（Ａ）が基（Ｉ）を２個以上有する場合、各基（Ｉ）は同一であっても異なっていてもよい。化合物（Ａ）の製造のしやすさの点では、全てが同一の基であることが好ましい。 The group (I) possessed by the compound (A) may be one or two or more. Two or more are preferable and three or more are particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the bond with the substrate. 10 or less is preferable, 5 or less is more preferable, and 4 or less is particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the density of molecules bonded to the substrate.
Accordingly, the group (I) possessed by the compound (A) is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 3 to 4.
When the compound (A) has two or more groups (I), each group (I) may be the same or different. In terms of ease of production of the compound (A), it is preferred that all are the same group.
　ＰＦＥ鎖の一方の末端には、基（ＩＩ）が結合していることが好ましい。すなわち、化合物（Ａ）は、ＰＦＥ鎖の一方の末端に結合した基（ＩＩ）をさらに有することが好ましい。これにより、表面層の潤滑性がさらに優れたものとなる。 It is preferable that the group (II) is bonded to one end of the PFE chain. That is, the compound (A) preferably further has a group (II) bonded to one end of the PFE chain. Thereby, the lubricity of the surface layer is further improved.
　化合物（Ａ）の数平均分子量（Ｍｎ）は、２，０００～２０，０００が好ましく、３，０００～１５，０００がより好ましく、４，０００～１２，０００が特に好ましい。化合物（Ａ）の数平均分子量が前記範囲の下限値以上であれば、表面層の潤滑性がさらに優れる。化合物（Ａ）の数平均分子量が前記範囲の下限値以上であれば、表面層の耐久性がさらに優れる。
　数平均分子量（Ｍｎ）は、後述する実施例に記載の測定方法により測定される。 The number average molecular weight (Mn) of the compound (A) is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and particularly preferably 4,000 to 12,000. If the number average molecular weight of the compound (A) is not less than the lower limit of the above range, the lubricity of the surface layer is further improved. When the number average molecular weight of the compound (A) is at least the lower limit of the above range, the durability of the surface layer is further improved.
The number average molecular weight (Mn) is measured by the measuring method described in the examples described later.
　化合物（Ａ）は、ＰＦＥ鎖と基（Ｉ）とを有する限り特に限定されない。たとえば以下の文献に記載されるような公知の含フッ素エーテル化合物のなかから適宜選択できる。
　特開２０１３－９１０４７号公報、特開２０１４－８０４７３号公報、国際公開第２０１３／０４２７３２号、国際公開第２０１３／０４２７３３号、国際公開第２０１３／１２１９８４号、国際公開第２０１３／１２１９８５号、国際公開第２０１３／１２１９８６号、国際公開第２０１４／１６３００４号、国際公開第２０１４／１７５１２４号、国際公開第２０１５／０８７９０２号、特開２０１３－２２７２７９号公報、特開２０１３－２４１５６９号公報、特開２０１３－２５６６４３号公報、特開２０１４－１５６０９号公報、特開２０１４－３７５４８号公報、特開２０１４－６５８８４号公報、特開２０１４－２１０２５８号公報、特開２０１４－２１８６３９号公報、特開２０１５－２００８８４号公報、特開２０１５－２２１８８８号公報、国際公開第２０１３／１４６１１２号、国際公開第２０１３／１８７４３２号、国際公開第２０１４／０６９５９２号、国際公開第２０１５／０９９０８５号、国際公開第２０１５／１６６７６０号、特開２０１３－１４４７２６号公報、特開２０１４－７７８３６号公報、特開２０１３－１１７０１２号公報、特開２０１４－２１４１９４号公報、特開２０１４－１９８８２２号公報、特開２０１５－１２９２３０号公報、特開２０１５－１９６７２３号公報、特開２０１５－１３９８３号公報、特開２０１５－１９９９１５号公報、特開２０１５－１９９９０６号公報等。 The compound (A) is not particularly limited as long as it has a PFE chain and a group (I). For example, it can be appropriately selected from known fluorine-containing ether compounds described in the following documents.
JP 2013-91047 A, JP 2014-80473 A, International Publication No. 2013/042732, International Publication No. 2013/042733, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, International Publication No. 2014/175124, International Publication No. 2015/0887902, Japanese Unexamined Patent Publication No. 2013-227279, Japanese Unexamined Patent Publication No. 2013-241369, Japanese Unexamined Patent Publication No. 2013-2013. No. 256643, JP 2014-15609, JP 2014-37548, JP 2014-65884, JP 2014-210258, JP 2014-218639, JP 2015-2000884. Gazette, JP2015-2015 No. 21888, International Publication No. 2013/146112, International Publication No. 2013/187432, International Publication No. 2014/069592, International Publication No. 2015/099085, International Publication No. 2015/166760, Japanese Patent Application Laid-Open No. 2013-144726. Gazette, JP-A No. 2014-77836, JP-A No. 2013-1117012, JP-A No. 2014-214194, JP-A No. 2014-198822, JP-A No. 2015-129230, JP-A No. 2015-196723, JP-A-2015-13983, JP-A-2015-199915, JP-A-2015-199906, etc.
　本組成物において、化合物（Ａ）は、１種の化合物（Ａ）からなる単一化合物であってもよく、２種以上の化合物（Ａ）からなる混合物であってもよい。
　本明細書において、ポリ（オキシペルフルオロアルキレン）鎖におけるオキシペルフルオロアルキレン基の繰り返し数の数に分布を有する以外は同一の化合物群である含フッ素エーテル化合物は単一化合物とみなす。たとえばＰＦＥ鎖が（ＣＦ２Ｏ）ｍ１１（Ｒｆ２Ｏ）ｍ１２である化合物（Ａ）の場合、ｍ１１とｍ１２に分布を有する以外は同一の化合物群は、単一化合物である含フッ素エーテル化合物とする。 In the present composition, the compound (A) may be a single compound composed of one kind of compound (A) or a mixture composed of two or more kinds of compounds (A).
In the present specification, fluorine-containing ether compounds that are the same compound group except that they have a distribution in the number of repeating oxyperfluoroalkylene groups in the poly (oxyperfluoroalkylene) chain are regarded as a single compound. For example, in the case of the compound (A) in which the PFE chain is (CF 2 O) m11 (R f2 O) m12 , the same group of compounds, except for the distribution in m11 and m12, includes a fluorine-containing ether compound that is a single compound. To do.
　「好ましい態様」
　化合物（Ａ）としては、国際公開第２０１４／１６３００４号、国際公開第２０１３／１２１９８４号、特開２０１５－１９９９０６号公報に記載される含フッ素エーテル化合物、および下記化合物（Ａ１）が好ましい。 "Preferred embodiment"
As the compound (A), the fluorine-containing ether compounds described in International Publication No. 2014/163004, International Publication No. 2013/121984, and Japanese Unexamined Patent Publication No. 2015-199906, and the following Compound (A1) are preferable.
　＜化合物（Ａ１）＞
　化合物（Ａ）の好ましい一態様として、下式（Ａ１）で表される含フッ素エーテル化合物（以下、化合物（Ａ１）とも記す。）が挙げられる。
　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］ａＺ１［－ＳｉＲｎＬ３－ｎ］ｂ　・・・（Ａ１）
　ただし、Ｒｆ１、Ｑ、Ｌ、Ｒおよびｎはそれぞれ前記と同義であり、
　Ｒｆｅは、ＰＦＥ鎖であり、
　Ｚ１は、（ａ＋ｂ）価の連結基であり、
　ａは、１以上の整数であり、
　ｂは、１以上の整数であり、
　ａが２以上のときａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は、同一であっても異なっていてもよく、
　ｂが２以上のときｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。 <Compound (A1)>
As a preferable embodiment of the compound (A), a fluorine-containing ether compound represented by the following formula (A1) (hereinafter also referred to as compound (A1)) can be mentioned.
[R f1 -OQR fe- ] a Z 1 [-SiR n L 3-n ] b (A1)
However, R f1 , Q, L, R and n are as defined above,
R fe is a PFE chain;
Z 1 is a (a + b) -valent linking group,
a is an integer of 1 or more,
b is an integer of 1 or more,
When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different,
When b is 2 or more, b [-SiR n L 3-n ] may be the same or different.
　Ｒｆ１は前記基（ＩＩ）中のＲｆ１と同様であり、好ましい態様も同様である。
　ａが２以上のときａ個のＲｆ１は、炭素数が同一であることが好ましく、製造しやすさの点から、同一の基、すなわち炭素数が同一かつ化学構造が同一の基であることが好ましい。炭素数が同一かつ化学構造が同一の基であるとは、たとえばａが２の場合に、２個のＲｆ１がＣＦ３ＣＦ２ＣＦ２－であるということである（２個のＲｆ１の炭素数が同一であっても化学構造が異なる、ＣＦ３ＣＦ２ＣＦ２－、ＣＦ３ＣＦ（ＣＦ３）－の組み合わせではない。） R f1 is the same as R f1 in the group (II), preferable embodiments thereof are also the same.
When a is 2 or more, a R f1 is preferably the same in number of carbon atoms, and from the viewpoint of ease of production, the same group, that is, the same number of carbon atoms and the same chemical structure. Is preferred. The group having the same carbon number and the same chemical structure means that, for example, when a is 2, two R f1 are CF 3 CF 2 CF 2 — (the two R f1 (It is not a combination of CF 3 CF 2 CF 2 — and CF 3 CF (CF 3 ) —, which have the same carbon number but different chemical structures.)
　Ｑは前記基（ＩＩ）中のＱと同様であり、好ましい態様も同様である。
　ＲｆｅのＰＦＥ鎖は前記と同様であり、好ましい態様も同様である。
　Ｌは前記基（Ｉ）中のＬと同様であり、好ましい態様も同様である。
　Ｒは前記基（Ｉ）中のＲと同様であり、好ましい態様も同様である。
　ｎは前記基（Ｉ）中のｎと同様であり、好ましい態様も同様である。
　ａの好ましい値はそれぞれ、化合物（Ａ）が有するＰＦＥ鎖の好ましい数と同様である。すなわち、ａはそれぞれ、１～３の整数が好ましい。
　ｂの好ましい値は、化合物（Ａ）が有する基（Ｉ）の好ましい数と同様である。すなわち、ｂは１～１０の整数が好ましく、２～５の整数がより好ましく、３～４の整数が特に好ましい。
　（ａ＋ｂ）は、２～１３が好ましく、３～８がより好ましく、４～７が特に好ましい。
　また、ａが２以上のときａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は、同一であることが好ましく、ｂが２以上のときｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一であることが好ましい。 Q is the same as Q in the group (II), and preferred embodiments are also the same.
The PFE chain of R fe is the same as described above, and the preferred embodiment is also the same.
L is the same as L in the group (I), and preferred embodiments are also the same.
R is the same as R in the group (I), and preferred embodiments are also the same.
n is the same as n in the group (I), and preferred embodiments are also the same.
Preferred values for a are the same as the preferred number of PFE chains that compound (A) has. That is, each a is preferably an integer of 1 to 3.
The preferable value of b is the same as the preferable number of groups (I) that the compound (A) has. That is, b is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and particularly preferably an integer of 3 to 4.
(A + b) is preferably 2 to 13, more preferably 3 to 8, and particularly preferably 4 to 7.
Further, when a is 2 or more, a [R f1 -OQR fe- ] are preferably the same, and when b is 2 or more, b [-SiR n L 3-n ] Are preferably the same.
　Ｚ１としては、たとえば、（ａ＋ｂ）価の置換または無置換の炭化水素基、置換または無置換の炭化水素基の炭素－炭素原子間または／および末端に、炭化水素基以外の基または原子を有する（ａ＋ｂ）価の基、（ａ＋ｂ）価のオルガノポリシロキサン基等が挙げられる。 Z 1 is, for example, a (a + b) -valent substituted or unsubstituted hydrocarbon group, a group or atom other than a hydrocarbon group at the carbon-carbon atom or / and terminal of the substituted or unsubstituted hydrocarbon group. Examples thereof include (a + b) -valent groups and (a + b) -valent organopolysiloxane groups.
　無置換の炭化水素基としては、たとえば直鎖状または分岐状の飽和炭化水素基、芳香族炭化水素環式基（たとえばベンゼン環、ナフタレン環等の芳香族炭化水素環から（ａ＋ｂ）個の水素原子を除いた基）、直鎖状または分岐状の飽和炭化水素基と芳香族炭化水素環式基との組み合わせからなる基（たとえば前記芳香族炭化水素環式基に置換基としてアルキル基が結合した基、前記飽和炭化水素基の炭素原子間または／および末端にフェニレン基等のアリーレン基を有する基等）、２以上の芳香族炭化水素環式基の組み合わせからなる基等が挙げられる。これらの中でも直鎖状または分岐状の飽和炭化水素基が好ましい。無置換の炭化水素基の炭素数は、２０以下が好ましい。
　置換の炭化水素基は、炭化水素基の水素原子の一部または全部が置換基で置換された基である。置換基としては、たとえば水酸基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、アミノ基、ニトロ基、シアノ基、アミノカルボニル基等が挙げられる。 Examples of the unsubstituted hydrocarbon group include a linear or branched saturated hydrocarbon group, an aromatic hydrocarbon cyclic group (for example, (a + b) hydrogen atoms from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring). A group excluding an atom), a group composed of a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, an alkyl group bonded to the aromatic hydrocarbon cyclic group as a substituent) And groups having an arylene group such as a phenylene group between and / or at the terminal of the saturated hydrocarbon group), and a group formed of a combination of two or more aromatic hydrocarbon cyclic groups. Among these, a linear or branched saturated hydrocarbon group is preferable. The number of carbon atoms of the unsubstituted hydrocarbon group is preferably 20 or less.
The substituted hydrocarbon group is a group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with a substituent. Examples of the substituent include a hydroxyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an amino group, a nitro group, a cyano group, and an aminocarbonyl group.
　炭化水素基の炭素－炭素原子間または／および末端に有する炭化水素基以外の基または原子としては、たとえばエーテル性酸素原子（－Ｏ－）、チオエーテル性硫黄原子（－Ｓ－）、窒素原子（－Ｎ＜）、ケイ素原子（＞Ｓｉ＜）、炭素原子（＞Ｃ＜）、－Ｎ（Ｒ１５）－、－Ｃ（Ｏ）Ｎ（Ｒ１５）－、－ＯＣ（Ｏ）Ｎ（Ｒ１５）－、－Ｓｉ（Ｒ１６）（Ｒ１７）－、オルガノポリシロキサン基、－Ｃ（Ｏ）－、－Ｃ（Ｏ）－Ｏ－、－Ｃ（Ｏ）－Ｓ－等が挙げられる。ただし、Ｒ１５は水素原子、アルキル基またはフェニル基であり、Ｒ１６～Ｒ１７はそれぞれ独立にアルキル基またはフェニル基である。アルキル基の炭素数は、１～６が好ましい。
　オルガノポリシロキサン基は、直鎖状でもよく、分岐鎖状でもよく、環状でもよい。 Examples of the group or atom other than the hydrocarbon group between the carbon-carbon atoms and / or the terminal of the hydrocarbon group include an etheric oxygen atom (—O—), a thioetheric sulfur atom (—S—), a nitrogen atom ( —N <), silicon atom (> Si <), carbon atom (> C <), —N (R 15 ) —, —C (O) N (R 15 ) —, —OC (O) N (R 15 )-, -Si (R 16 ) (R 17 )-, organopolysiloxane groups, -C (O)-, -C (O) -O-, -C (O) -S- and the like. However, R 15 is a hydrogen atom, an alkyl group or a phenyl group, and R 16 to R 17 are each independently an alkyl group or a phenyl group. The alkyl group preferably has 1 to 6 carbon atoms.
The organopolysiloxane group may be linear, branched, or cyclic.
　＜化合物（Ａ１）の好ましい形態＞
　化合物（Ａ１）としては、表面層の耐摩擦性および指紋汚れ除去性にさらに優れる点から、以下の化合物（Ａ１１）、化合物（Ａ１２）および化合物（Ａ１３）からなる群から選ばれる少なくとも１種が好ましい。 <Preferred Form of Compound (A1)>
As the compound (A1), at least one selected from the group consisting of the following compound (A11), compound (A12) and compound (A13) is used because the surface layer is further excellent in friction resistance and fingerprint stain removability. preferable.
　「化合物（Ａ１１）」
　化合物（Ａ１１）は、下式（Ａ１１）で表される。
　Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－Ｑ３２－［Ｃ（Ｏ）Ｎ（Ｒ３３）］ｐ１－Ｒ３４－Ｃ［－Ｒ３５－ＳｉＲｎＬ３－ｎ］３　・・・（Ａ１１）
　ただし、Ｒｆ１、Ｑ、Ｒｆｅ、Ｒ、Ｌおよびｎはそれぞれ前記と同義であり、
　Ｑ３２は、炭素数１～２０のフルオロアルキレン基、または炭素数２～２０のフルオロアルキレン基の炭素－炭素原子間にエーテル性酸素原子を有する基（ただし、一端がエーテル性酸素原子に結合し他端がＲｆｅと結合するフルオロアルキレン基がペルフルオロアルキレン基である場合を除く。）であり、
　Ｒ３３は、水素原子または炭素数１～６のアルキル基であり、
　ｐ１は、０または１であり、
　Ｒ３４は、単結合、炭素数１～６のアルキレン基、該アルキレン基の末端（ただし、Ｃ［－Ｒ３５－ＳｉＲｎＬ３－ｎ］３と結合する側の末端。）にエーテル性酸素原子を有する基、炭素数２～６のアルキレン基の炭素－炭素原子間にエーテル性酸素原子を有する基、または炭素数２～６のアルキレン基の末端（ただしＣ［－Ｒ３５－ＳｉＲｎＬ３－ｎ］３と結合する側の末端。）および炭素－炭素原子間にエーテル性酸素原子を有する基であり、
　Ｒ３５は、炭素数１～６のアルキレン基、該アルキレン基の末端（ただし、Ｓｉと結合する側の末端を除く。）にエーテル性酸素原子を有する基、または炭素数２～６のアルキレン基の炭素－炭素原子間にエーテル性酸素原子を有する基であり、
　３個の［－Ｒ３５－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。 “Compound (A11)”
The compound (A11) is represented by the following formula (A11).
R f1 —O—Q—R fe —Q 32 — [C (O) N (R 33 )] p1 —R 34 —C [—R 35 —SiR n L 3-n ] 3 ... (A11)
However, R f1 , Q, R fe , R, L and n are as defined above,
Q 32 represents a fluoroalkylene group having 1 to 20 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 to 20 carbon atoms (however, one end is bonded to the etheric oxygen atom). The other end of the fluoroalkylene group bonded to R fe is a perfluoroalkylene group).
R 33 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
p1 is 0 or 1,
R 34 is a single bond, an alkylene group having 1 to 6 carbon atoms, and an etheric oxygen at the terminal of the alkylene group (provided that the terminal is bonded to C [—R 35 —SiR n L 3-n ] 3 ). A group having an atom, a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a terminal of an alkylene group having 2 to 6 carbon atoms (provided that C [—R 35 —SiR n L 3-n ] is a terminal bonded to 3 )) and a group having an etheric oxygen atom between carbon-carbon atoms,
R 35 represents an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (excluding the terminal bonded to Si), or an alkylene group having 2 to 6 carbon atoms A group having an etheric oxygen atom between carbon-carbon atoms of
Three [—R 35 —SiR n L 3-n ] may be the same or different.
　化合物（Ａ１１）は、上述の式（Ａ１）において、ａが１であり、ｂが３であり、Ｚ１が－Ｑ３２－［Ｃ（Ｏ）Ｎ（Ｒ３３）］ｐ１－Ｒ３４－Ｃ［－Ｒ３５－］３の化合物である。
　ただし、Ｒｆｅ中の（ＣＦ２Ｏ）の数は４個以上であって、かつＱ３２中の（ＣＦ２Ｏ）の数は０～３個であることが好ましい。また、３個の［－Ｒ３５－ＳｉＲｎＬ３－ｎ］は、同一であることが好ましい。 In the compound (A11), in the above formula (A1), a is 1, b is 3, and Z 1 is —Q 32 — [C (O) N (R 33 )] p1 —R 34 —C [—R 35 —] 3
However, the number of (CF 2 O) in R fe is preferably 4 or more, and the number of (CF 2 O) in Q 32 is preferably 0 to 3. The three [—R 35 —SiR n L 3-n ] are preferably the same.
　Ｑ３２において、炭素数１～２０のフルオロアルキレン基としては、ペルフルオロアルキレン基、および、１個以上の水素原子を含むフルオロアルキレン基が好ましい。フルオロアルキレン基は、表面層の耐摩擦性および潤滑性の点から、直鎖状が好ましい。
　炭素数２～２０のフルオロアルキレン基の炭素－炭素原子間にエーテル性酸素原子を有する基としては、例えば、後述する（ｉｉ）の基が挙げられる。
　Ｑ３２としては、炭素数１～２０のペルフルオロアルキレン基、１個以上の水素原子を含む炭素数１～２０のフルオロアルキレン基、および、１個以上の水素原子を含む炭素数２～２０のフルオロアルキレン基の炭素－炭素原子間にエーテル性酸素原子を有する基が好ましい。 In Q 32 , the fluoroalkylene group having 1 to 20 carbon atoms is preferably a perfluoroalkylene group or a fluoroalkylene group containing one or more hydrogen atoms. The fluoroalkylene group is preferably linear from the viewpoint of friction resistance and lubricity of the surface layer.
Examples of the group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group having 2 to 20 carbon atoms include the group (ii) described later.
Q 32 includes a perfluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 1 to 20 carbon atoms containing one or more hydrogen atoms, and a fluoro having 2 to 20 carbon atoms containing one or more hydrogen atoms. A group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group is preferred.
　ｐ１が０で、Ｒｆｅが｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝である場合、Ｑ３２は、典型的には、炭素数１のペルフルオロアルキレン基である。
　ｐ１が１の場合、Ｑ３２としては、下記の基が挙げられる。
　（ｉ）ペルフルオロアルキレン基。
　（ｉｉ）ＲＦＣＨ２Ｏ（ただし、ＲＦは、炭素数１～６のペルフルオロアルキレン基である。）をＲｆｅと結合する側に有し、１個以上の水素原子を含むフルオロアルキレン基（炭素－炭素原子間にエーテル性酸素原子を有してもよい。）をＣ（Ｏ）Ｎ（Ｒ３３）と結合する側に有する基。 When p1 is 0 and R fe is {(CF 2 O) m11 (CF 2 CF 2 O) m12 }, Q 32 is typically a C 1 perfluoroalkylene group.
If p1 is 1, the Q 32, include the following groups.
(I) a perfluoroalkylene group.
(Ii) a fluoroalkylene group having R F CH 2 O (wherein R F is a C 1-6 perfluoroalkylene group) on the side bonded to R fe and containing one or more hydrogen atoms A group having (on the side bonded to C (O) N (R 33 )) (which may have an etheric oxygen atom between carbon-carbon atoms).
　（ｉｉ）のＱ３２としては、表面層の耐久性および潤滑性、化合物（Ａ１１）の製造のしやすさの点から、下記の基が好ましい。
　－ＲＦＣＨ２Ｏ－ＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、－ＲＦＣＨ２Ｏ－ＣＦ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、－ＲＦＣＨ２Ｏ－ＣＦ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、－ＲＦＣＨ２Ｏ－ＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－。 The Q 32 of (ii), the durability and lubricity of the surface layer, from the viewpoint of ease of preparation of the compound (A11), the following groups are preferred.
-R F CH 2 O-CF 2 CHFOCF 2 CF 2 CF 2- , -R F CH 2 O-CF 2 CHFCF 2 OCF 2 CF 2- , -R F CH 2 O-CF 2 CHFCF 2 OCF 2 CF 2 CF 2 —, —R F CH 2 O—CF 2 CHFOCF 2 CF 2 CF 2 OCF 2 CF 2 —.
　［Ｃ（Ｏ）Ｎ（Ｒ３３）］ｐ１基におけるｐ１が０と１の場合で、含フッ素エーテル化合物の特性はほとんど変わらない。ｐ１が１の場合にはアミド結合を有するが、Ｑ３２の［Ｃ（Ｏ）Ｎ（Ｒ３３）］と結合する側の末端の炭素原子に少なくとも１個のフッ素原子が結合していることにより、アミド結合の極性は小さくなり、表面層の撥水撥油性が低下しにくい。ｐ１が０か１かは、製造のしやすさの点から選択できる。
　［Ｃ（Ｏ）Ｎ（Ｒ３３）］ｐ１基中のＲ３３としては、化合物（Ａ１１）の製造のしやすさの点から、水素原子が好ましい。
　Ｒ３３がアルキル基の場合、アルキル基としては、炭素数１～４のアルキル基が好ましい。 [C (O) N (R 33 )] When p1 in the p1 group is 0 and 1, the characteristics of the fluorine-containing ether compound are hardly changed. When p1 is 1, it has an amide bond, but at least one fluorine atom is bonded to the terminal carbon atom bonded to [C (O) N (R 33 )] of Q 32 The polarity of the amide bond becomes small, and the water / oil repellency of the surface layer is hardly lowered. Whether p1 is 0 or 1 can be selected from the viewpoint of ease of manufacture.
The [C (O) N (R 33)] R 33 in p1 groups, from the viewpoint of ease of preparation of the compound (A11), a hydrogen atom is preferable.
When R 33 is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.
　ｐ１が０の場合、Ｒ３４としては、化合物（Ａ１１）の製造のしやすさの点から、単結合、－ＣＨ２Ｏ－、－ＣＨ２ＯＣＨ２－、－ＣＨ２ＯＣＨ２ＣＨ２Ｏ－および－ＣＨ２ＯＣＨ２ＣＨ２ＯＣＨ２－からなる群から選ばれる基（ただし、左側がＱ３２に結合する。）が好ましい。
　ｐ１が１の場合、Ｒ３４としては、化合物（Ａ１１）の製造のしやすさの点から、単結合、－ＣＨ２－および－ＣＨ２ＣＨ２－からなる群から選ばれる基が好ましい。 When p1 is 0, R 34 represents a single bond, —CH 2 O—, —CH 2 OCH 2 —, —CH 2 OCH 2 CH 2 O— from the viewpoint of ease of production of the compound (A11). And a group selected from the group consisting of —CH 2 OCH 2 CH 2 OCH 2 — (wherein the left side is bonded to Q 32 ) is preferable.
When p1 is 1, R 34 is preferably a group selected from the group consisting of a single bond, —CH 2 —, and —CH 2 CH 2 — from the viewpoint of easy production of the compound (A11).
　Ｒ３５としては、化合物（Ａ１１）の製造のしやすさの点から、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２－、－ＯＣＨ２ＣＨ２ＣＨ２－からなる群から選ばれる基（ただし、右側がＳｉに結合する。）が好ましい。
　Ｒ３５としては、表面層の耐光性に優れる点から、エーテル性酸素原子を有しないものが特に好ましい。屋外使用のタッチパネル（自動販売機、案内板等のデジタルサイネージ）、車載タッチパネル等においては、撥水撥油層に耐光性が求められる。
　化合物（Ａ１１）中の３個のＲ３５は、同一であっても異なっていてもよい。 R 35 represents —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 OCH 2 CH 2 CH 2 —, —OCH 2 CH from the viewpoint of ease of production of the compound (A11). A group selected from the group consisting of 2 CH 2 — (where the right side is bonded to Si) is preferred.
As R 35 , those having no etheric oxygen atom are particularly preferred from the viewpoint of excellent light resistance of the surface layer. In outdoor touch panels (digital signage such as vending machines and guide plates), in-vehicle touch panels, and the like, the water and oil repellent layers are required to have light resistance.
Three R 35 in the compound (A11) may be the same or different.
　化合物（Ａ１１）としては、たとえば、下式の化合物が挙げられる。該化合物は、工業的に製造しやすく、取扱いやすく、表面層の撥水撥油性、耐摩擦性、指紋汚れ除去性、潤滑性、外観にさらに優れる点から好ましい。 Examples of the compound (A11) include compounds of the following formula. The compound is preferable because it is easy to produce industrially, is easy to handle, and is excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity and appearance of the surface layer.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　ただし、これらの式中のＷは、Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－である。Ｗの好ましい形態は、上述した好ましいＲｆ１、ＱおよびＲｆｅを組み合わせたものとなる。Ｑ３２の好ましい範囲は上述した通りである。 However, W in these formulas is R f1 —OQRfe —. A preferred form of W is a combination of the preferred R f1 , Q and R fe described above. A preferred range of Q 32 are as described above.
　「化合物（Ａ１２）」
　化合物（Ａ１２）は、下式（Ａ１２）で表される。
　Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－Ｒ４２－Ｒ４３－Ｎ［－Ｒ４４－ＳｉＲｎＬ３－ｎ］２　・・・（Ａ１２）
　ただし、Ｒｆ１、Ｑ、Ｒｆｅ、Ｒ、Ｌおよびｎはそれぞれ前記と同義であり、
　Ｒ４２は、炭素数１～６のペルフルオロアルキレン基であり、
　Ｒ４３は、単結合、炭素数１～６のアルキレン基、該アルキレン基の末端（ただし、Ｎと結合する側の末端を除く。）にエーテル性酸素原子もしくは－ＮＨ－を有する基、炭素数２～６のアルキレン基の炭素－炭素原子間にエーテル性酸素原子もしくは－ＮＨ－を有する基、または炭素数２～６のアルキレン基の末端（ただし、Ｎと結合する側の末端を除く。）および炭素－炭素原子間にエーテル性酸素原子もしくは－ＮＨ－を有する基であり、
　Ｒ４４は、炭素数１～６のアルキレン基、または炭素数２～６のアルキレン基の炭素－炭素原子間にエーテル性酸素原子もしくは－ＮＨ－を有する基であり、
　２個の［－Ｒ４４－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。 “Compound (A12)”
The compound (A12) is represented by the following formula (A12).
R f1 -OQR fe -R 42 -R 43 -N [-R 44 -SiR n L 3-n ] 2 (A12)
However, R f1 , Q, R fe , R, L and n are as defined above,
R 42 is a C 1-6 perfluoroalkylene group,
R 43 represents a single bond, an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom or —NH— at the terminal of the alkylene group (excluding the terminal bonded to N), A group having an etheric oxygen atom or —NH— between carbon and carbon atoms of an alkylene group of 2 to 6 or an alkylene group having 2 to 6 carbon atoms (excluding the terminal on the side bonded to N) And a group having an etheric oxygen atom or —NH— between carbon-carbon atoms,
R 44 is an alkylene group having 1 to 6 carbon atoms or a group having an etheric oxygen atom or —NH— between carbon-carbon atoms of an alkylene group having 2 to 6 carbon atoms;
Two [—R 44 —SiR n L 3-n ] may be the same or different.
　化合物（Ａ１２）は、上述の式（Ａ１）において、ａが１であり、ｂが２であり、Ｚ１が－Ｒ４２－Ｒ４３－Ｎ［－Ｒ４４－］２の化合物である。 The compound (A12) is a compound in which a is 1, b is 2, and Z 1 is —R 42 —R 43 —N [—R 44 —] 2 in the above formula (A1).
　Ｒ４２は、直鎖状のペルフルオロアルキレン基であることが好ましい。Ｒ４２が直鎖状のペルフルオロアルキレン基であれば、表面層の耐摩擦性および潤滑性がさらに優れる。
　Ｒ４２は、Ｒｆｅが｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝である場合、典型的には、炭素数１のペルフルオロアルキレン基である。 R 42 is preferably a linear perfluoroalkylene group. If R 42 is a linear perfluoroalkylene group, abrasion resistance and lubricity of the surface layer is further excellent.
R 42 is typically a C 1 perfluoroalkylene group when R fe is {(CF 2 O) m11 (CF 2 CF 2 O) m12 }.
　Ｒ４３としては、化合物（Ａ１２）の製造のしやすさの点から、－ＣＨ２－、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＯＣＨ２ＣＨ２－および－ＣＨ２ＮＨＣＨ２ＣＨ２－からなる群から選ばれる基（ただし、左側がＲ４２に結合する。）が好ましい。
　Ｒ４３は、極性が高くかつ耐薬品性や耐光性が不充分なエステル結合を有しないため、表面層の初期の撥水性、耐薬品性および耐光性に優れる。 R 43 represents —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 OCH 2 CH 2 — and — from the viewpoint of ease of production of the compound (A12). A group selected from the group consisting of CH 2 NHCH 2 CH 2 — (where the left side is bonded to R 42 ) is preferred.
R 43 has a high polarity and does not have an ester bond with insufficient chemical resistance and light resistance, and therefore is excellent in the initial water repellency, chemical resistance and light resistance of the surface layer.
　Ｒ４４としては、化合物（Ａ１２）の製造のしやすさの点から、－ＣＨ２ＣＨ２ＣＨ２－および－ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２－（ただし、右側がＳｉに結合する。）が好ましい。
　Ｒ４４は、極性が高くかつ耐薬品性や耐光性が不充分なエステル結合を有しないため、表面層の初期の撥水性、耐薬品性および耐光性に優れる。
　Ｒ４４としては、表面層の耐光性に優れる点からは、エーテル性酸素原子を有しないものが特に好ましい。
　化合物（Ａ１２）中の２個のＲ４４は、同一であっても異なっていてもよい。２個のＲ４４は、同一であることが好ましく、また、２個の［－Ｒ４４－ＳｉＲｎＬ３－ｎ］は、同一であることが好ましい。 As R 44 , —CH 2 CH 2 CH 2 — and —CH 2 CH 2 OCH 2 CH 2 CH 2 — (provided that the right side is bonded to Si from the viewpoint of easy production of the compound (A12)). ) Is preferred.
Since R 44 has high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, it is excellent in the initial water repellency, chemical resistance and light resistance of the surface layer.
R 44 is particularly preferably one having no etheric oxygen atom from the viewpoint of excellent light resistance of the surface layer.
Two R 44 in the compound (A12) may be the same or different. The two R 44 are preferably the same, and the two [—R 44 —SiR n L 3-n ] are preferably the same.
　化合物（Ａ１２）としては、たとえば、下式の化合物が挙げられる。該化合物は、工業的に製造しやすく、取扱いやすく、撥水撥油性、耐摩擦性、指紋汚れ除去性、潤滑性、耐薬品性および耐光性にさらに優れる点から好ましい。 Examples of the compound (A12) include compounds of the following formula. The compound is preferred because it is easy to produce industrially, is easy to handle, and is further excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity, chemical resistance and light resistance.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　ただし、これらの式中のＷは、Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－である。Ｗの好ましい形態は、上述した好ましいＲｆ１、ＱおよびＲｆｅを組み合わせたものとなる。Ｒ４２の好ましい範囲は上述した通りである。 However, W in these formulas is R f1 —OQRfe —. A preferred form of W is a combination of the preferred R f1 , Q and R fe described above. A preferred range for R 42 is as described above.
　「化合物（Ａ１３）」
　化合物（Ａ１３）は、下式（Ａ１３）で表される。
　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－Ｒ５１－Ｒ５２－Ｏ－］ｅＺ３［－Ｏ－Ｒ５３－ＳｉＲｎＬ３－ｎ］ｆ　・・・（Ａ１３）
　ただし、Ｒｆ１、Ｑ、Ｒｆｅ、Ｒ、Ｌおよびｎはそれぞれ前記と同義であり、
　Ｒ５１は、炭素数１～６のペルフルオロアルキレン基であり、
　Ｒ５２は、炭素数１～６のアルキレン基であり、
　Ｚ３は、（ｅ＋ｆ）価の炭化水素基、または炭化水素基の炭素原子－炭素原子間にエーテル性酸素原子を１個以上有する、炭素数２以上で（ｅ＋ｆ）価の基であり、
　Ｒ５３は、炭素数１～２０のアルキレン基であり、
　ｅは、１以上の整数であり、
　ｆは、１以上の整数であり、
　（ｅ＋ｆ）は３以上であり、
　ｅが２以上のときｅ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－Ｒ５１－Ｒ５２－Ｏ－］は、同一であっても異なっていてもよく、
　ｆが２以上のときｆ個の［－Ｏ－Ｒ５３－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。 “Compound (A13)”
Compound (A13) is represented by the following formula (A13).
[R f1 -OQR fe -R 51 -R 52 -O-] e Z 3 [-O-R 53 -SiR n L 3-n ] f (A13)
However, R f1 , Q, R fe , R, L and n are as defined above,
R 51 is a C 1-6 perfluoroalkylene group,
R 52 is an alkylene group having 1 to 6 carbon atoms,
Z 3 is an (e + f) -valent hydrocarbon group, or a group having 2 or more carbon atoms and an (e + f) -valent group having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group,
R 53 is an alkylene group having 1 to 20 carbon atoms,
e is an integer greater than or equal to 1,
f is an integer of 1 or more,
(E + f) is 3 or more,
When e is 2 or more, e [R f1 -OQR fe -R 51 -R 52 -O-] may be the same or different,
f [-O-R 53 -SiR n L 3-n] of f-number when 2 or more may be be the same or different.
　化合物（Ａ１３）は、上述の式（Ａ１）において、ａがｅであり、ｂがｆであり、Ｚ１が［－Ｒ５１－Ｒ５２－Ｏ－］ｅＺ３［－Ｏ－Ｒ５３－］ｆの化合物である。 In the compound (A13), in formula (A1), a is e, b is f, and Z 1 is [—R 51 —R 52 —O—] e Z 3 [—O—R 53 —. ] A compound of f .
　ｅは１～３の整数が好ましい。ｆは１～１０の整数が好ましく、２～５の整数がより好ましく、３～４の整数が特に好ましい。
　また、ｅが２以上のときｅ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－Ｒ５１－Ｒ５２－Ｏ－］は、同一であることが好ましく、ｆが２以上のときｆ個の［－Ｏ－Ｒ５３－ＳｉＲｎＬ３－ｎ］は、同一であることが好ましい。 e is preferably an integer of 1 to 3. f is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and particularly preferably an integer of 3 to 4.
Further, when e is 2 or more, it is preferable that e [R f1 -OQR fe -R 51 -R 52 -O-] are the same, and when f is 2 or more, f [[ —O—R 53 —SiR n L 3-n ] are preferably the same.
　Ｒ５１は、たとえばＲｆｅが｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝である場合、－ＣＦ２－である。
　Ｒ５１は直鎖状が好ましい。Ｒ５１が直鎖状である化合物（Ａ１３）であれば、耐摩擦性および潤滑性により優れる表面層を形成できる。 R 51 is —CF 2 — when, for example, R fe is {(CF 2 O) m11 (CF 2 CF 2 O) m12 }.
R 51 is preferably linear. If R51 is a straight-chain compound (A13), a surface layer having better friction resistance and lubricity can be formed.
　Ｒ５２としては、化合物（Ａ１３）の製造のしやすさの点から、炭素数１～４のアルキレン基が好ましく、－ＣＨ２－が特に好ましい。 R 52 is preferably an alkylene group having 1 to 4 carbon atoms, particularly preferably —CH 2 —, from the viewpoint of easy production of the compound (A13).
　Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－Ｒ５１－基としては、表面層の撥水撥油性、耐久性、指紋汚れ除去性、潤滑性、さらに外観にもさらに優れる点および化合物（Ａ１３）の製造のしやすさの点から、基（Ｒｆ－１）、および基（Ｒｆ－２）が好ましい。
　Ｒｆ１１Ｏ｛（ＣＦ２Ｏ）ｍ２１（ＣＦ２ＣＦ２Ｏ）ｍ２２｝ＣＦ２－　　（Ｒｆ－１）
　Ｒｆ１１ＯＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ｛（ＣＦ２Ｏ）ｍ２１（ＣＦ２ＣＦ２Ｏ）ｍ２２｝ＣＦ２－　　（Ｒｆ－２）
　ただし、Ｒｆ１１は、炭素数１～２０で直鎖状のペルフルオロアルキル基であり；ｍ２１およびｍ２２は、それぞれ１以上の整数であり、ｍ２１＋ｍ２２は、２～２００の整数であり、ｍ２１個のＣＦ２Ｏおよびｍ２２個のＣＦ２ＣＦ２Ｏの結合順序は限定されない。 The R f1 —O—Q—R fe —R 51 — group has the following features: water / oil repellency, durability, fingerprint stain removability, lubricity, and further appearance of the surface layer; and production of compound (A13) From the viewpoint of easy handling, the group (R f -1) and the group (R f -2) are preferable.
R f11 O {(CF 2 O ) m21 (CF 2 CF 2 O) m22} CF 2 - (R f -1)
R f11 OCHFCF 2 OCH 2 CF 2 O {(CF 2 O) m21 (CF 2 CF 2 O) m22} CF 2 - (R f -2)
However, R f11 is a linear perfluoroalkyl group with 1 to 20 carbon atoms; m21 and m22 are each an integer of 1 or more, m21 + m22 is an integer of 2 ~ 200, m21 amino CF The bonding order of 2 O and m22 CF 2 CF 2 O is not limited.
　Ｚ３としては、（ｅ＋ｆ）個の水酸基を有する多価アルコールから水酸基を除いた残基が挙げられる。
　Ｚ３の具体例としては、たとえば、下式の基が挙げられる。Ｚ３としては、水酸基の反応性に優れる点から、１級の水酸基を有する多価アルコールから水酸基を除いた残基が好ましく、原料の入手容易性の点から、基（Ｚ－１）、基（Ｚ－２）、および、基（Ｚ－３）が特に好ましい。ただし、Ｒ４は、アルキル基であり、メチル基またはエチル基であることが好ましい。 Examples of Z 3 include a residue obtained by removing a hydroxyl group from a polyhydric alcohol having (e + f) hydroxyl groups.
Specific examples of Z 3 include groups represented by the following formula. Z 3 is preferably a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a primary hydroxyl group from the viewpoint of excellent hydroxyl reactivity. From the viewpoint of availability of raw materials, Z (3), (Z-2) and the group (Z-3) are particularly preferred. However, R 4 is an alkyl group, and is preferably a methyl group or an ethyl group.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　Ｒ５３としては、化合物（Ａ１３）の製造のしやすさの点から、炭素数３～１４のアルキレン基が好ましい。さらに、後述する化合物（Ａ１３）の製造におけるヒドロシリル化の際に、アリル基（－ＣＨ２ＣＨ＝ＣＨ２）の一部または全部がインナーオレフィン（－ＣＨ＝ＣＨＣＨ３）に異性化した副生物が生成しにくい点から、炭素数４～１０のアルキレン基が特に好ましい。 R 53 is preferably an alkylene group having 3 to 14 carbon atoms from the viewpoint of easy production of the compound (A13). Furthermore, a by-product in which part or all of the allyl group (—CH 2 CH═CH 2 ) is isomerized to the inner olefin (—CH═CHCH 3 ) during hydrosilylation in the production of the compound (A13) described later is obtained. An alkylene group having 4 to 10 carbon atoms is particularly preferred because it is difficult to form.
　化合物（Ａ１３）としては、たとえば、下式の化合物が挙げられる。これらの化合物は、工業的に製造しやすく、取扱いやすく、表面層の撥水撥油性、耐摩擦性、指紋汚れ除去性、潤滑性、外観にさらに優れる点から好ましい。 Examples of the compound (A13) include compounds represented by the following formula. These compounds are preferable because they are easy to produce industrially, are easy to handle, and are excellent in water / oil repellency, friction resistance, fingerprint stain removability, lubricity and appearance of the surface layer.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　ただし、これらの式中のＷは、Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－である。Ｗの好ましい形態は、上述した好ましいＲｆ１、ＱおよびＲｆｅを組み合わせたものとなる。Ｒ５１の好ましい形態は上述した通りである。 However, W in these formulas is R f1 —OQRfe —. A preferred form of W is a combination of the preferred R f1 , Q and R fe described above. A preferred form of R 51 is as described above.
（遷移金属化合物）
　遷移金属化合物としては、後述するヒドロシリル化反応、加水分解性シリル基のシラノール基への加水分解反応、該シラノール基と基材の表面の水酸基（基材－ＯＨ）との脱水縮合反応等において触媒として作用するものが挙げられる。このような作用を有する遷移金属化合物としては、第８～１０族の遷移金属を含む化合物が挙げられる。
　第８～１０族の遷移金属を含む化合物としては、ルテニウム（Ｒｕ）化合物、鉄（Ｆｅ）化合物、ロジウム（Ｒｈ）化合物、コバルト（Ｃｏ）化合物、白金（Ｐｔ）化合物、ニッケル（Ｎｉ）化合物、パラジウム（Ｐｄ）化合物等が挙げられる。前記加水分解反応、脱水縮合反応に対し高い触媒作用を示す点から、白金化合物が特に好ましい。
　なお、第８～１０族とは、ＩＵＰＡＣ無機化学命名法改訂版（１９８９年）による族番号である。 (Transition metal compounds)
Transition metal compounds include catalysts in hydrosilylation reactions described later, hydrolysis reactions of hydrolyzable silyl groups into silanol groups, and dehydration condensation reactions between the silanol groups and hydroxyl groups on the surface of the substrate (substrate-OH). The thing which acts as is mentioned. Examples of the transition metal compound having such an action include compounds containing a group 8-10 transition metal.
Examples of the compound containing a Group 8-10 transition metal include ruthenium (Ru) compounds, iron (Fe) compounds, rhodium (Rh) compounds, cobalt (Co) compounds, platinum (Pt) compounds, nickel (Ni) compounds, Examples thereof include palladium (Pd) compounds. A platinum compound is particularly preferable because it exhibits a high catalytic action for the hydrolysis reaction and dehydration condensation reaction.
Groups 8 to 10 are group numbers according to the revised IUPAC inorganic chemical nomenclature (1989).
　白金化合物としては、白金単体、白金／ジビニルテトラメチルジシロキサン錯体、白金／テトラメチルテトラビニルシクロテトラシロキサン錯体、塩化白金酸、酸化白金等が挙げられる。なかでも、白金／ジビニルテトラメチルジシロキサン錯体、および、白金／テトラメチルテトラビニルシクロテトラシロキサン錯体が好ましい。 Examples of the platinum compound include platinum alone, platinum / divinyltetramethyldisiloxane complex, platinum / tetramethyltetravinylcyclotetrasiloxane complex, chloroplatinic acid, and platinum oxide. Of these, platinum / divinyltetramethyldisiloxane complexes and platinum / tetramethyltetravinylcyclotetrasiloxane complexes are preferred.
（他の含フッ素エーテル化合物）
　本組成物は、化合物（Ａ）と、遷移金属化合物とからなるものでもよく、化合物（Ａ）以外の他の含フッ素エーテル化合物をさらに含むものでもよい。
　他の含フッ素エーテル化合物としては、たとえば、ポリ（オキシペルフルオロアルキレン）鎖を有し、基（Ｉ）を有しない含フッ素エーテル化合物（以下、化合物（Ｃ）とも記す。）が挙げられる。該ポリ（オキシペルフルオロアルキレン）鎖は、ＰＦＥ鎖であってもよい。 (Other fluorine-containing ether compounds)
This composition may consist of a compound (A) and a transition metal compound, and may further contain other fluorine-containing ether compounds other than a compound (A).
Examples of other fluorine-containing ether compounds include fluorine-containing ether compounds having a poly (oxyperfluoroalkylene) chain and having no group (I) (hereinafter also referred to as compound (C)). The poly (oxyperfluoroalkylene) chain may be a PFE chain.
　化合物（Ｃ）としては、たとえば化合物（Ｃ１）が挙げられる。
　Ａ３１－Ｏ－Ｑ５１－（ＲＦ３Ｏ）ｍ３０－［Ｑ５２－Ｏ］ｐ３－Ａ３２　・・・（Ｃ１）
　ただし、Ａ３１およびＡ３２は、それぞれ独立に炭素数１～２０のペルフルオロアルキル基であり；Ｑ５１は、単結合、１個以上の水素原子を含む分岐構造を有しない炭素数１～６のフルオロアルキレン基、１個以上の水素原子を含む分岐構造を有しない炭素数１～６のフルオロアルキレン基の末端（ただし、Ａ３１－Ｏと結合する側の末端を除く。）にエーテル性酸素原子を有する基、１個以上の水素原子を含む分岐構造を有しない炭素数２～６のフルオロアルキレン基の炭素－炭素原子間にエーテル性酸素原子を有する基、または１個以上の水素原子を含む分岐構造を有しない炭素数２～６のフルオロアルキレン基の末端（ただし、Ａ３１－Ｏと結合する側の末端を除く。）および炭素－炭素原子間にエーテル性酸素原子を有する基であり（ただし、酸素数は１０以下である。）；Ｑ５２は、１個以上の水素原子を含む分岐構造を有しない炭素数１～２０のフルオロアルキレン基、または１個以上の水素原子を含む分岐構造を有しない炭素数２～６のフルオロアルキレン基の炭素－炭素原子間にエーテル性酸素原子を有する基であり（ただし、酸素数は１０以下である。）；ＲＦ３は、分岐構造を有しない炭素数１～６のペルフルオロアルキレン基であり；ｍ３０は、２～２００の整数であり；（ＲＦ３Ｏ）ｍ３０は、炭素数の異なる２種以上のＲＦ３Ｏからなるものであってもよく；ｐ３は、Ｑ５１が単結合の場合は０であり、Ｑ５１が単結合以外の場合は１である。 Examples of the compound (C) include the compound (C1).
A 31 —O—Q 51 — (R F3 O) m30 — [Q 52 —O] p3 —A 32 ... (C1)
Provided that A 31 and A 32 are each independently a perfluoroalkyl group having 1 to 20 carbon atoms; Q 51 is a single bond having 1 to 6 carbon atoms that does not have a branched structure containing one or more hydrogen atoms. An etheric oxygen atom at the terminal of a fluoroalkylene group having 1 to 6 carbon atoms not having a branched structure containing one or more hydrogen atoms (excluding the terminal on the side bonded to A 31 —O) A group having 1 or more, a group having an etheric oxygen atom between carbon-carbon atoms of a C 2-6 fluoroalkylene group not having a branched structure containing one or more hydrogen atoms, or one or more hydrogen atoms A group having an etheric oxygen atom between the terminal of a fluoroalkylene group having 2 to 6 carbon atoms not having a branched structure (excluding the terminal on the side bonded to A 31 —O) and the carbon-carbon atom (Provided that the oxygen number is 10 or less); Q 52 represents a fluoroalkylene group having 1 to 20 carbon atoms which does not have a branched structure containing one or more hydrogen atoms, or one or more hydrogen atoms. A group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 to 6 carbon atoms not having a branched structure (provided that the oxygen number is 10 or less); R F3 is a branched structure M30 is an integer of 2 to 200; (R F3 O) m30 is composed of two or more types of R F3 O having different carbon numbers. at best; p3, if Q 51 is a single bond is 0, if Q 51 is other than a single bond is 1.
　化合物（Ｃ１）は、公知の製造方法により製造したものを用いてもよく、市販品を用いてもよい。たとえば、Ｑ５１が単結合であり、ｐ３が０である化合物（Ｃ１）の市販品としては、ＦＯＭＢＬＩＮ（登録商標）Ｍ、ＦＯＭＢＬＩＮ（登録商標）Ｙ、ＦＯＭＢＬＩＮ（登録商標）Ｚ（以上、ソルベイソレクシス社製）、Ｋｒｙｔｏｘ（登録商標）（デュポン社製）、デムナム（登録商標）（ダイキン工業社製）等が挙げられる。 As the compound (C1), one produced by a known production method may be used, or a commercially available product may be used. For example, commercial products of compound (C1) in which Q 51 is a single bond and p3 is 0 include FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, FOMBLIN (registered trademark) Z (above, Solvaiso Lexis), Krytox (registered trademark) (manufactured by DuPont), and Demnam (registered trademark) (manufactured by Daikin Industries).
（本組成物の組成）
　本組成物において、化合物（Ａ）に対する遷移金属化合物の質量割合は遷移金属換算で、３００～４，０００ｐｐｍである。遷移金属化合物の質量割合が前記範囲内であれば、基材の透明性を損なうことなく、表面層の耐久性を向上できる。化合物（Ａ）に対する遷移金属化合物の質量割合は遷移金属換算で、４００～２，０００ｐｐｍが好ましく、５００～１，０００ｐｐｍが特に好ましい。 (Composition of this composition)
In the present composition, the mass ratio of the transition metal compound to the compound (A) is 300 to 4,000 ppm in terms of transition metal. If the mass ratio of the transition metal compound is within the above range, the durability of the surface layer can be improved without impairing the transparency of the substrate. The mass ratio of the transition metal compound to the compound (A) is preferably 400 to 2,000 ppm, particularly preferably 500 to 1,000 ppm, in terms of transition metal.
　本組成物において、化合物（Ａ）および遷移金属化合物の合計量は、本組成物の総質量に対し、０．１質量％以上が好ましく、５質量％以上がより好ましく、３０質量％以上がさらに好ましく、５０質量％以上が特に好ましく、８０質量％以上が最も好ましい。上限は特に限定されず、１００質量％であってもよい。 In the present composition, the total amount of the compound (A) and the transition metal compound is preferably 0.1% by mass or more, more preferably 5% by mass or more, and further preferably 30% by mass or more with respect to the total mass of the present composition. Preferably, 50% by mass or more is particularly preferable, and 80% by mass or more is most preferable. An upper limit is not specifically limited, 100 mass% may be sufficient.
　本組成物中の遷移金属化合物の質量割合を前記範囲内とするには、たとえば、以下のようにして化合物（ＡＸ）を製造すればよい。 In order to make the mass ratio of the transition metal compound in the composition within the above range, for example, the compound (AX) may be produced as follows.
〔含フッ素エーテル組成物の製造方法〕
（１）第１実施形態例
　第１実施形態例の含フッ素エーテル組成物の製造方法は、以下に示す化合物（Ｂ）と、下式（Ｓ）で表される化合物（以下、化合物（Ｓ）とも記す。）とを、遷移金属化合物の存在下に反応（以下、ヒドロシリル化反応とも記す。）させて、以下に示す化合物（ＡＸ）と該遷移金属化合物とを含む組成物を得る方法であり、遷移金属化合物の使用量が、化合物（Ｂ）に対する前記遷移金属化合物の質量割合として遷移金属換算で３００～４，０００ｐｐｍである。ヒドロシリル化反応は、溶媒の存在下で行ってもよいし、非存在下で行ってもよい。
　得られる含フッ素エーテル組成物は、反応により生成する化合物（ＡＨ）と遷移金属化合物とを含み、化合物（ＡＨ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍである、組成物である。
　ＨＳｉＲｎＬ３－ｎ　・・・（Ｓ）
　ただし、Ｌは水酸基または加水分解性基であり、
　Ｒは水素原子または１価の炭化水素基であり、
　ｎは０～２の整数であり、
　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。 [Method for producing fluorine-containing ether composition]
(1) First Embodiment Example The method for producing a fluorinated ether composition of the first embodiment includes a compound (B) shown below and a compound represented by the following formula (S) (hereinafter referred to as compound (S)). In the presence of a transition metal compound (hereinafter also referred to as a hydrosilylation reaction) to obtain a composition containing the following compound (AX) and the transition metal compound. The amount of the transition metal compound used is 300 to 4,000 ppm in terms of transition metal as the mass ratio of the transition metal compound to the compound (B). The hydrosilylation reaction may be performed in the presence or absence of a solvent.
The resulting fluorine-containing ether composition contains a compound (AH) produced by the reaction and a transition metal compound, and the mass ratio of the transition metal compound to the compound (AH) is 300 to 4,000 ppm in terms of transition metal. It is a composition.
HSiR n L 3-n (S)
However, L is a hydroxyl group or a hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
When n is 2, n R may be the same or different.
（化合物（Ｂ））
　化合物（Ｂ）は、ポリ（オキシペルフルオロアルキレン）鎖および基（ＩＩＩ）を有する。
　－ＣＨ＝ＣＨ２　・・・（ＩＩＩ） (Compound (B))
Compound (B) has a poly (oxyperfluoroalkylene) chain and a group (III).
-CH = CH 2 (III)
　化合物（Ｂ）が有するポリ（オキシペルフルオロアルキレン）鎖は、生成物である化合物（ＡＸ）が有するポリ（オキシペルフルオロアルキレン）鎖と同じである。化合物（ＡＸ）が有するポリ（オキシペルフルオロアルキレン）鎖は、前記化合物（Ａ）が有するＰＦＥ鎖と同じである。 The poly (oxyperfluoroalkylene) chain of the compound (B) is the same as the poly (oxyperfluoroalkylene) chain of the product compound (AX). The poly (oxyperfluoroalkylene) chain that the compound (AX) has is the same as the PFE chain that the compound (A) has.
　化合物（Ｂ）が有する基（ＩＩＩ）は１個でもよく２個以上でもよい。基材との結合が増えることにより表面層の耐久性がより優れる点から、２個以上が好ましく、３個以上が特に好ましい。基材に結合する分子密度を高くすることにより表面層の耐久性がより優れる点から、１０個以下が好ましく、５個以下がより好ましく、４個以下が特に好ましい。
　したがって、化合物（Ｂ）が有する基（ＩＩＩ）は１～１０個が好ましく、２～５個がより好ましく、３～４個が特に好ましい。
　化合物（Ｂ）が有する基（ＩＩＩ）が後述する化合物（Ｓ）と反応（ヒドロシリル化反応）することで、後述の化合物（ＡＸ）が有する基（ＩＸ）となる。 The group (III) possessed by the compound (B) may be one or two or more. Two or more are preferable and three or more are particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the bond with the substrate. 10 or less is preferable, 5 or less is more preferable, and 4 or less is particularly preferable from the viewpoint that the durability of the surface layer is further improved by increasing the density of molecules bonded to the substrate.
Accordingly, the group (III) of the compound (B) is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 3 to 4.
The group (III) possessed by the compound (B) reacts with the compound (S) described later (hydrosilylation reaction), whereby the group (IX) possessed by the compound (AX) described later is obtained.
　化合物（Ｂ）の好ましい一態様として、化合物（Ｂ１）が挙げられる。
　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］ａＹ１［－ＣＨ＝ＣＨ２］ｂ　・・・（Ｂ１）
　ただし、Ｒｆ１、Ｑ、Ｒｆｅ、ａおよびｂはそれぞれ前記と同義であり、
　Ｙ１は、（ａ＋ｂ）価の連結基であり、
　ａが２以上のときａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は、同一であっても異なっていてもよい。 A preferred embodiment of compound (B) is compound (B1).
[R f1 —OQR fe —] a Y 1 [—CH═CH 2 ] b (B1)
However, R f1 , Q, R fe , a and b are as defined above,
Y 1 is a (a + b) -valent linking group,
When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different.
　Ｒｆ１は前記基（ＩＩ）中のＲｆ１と同様であり、好ましい態様も同様である。
　ａが２以上のときａ個のＲｆ１は、炭素数が同一であることが好ましく、製造しやすさの点から、同一の基、すなわち炭素数が同一かつ化学構造が同一の基であることが好ましい。炭素数が同一かつ化学構造が同一の基であるとは、たとえばａが２の場合に、２個のＲｆ１がＣＦ３ＣＦ２ＣＦ２－であるということである（２個のＲｆ１の炭素数が同一であっても化学構造が異なる、ＣＦ３ＣＦ２ＣＦ２－、ＣＦ３ＣＦ（ＣＦ３）－の組み合わせではない。） R f1 is the same as R f1 in the group (II), preferable embodiments thereof are also the same.
When a is 2 or more, a R f1 is preferably the same in number of carbon atoms, and from the viewpoint of ease of production, the same group, that is, the same number of carbon atoms and the same chemical structure. Is preferred. The group having the same carbon number and the same chemical structure means that, for example, when a is 2, two R f1 are CF 3 CF 2 CF 2 — (the two R f1 (It is not a combination of CF 3 CF 2 CF 2 — and CF 3 CF (CF 3 ) —, which have the same carbon number but different chemical structures.)
　Ｑは前記基（ＩＩ）中のＱと同様であり、好ましい態様も同様である。
　Ｒｆｅのポリ（オキシペルフルオロアルキレン）鎖は前記と同様であり、好ましい態様も同様である。
　ａの好ましい値はそれぞれ、化合物（Ａ）が有するＰＦＥ鎖の好ましい数と同様である。すなわち、ａはそれぞれ、１～３の整数が好ましい。
　ｂの好ましい値は、化合物（Ａ）が有する基（Ｉ）の好ましい数と同様である。すなわち、ｂは１～１０の整数が好ましく、２～５の整数がより好ましく、３～４の整数が特に好ましい。 Q is the same as Q in the group (II), and preferred embodiments are also the same.
The poly (oxyperfluoroalkylene) chain of R fe is the same as described above, and the preferred embodiment is also the same.
Preferred values for a are the same as the preferred number of PFE chains that compound (A) has. That is, each a is preferably an integer of 1 to 3.
The preferable value of b is the same as the preferable number of groups (I) that the compound (A) has. That is, b is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and particularly preferably an integer of 3 to 4.
　Ｙ１としては、たとえば、（ａ＋ｂ）価の置換または無置換の炭化水素基、置換または無置換の炭化水素基の炭素－炭素原子間または／および末端に、炭化水素基以外の基または原子を有する（ａ＋ｂ）価の基、（ａ＋ｂ）価のオルガノポリシロキサン基等が挙げられる。 Y 1 is, for example, a (a + b) -valent substituted or unsubstituted hydrocarbon group, a group or atom other than a hydrocarbon group at the carbon-carbon atom or / and terminal of the substituted or unsubstituted hydrocarbon group. Examples thereof include (a + b) -valent groups and (a + b) -valent organopolysiloxane groups.
　無置換の炭化水素基としては、たとえば直鎖状または分岐状の飽和炭化水素基、芳香族炭化水素環式基（たとえばベンゼン環、ナフタレン環等の芳香族炭化水素環から（ａ＋ｂ）個の水素原子を除いた基）、直鎖状または分岐状の飽和炭化水素基と芳香族炭化水素環式基との組み合わせからなる基（たとえば前記芳香族炭化水素環式基に置換基としてアルキル基が結合した基、前記飽和炭化水素基の炭素原子間または／および末端にフェニレン基等のアリーレン基を有する基等）、２以上の芳香族炭化水素環式基の組み合わせからなる基等が挙げられる。これらの中でも直鎖状または分岐状の飽和炭化水素基が好ましい。無置換の炭化水素基の炭素数は、２０以下が好ましい。
　置換の炭化水素基は、炭化水素基の水素原子の一部または全部が置換基で置換された基である。置換基としては、たとえば水酸基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、アミノ基、ニトロ基、シアノ基、アミノカルボニル基等が挙げられる。 Examples of the unsubstituted hydrocarbon group include a linear or branched saturated hydrocarbon group, an aromatic hydrocarbon cyclic group (for example, (a + b) hydrogen atoms from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring). A group excluding an atom), a group composed of a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, an alkyl group bonded to the aromatic hydrocarbon cyclic group as a substituent) And groups having an arylene group such as a phenylene group between and / or at the terminal of the saturated hydrocarbon group), and a group formed of a combination of two or more aromatic hydrocarbon cyclic groups. Among these, a linear or branched saturated hydrocarbon group is preferable. The number of carbon atoms of the unsubstituted hydrocarbon group is preferably 20 or less.
The substituted hydrocarbon group is a group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with a substituent. Examples of the substituent include a hydroxyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an amino group, a nitro group, a cyano group, and an aminocarbonyl group.
　炭化水素基の炭素－炭素原子間または／および末端に有する炭化水素基以外の基または原子としては、たとえばエーテル性酸素原子（－Ｏ－）、チオエーテル性硫黄原子（－Ｓ－）、窒素原子（－Ｎ＜）、ケイ素原子（＞Ｓｉ＜）、炭素原子（＞Ｃ＜）、－Ｎ（Ｒ１５）－、－Ｃ（Ｏ）Ｎ（Ｒ１５）－、－ＯＣ（Ｏ）Ｎ（Ｒ１５）－、－Ｓｉ（Ｒ１６）（Ｒ１７）－、オルガノポリシロキサン基、－Ｃ（Ｏ）－、－Ｃ（Ｏ）－Ｏ－、－Ｃ（Ｏ）－Ｓ－等が挙げられる。ただし、Ｒ１５は水素原子、アルキル基またはフェニル基であり、Ｒ１６～Ｒ１７はそれぞれ独立にアルキル基またはフェニル基である。アルキル基の炭素数は、１～６が好ましい。
　オルガノポリシロキサン基は、直鎖状でもよく、分岐鎖状でもよく、環状でもよい。 Examples of the group or atom other than the hydrocarbon group between the carbon-carbon atoms and / or the terminal of the hydrocarbon group include an etheric oxygen atom (—O—), a thioetheric sulfur atom (—S—), a nitrogen atom ( —N <), silicon atom (> Si <), carbon atom (> C <), —N (R 15 ) —, —C (O) N (R 15 ) —, —OC (O) N (R 15 )-, -Si (R 16 ) (R 17 )-, organopolysiloxane groups, -C (O)-, -C (O) -O-, -C (O) -S- and the like. However, R 15 is a hydrogen atom, an alkyl group or a phenyl group, and R 16 to R 17 are each independently an alkyl group or a phenyl group. The alkyl group preferably has 1 to 6 carbon atoms.
The organopolysiloxane group may be linear, branched, or cyclic.
　化合物（Ｂ１）は、後述する化合物（ＡＸ１）から［－ＳｉＲｎＬ３－ｎ］が外れ、かつＺ１Ｘの－ＳｉＲｎＬ３－ｎとの結合末端の－ＣＨ２ＣＨ２－が－ＣＨ＝ＣＨ２となった化合物である。 In the compound (B1), [—SiR n L 3-n ] is removed from the compound (AX1) described later, and —CH 2 CH 2 — at the bonding terminal of Z 1X to —SiR n L 3-n is —CH = CH 2 compound.
（化合物（Ｓ））
　化合物（Ｓ）は、下式（Ｓ）で表される化合物である。
　ＨＳｉＲｎＬ３－ｎ　・・・（Ｓ）
　ただし、Ｌは水酸基または加水分解性基であり、
　Ｒは水素原子または１価の炭化水素基であり、
　ｎは０～２の整数であり、
　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。 (Compound (S))
The compound (S) is a compound represented by the following formula (S).
HSiR n L 3-n (S)
However, L is a hydroxyl group or a hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
When n is 2, n R may be the same or different.
　前記式（Ｓ）のＲ、Ｌおよびｎは、基（Ｉ）におけるＲ、Ｌおよびｎと同じである。 R, L and n in the formula (S) are the same as R, L and n in the group (I).
　化合物（Ｓ）としては、ＨＳｉ（ＯＣＨ３）３、ＨＳｉＣＨ３（ＯＣＨ３）２、ＨＳｉ（ＯＣＨ２ＣＨ３）３、ＨＳｉＣｌ３、ＨＳｉ（ＯＣＯＣＨ３）３、ＨＳｉ（ＮＣＯ）３が好ましい。工業的な製造における取扱いやすさの点から、ＨＳｉ（ＯＣＨ３）３が特に好ましい。 As the compound (S), HSi (OCH 3 ) 3 , HSiCH 3 (OCH 3 ) 2 , HSi (OCH 2 CH 3 ) 3 , HSiCl 3 , HSi (OCOCH 3 ) 3 and HSi (NCO) 3 are preferable. HSi (OCH 3 ) 3 is particularly preferable from the viewpoint of easy handling in industrial production.
（遷移金属化合物）
　遷移金属化合物としては、先に例示したものが挙げられる。 (Transition metal compounds)
Examples of the transition metal compound include those exemplified above.
（溶媒）
　溶媒としては、有機溶媒が好ましい。有機溶媒は、フッ素系有機溶媒であっても非フッ素系有機溶媒であってもよく、両溶媒を用いてもよい。
　フッ素系有機溶媒としては、フッ素化アルカン、フッ素化芳香族化合物、フルオロアルキルエーテル、フッ素化アルキルアミン、フルオロアルコール等が挙げられる。
　フッ素化アルカンとしては、炭素数４～８の化合物が好ましい。市販品としては、たとえば、Ｃ６Ｆ１３Ｈ（旭硝子社製、アサヒクリン（登録商標）ＡＣ－２０００）、Ｃ６Ｆ１３Ｃ２Ｈ５（旭硝子社製、アサヒクリン（登録商標）ＡＣ－６０００）、Ｃ２Ｆ５ＣＨＦＣＨＦＣＦ３（ケマーズ社製、バートレル（登録商標）ＸＦ）等が挙げられる。
　フッ素化芳香族化合物としては、たとえば、ヘキサフルオロベンゼン、トリフルオロメチルベンゼン、ペルフルオロ卜ルエン、ビス（卜リフルオロメチル）ベンゼン等が挙げられる。
　フルオロアルキルエーテルとしては、炭素数４～１２の化合物が好ましい。市販品としては、たとえば、ＣＦ３ＣＨ２ＯＣＦ２ＣＦ２Ｈ (旭硝子社製、アサヒクリン（登録商標）ＡＥ－３０００）、Ｃ４Ｆ９ＯＣＨ３（３Ｍ社製、ノベック（登録商標）７１００）、Ｃ４Ｆ９ＯＣ２Ｈ５（３Ｍ社製、ノベック（登録商標）７２００）、Ｃ６Ｆ１３ＯＣＨ３（３Ｍ社製、ノベック（登録商標）７３００）等が挙げられる。
　フッ素化アルキルアミンとしては、たとえば、ペルフルオロ卜リプロピルアミン、ペルフルオロ卜リブチルアミン等が挙げられる。
　フルオロアルコールとしては、たとえば、２，２，３，３－テトラフルオロプロパノール、２，２，２－卜リフルオロエタノール、ヘキサフルオロイソプロパノール等が挙げられる。 (solvent)
As the solvent, an organic solvent is preferable. The organic solvent may be a fluorinated organic solvent or a non-fluorinated organic solvent, or both solvents may be used.
Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferable. Examples of commercially available products include C 6 F 13 H (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC-2000), C 6 F 13 C 2 H 5 (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC-6000). ), C 2 F 5 CHFCHFCF 3 (manufactured by Chemers, Bertrell (registered trademark) XF) and the like.
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorobenzene, bis (卜 trifluoromethyl) benzene, and the like.
As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. Examples of commercially available products include CF 3 CH 2 OCF 2 CF 2 H (Asahi Glass Co., Ltd., Asahiklin (registered trademark) AE-3000), C 4 F 9 OCH 3 (3M Co., Novec (registered trademark) 7100). C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200), C 6 F 13 OCH 3 (manufactured by 3M, Novec (registered trademark) 7300), and the like.
Examples of the fluorinated alkylamine include perfluoropolypropylamine and perfluoropolybutylamine.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
　フッ素系有機溶媒としては、化合物（Ｂ）および化合物（Ｓ）の相溶性等の点で、フッ素化アルカン、フッ素化芳香族化合物、フルオロアルキルエーテルからなる群から選択される少なくとも１種の含フッ素有機溶媒を使用することが好ましい。 The fluorine-based organic solvent is at least one fluorine-containing compound selected from the group consisting of a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether in terms of compatibility between the compound (B) and the compound (S). It is preferable to use an organic solvent.
　非フッ素系有機溶媒としては、水素原子および炭素原子のみからなる化合物、水素原子、炭素原子および酸素原子のみからなる化合物が好ましく、炭化水素系有機溶媒、ケトン系有機溶媒、エーテル系有機溶媒、エステル系有機溶媒が挙げられる。
　炭化水素系有機溶媒としては、ヘキサン、へブタン、シク口ヘキサン等が挙げられる。
　ケトン系有機溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン等が挙げられる。
　エーテル系有機溶媒としては、ジエチルエーテル、テ卜ラヒド口フラン、テ卜ラエチレングリコールジメチルエーテル等が挙げられる。
　エステル系有機溶媒としては、酢酸エチル、酢酸ブチル等が挙げられる。
　非フッ素系有機溶媒としては、化合物（Ｂ）および化合物（Ｓ）の相溶性等の点で、炭化水素系有機溶媒が特に好ましい。 As the non-fluorine organic solvent, a compound consisting only of hydrogen and carbon atoms, a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferred, hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, esters System organic solvents.
Examples of the hydrocarbon-based organic solvent include hexane, heptane, and hexane hexane.
Examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Examples of ether-based organic solvents include diethyl ether, terahydrofuran, and teraethylene glycol dimethyl ether.
Examples of the ester organic solvent include ethyl acetate and butyl acetate.
As the non-fluorine organic solvent, a hydrocarbon organic solvent is particularly preferable from the viewpoint of compatibility of the compound (B) and the compound (S).
　溶媒の使用量は、化合物（Ｂ）の１００質量部に対して、０．１～１０，０００質量部であることが好ましく、１～１，０００質量部が特に好ましい。溶媒の使用量が前記範囲内であれば、化合物（Ｂ）および化合物（Ｓ）を充分に相溶化させる効果があり、反応条件を穏やかにできる。 The amount of the solvent used is preferably 0.1 to 10,000 parts by mass, particularly preferably 1 to 1,000 parts by mass with respect to 100 parts by mass of the compound (B). When the amount of the solvent used is within the above range, there is an effect of sufficiently compatibilizing the compound (B) and the compound (S), and the reaction conditions can be moderated.
（ヒドロシリル化反応）
　遷移金属化合物の存在下における、化合物（Ｂ）と化合物（Ｓ）とのヒドロシリル化反応は、たとえば、ポリオレフィン、含フッ素樹脂等の樹脂製容器、ガラス製容器、ＳＵＳ等の金属製容器、または含フッ素樹脂等で被覆したライニング容器等を用いて行う。
　反応温度は、反応が充分に進行し、副生物の生成が抑制される点から、０～１００℃が好ましく、２０～５０℃が特に好ましい。
　反応時間は、１～１００時間が好ましく、２～２０時間が特に好ましい。
　反応圧力は、－０．０１～１ＭＰａＧが好ましく、０～０．１ＭＰａＧが特に好ましい。ここで、「ＭＰａＧ」における「Ｇ」は、ゲージ圧を示す。 (Hydrosilylation reaction)
The hydrosilylation reaction between the compound (B) and the compound (S) in the presence of the transition metal compound is, for example, a resin container such as a polyolefin or a fluorine-containing resin, a glass container, a metal container such as SUS, or the like. A lining container coated with a fluororesin is used.
The reaction temperature is preferably 0 to 100 ° C., particularly preferably 20 to 50 ° C., from the viewpoint that the reaction proceeds sufficiently and the formation of by-products is suppressed.
The reaction time is preferably 1 to 100 hours, particularly preferably 2 to 20 hours.
The reaction pressure is preferably −0.01 to 1 MPaG, particularly preferably 0 to 0.1 MPaG. Here, “G” in “MPaG” indicates a gauge pressure.
　第１実施形態例の含フッ素エーテル組成物の製造方法では、ヒドロシリル化反応において遷移金属化合物を、化合物（Ｂ）に対する質量割合として遷移金属換算で３００～４，０００ｐｐｍ使用する。遷移金属化合物の使用量は遷移金属換算で、４００～２，０００ｐｐｍが好ましく、５００～１，０００ｐｐｍが特に好ましい。
　ここでの遷移金属化合物の使用量は化合物（Ｂ）に対する量であるが、該遷移金属化合物の使用量は、生成物である化合物（ＡＸ）に対する遷移金属化合物の割合とほぼ等しい。 In the method for producing a fluorine-containing ether composition of the first embodiment, a transition metal compound is used in a hydrosilylation reaction in a mass ratio of 300 to 4,000 ppm in terms of transition metal relative to the compound (B). The amount of the transition metal compound used is preferably 400 to 2,000 ppm, particularly preferably 500 to 1,000 ppm, in terms of transition metal.
The amount of the transition metal compound used here is the amount relative to the compound (B), but the amount of the transition metal compound used is approximately equal to the ratio of the transition metal compound to the product compound (AX).
　化合物（Ｓ）としてＬがハロゲン原子のもの（たとえば、ＨＳｉＣｌ３等）を用いる場合、オルト蟻酸メチル等のオルトエステルを併用してもよい。オルトエステルを併用することで、Ｌのハロゲン原子がアルコキシ基に置換されたものが、化合物（Ｂ）に導入される。 In the case where L is a halogen atom (for example, HSiCl 3 or the like) as the compound (S), an ortho ester such as methyl orthoformate may be used in combination. By using an ortho ester in combination, the compound in which the halogen atom of L is substituted with an alkoxy group is introduced into the compound (B).
　ヒドロシリル化反応において溶媒を使用する場合、反応後に反応液を濃縮して溶媒を除去してもよい。 When a solvent is used in the hydrosilylation reaction, the reaction solution may be concentrated after the reaction to remove the solvent.
　第１実施形態例の含フッ素エーテル組成物の製造方法では、原則として生成した化合物（ＡＸ）に遷移金属化合物を添加しないが、必要に応じて生成した化合物（ＡＸ）に遷移金属化合物を添加してもよい。化合物（ＡＸ）に遷移金属化合物を添加する場合の遷移金属化合物の添加量は、化合物（ＡＸ）に対する遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍとなる量が好ましく、４００～２，０００ｐｐｍとなる量がより好ましく、５００～１，０００ｐｐｍとなる量が特に好ましい。 In the method for producing a fluorine-containing ether composition of the first embodiment, in principle, a transition metal compound is not added to the compound (AX) produced, but a transition metal compound is added to the compound (AX) produced as necessary. May be. When the transition metal compound is added to the compound (AX), the addition amount of the transition metal compound is preferably such that the mass ratio of the transition metal compound to the compound (AX) is 300 to 4,000 ppm in terms of transition metal. An amount of 2,000 ppm is more preferable, and an amount of 500 to 1,000 ppm is particularly preferable.
（化合物（ＡＸ））
　化合物（ＡＸ）は、ポリ（オキシペルフルオロアルキレン）鎖および基（ＩＸ）を有する。
　－ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ　・・・（ＩＸ）
　ただし、Ｌは水酸基または加水分解性基であり、
　Ｒは水素原子または１価の炭化水素基であり、
　ｎは０～２の整数であり、
　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。 (Compound (AX))
Compound (AX) has a poly (oxyperfluoroalkylene) chain and a group (IX).
—CH 2 CH 2 —SiR n L 3-n (IX)
However, L is a hydroxyl group or a hydrolysable group,
R is a hydrogen atom or a monovalent hydrocarbon group,
n is an integer from 0 to 2,
when n is 0 or 1, (3-n) L's may be the same or different;
When n is 2, n R may be the same or different.
　化合物（ＡＸ）が有するポリ（オキシペルフルオロアルキレン）鎖は、前記化合物（Ａ）が有するＰＦＥ鎖と同じである。 The poly (oxyperfluoroalkylene) chain of the compound (AX) is the same as the PFE chain of the compound (A).
　化合物（ＡＸ）としては、国際公開第２０１４／１６３００４号、国際公開第２０１３／１２１９８４号、特開２０１５－１９９９０６号公報に記載される含フッ素エーテル化合物、および下記化合物（ＡＸ１）が好ましい。 As the compound (AX), the fluorine-containing ether compounds described in International Publication No. 2014/163004, International Publication No. 2013/121984, and Japanese Patent Application Laid-Open No. 2015-199906, and the following compound (AX1) are preferable.
　＜化合物（ＡＸ１）＞
　化合物（ＡＸ）の好ましい一態様として、化合物（ＡＸ１）が挙げられる。
　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］ａＺ１Ｘ［－ＳｉＲｎＬ３－ｎ］ｂ　・・・（ＡＸ１）
　ただし、Ｒｆ１、Ｑ、Ｒｆｅ、Ｌ、Ｒ、ｎ、ａおよびｂはそれぞれ前記と同義であり、
　Ｚ１Ｘは、（ａ＋ｂ）価の連結基であり、－ＳｉＲｎＬ３－ｎとの結合末端に－ＣＨ２ＣＨ２－を有し、
　ａが２以上のときａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は、同一であっても異なっていてもよく、
　ｂが２以上のときｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。 <Compound (AX1)>
A preferred embodiment of compound (AX) is compound (AX1).
[R f1 -OQR fe- ] a Z 1X [-SiR n L 3-n ] b (AX1)
However, R f1 , Q, R fe , L, R, n, a and b are as defined above,
Z 1X is a (a + b) -valent linking group, and has —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n ,
When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different,
When b is 2 or more, b [-SiR n L 3-n ] may be the same or different.
　Ｚ１Ｘとしては、前記式（Ａ１）のＺ１において、－ＳｉＲｎＬ３－ｎとの結合末端に－ＣＨ２ＣＨ２－を有するものが挙げられる。
　すなわち、化合物（ＡＸ１）は、前記化合物（Ａ１）において、Ｚ１が－ＳｉＲｎＬ３－ｎとの結合末端に－ＣＨ２ＣＨ２－を有するものである。 Examples of Z 1X include a group having —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n in Z 1 of the formula (A1).
That is, the compound (AX1) is the compound (A1) in which Z 1 has —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n .
　以下に、前記化合物（Ａ１１）～（Ａ１３）を得るための具体的な方法の一例について説明する。 Hereinafter, an example of a specific method for obtaining the compounds (A11) to (A13) will be described.
　「化合物（Ａ１１）の製造方法」
　ｐ１が０の場合、化合物（Ａ１１）の製造方法としては、たとえば下記の方法（１）～（６）が挙げられる。
　ｐ１が１の場合、化合物（Ａ１１）の製造方法としては、たとえば下記の方法（１１）～（１６）が挙げられる。 “Production Method of Compound (A11)”
When p1 is 0, examples of the method for producing compound (A11) include the following methods (1) to (6).
When p1 is 1, examples of the method for producing compound (A11) include the following methods (11) to (16).
　方法（１）：
　出発物質として市販の化合物（１０）を用いる。
　ＨＯ－ＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＨ　・・・（１０）
　ただし、（ＲＦ１Ｏ）ｘは、ポリ（オキシペルフルオロアルキレン）鎖であり、ｘは、１以上の整数である。 Method (1):
Commercially available compound (10) is used as starting material.
HO—CH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (10)
However, (R F1 O) x is a poly (oxyperfluoroalkylene) chain, and x is an integer of 1 or more.
　塩基性化合物の存在下、化合物（１０）にＲｆ１－Ｏ－ＣＦ＝ＣＦ２を反応させて、化合物（１１）、化合物（３Ａ）および未反応の化合物（１０）の混合物を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＨ　・・・（１１）
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＦ２ＣＨＦ－Ｏ－Ｒｆ１　・・・（３Ａ） In the presence of a basic compound, compound (10) is reacted with R f1 —O—CF═CF 2 to obtain a mixture of compound (11), compound (3A) and unreacted compound (10).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (11)
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OCF 2 CHF—O—R f1 (3A)
　混合物から化合物（１１）を単離し、化合物（１１）とＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）Ｃ（Ｏ）Ｆとのエステル化反応によって、化合物（１２）を得る。該エステル化反応は、化合物（１１）と、他の酸フロリド、酸クロリド、酸ブロミド、酸無水物等との反応であってもよい。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＣ（Ｏ）ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３　・・・（１２） Compound (11) is isolated from the mixture, and compound (12) is obtained by esterification reaction of compound (11) and CF 3 CF 2 CF 2 OCF (CF 3 ) C (O) F. The esterification reaction may be a reaction between the compound (11) and another acid fluoride, acid chloride, acid bromide, acid anhydride or the like.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OC (O) CF (CF 3 ) OCF 2 CF 2 CF 3 (12)
　フッ素ガスを用いて化合物（１２）の水素原子をフッ素原子に置換することによって、化合物（１３）を得る。該フッ素化工程は、たとえば、国際公開第２０００／５６６９４号に記載の方法等にしたがって実施できる。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ（ＣＦ２ＣＦ２Ｏ）－Ｃ（Ｏ）ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３　・・・（１３） A compound (13) is obtained by substituting the fluorine atom for the hydrogen atom of the compound (12) using fluorine gas. The fluorination step can be performed, for example, according to the method described in International Publication No. 2000/56694.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x (CF 2 CF 2 O) —C (O) CF (CF 3 ) OCF 2 CF 2 CF 3 ..・ (13)
　化合物（１３）にアルコール（メタノール、エタノール、１－プロパノール、２－プロパノール等。以下、Ｒ１０ＯＨと記す。Ｒ１０はアルキル基である。）を作用させることによって、化合物（１４）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－Ｃ（Ｏ）ＯＲ１０　・・・（１４） Compound (14) is obtained by reacting compound (13) with an alcohol (methanol, ethanol, 1-propanol, 2-propanol, etc., hereinafter referred to as R 10 OH, R 10 is an alkyl group).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —C (O) OR 10 (14)
　化合物（１４）を、還元剤（水素化ホウ素ナトリウム、水素化リチウムアルミニウム等）を用いて水素還元することによって、化合物（１５）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＨ　・・・（１５） Compound (15) is obtained by subjecting compound (14) to hydrogen reduction using a reducing agent (sodium borohydride, lithium aluminum hydride, etc.).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OH (15)
　塩基性化合物の存在下、化合物（１５）にＣＦ３ＳＯ２Ｃｌを反応させて、化合物（１６）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＳＯ２ＣＦ３　・・・（１６） Compound (15) is reacted with CF 3 SO 2 Cl in the presence of a basic compound to give compound (16).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OSO 2 CF 3 (16)
　塩基性化合物の存在下、化合物（１６）にＨＯＣＨ２Ｃ（ＣＨ２ＯＣＨ２ＣＨ＝ＣＨ２）３を反応させて、化合物（１７）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＨ２－Ｃ（ＣＨ２ＯＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７） Compound (16) is reacted with HOCH 2 C (CH 2 OCH 2 CH═CH 2 ) 3 in the presence of a basic compound to give compound (17).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OCH 2 —C (CH 2 OCH 2 CH═CH 2 ) 3. 17)
　化合物（１７）と化合物（Ｓ）とを、化合物（１７）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ａ）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＨ２－Ｃ［ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ａ） The compound (17) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (17). 1A) is obtained.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OCH 2 —C [CH 2 OCH 2 CH 2 CH 2 —SiR n L 3 − n ] 3 ... (1A)
　方法（２）：
　出発物質として方法（１）において得られた化合物（１１）を用いる。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＨ　・・・（１１） Method (2):
The compound (11) obtained in method (1) is used as starting material.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (11)
　塩基性化合物の存在下、化合物（１１）にＣＦ３ＳＯ２Ｃｌを反応させて、化合物（１６Ｂ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＳＯ２ＣＦ３　・・・（１６Ｂ） Compound (16B) is obtained by reacting compound (11) with CF 3 SO 2 Cl in the presence of a basic compound.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OSO 2 CF 3 (16B)
　塩基性化合物の存在下、化合物（１６Ｂ）にＨＯＣＨ２Ｃ（ＣＨ２ＯＣＨ２ＣＨ＝ＣＨ２）３を反応させて、化合物（１７Ｂ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＨ２－Ｃ（ＣＨ２ＯＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｂ） In the presence of a basic compound, HOCH 2 C (CH 2 OCH 2 CH═CH 2 ) 3 is reacted with compound (16B) to obtain compound (17B).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OCH 2 —C (CH 2 OCH 2 CH═CH 2 ) 3 (17B)
　化合物（１７Ｂ）と化合物（Ｓ）とを、化合物（１７Ｂ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｂ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＨ２－Ｃ［ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｂ） The compound (17B) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal with respect to the compound (17B) and, if necessary, a solvent, to give a compound ( 1B) is obtained.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OCH 2 —C [CH 2 OCH 2 CH 2 CH 2 —SiR n L 3-n ] 3 ... (1B)
　方法（３）：
　出発物質として国際公開第２０１３／１２１９８４号に記載の方法で得られた化合物（１５Ｃ）を用いる。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－ＣＨ２ＯＨ　・・・（１５Ｃ） Method (3):
The compound (15C) obtained by the method described in International Publication No. 2013/121984 is used as a starting material.
R f1 —O— (R F1 O) x —Q 32 —CH 2 OH (15C)
　塩基性化合物の存在下、化合物（１５Ｃ）にＣＦ３ＳＯ２Ｃｌを反応させて、化合物（１６Ｃ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－ＣＨ２ＯＳＯ２ＣＦ３　・・・（１６Ｃ） Compound (16C) is obtained by reacting compound (15C) with CF 3 SO 2 Cl in the presence of a basic compound.
R f1 —O— (R F1 O) x -Q 32 —CH 2 OSO 2 CF 3 (16C)
　塩基性化合物の存在下、化合物（１６Ｃ）にＨＯＣＨ２Ｃ（ＣＨ２ＯＣＨ２ＣＨ＝ＣＨ２）３を反応させて、化合物（１７Ｃ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－ＣＨ２ＯＣＨ２－Ｃ（ＣＨ２ＯＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｃ） In the presence of a basic compound, HOCH 2 C (CH 2 OCH 2 CH═CH 2 ) 3 is reacted with compound (16C) to obtain compound (17C).
R f1 —O— (R F1 O) x —Q 32 —CH 2 OCH 2 —C (CH 2 OCH 2 CH═CH 2 ) 3 (17C)
　化合物（１７Ｃ）と化合物（Ｓ）とを、化合物（１７Ｃ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｃ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－ＣＨ２ＯＣＨ２－Ｃ［ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｃ） The compound (17C) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound and, if necessary, a solvent with respect to the compound (17C) as a transition metal. 1C) is obtained.
R f1 —O— (R F1 O) x —Q 32 —CH 2 OCH 2 —C [CH 2 OCH 2 CH 2 CH 2 —SiR n L 3-n ] 3 (1C)
　方法（４）：
　ＨＯＣＨ２Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３と（ＣＦ３ＳＯ２）２Ｏとを反応させて、化合物（２０）を得る。
　ＣＦ３ＳＯ２ＯＣＨ２Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（２０） Method (4):
HOCH 2 C (CH 2 CH═CH 2 ) 3 and (CF 3 SO 2 ) 2 O are reacted to obtain compound (20).
CF 3 SO 2 OCH 2 C (CH 2 CH═CH 2 ) 3 (20)
　出発物質として方法（１）において得られた化合物（１５）を用いる。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＨ　・・・（１５） The compound (15) obtained in method (1) is used as starting material.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OH (15)
　塩基性化合物の存在下、化合物（１５）に化合物（２０）を反応させて、化合物（１７Ｄ）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＨ２－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｄ） Compound (15) is reacted with compound (20) in the presence of a basic compound to give compound (17D).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OCH 2 —C (CH 2 CH═CH 2 ) 3 (17D)
　化合物（１７Ｄ）と化合物（Ｓ）とを、化合物（１７Ｄ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｄ）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＨ２－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｄ） The compound (17D) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (17D). 1D).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OCH 2 —C [CH 2 CH 2 CH 2 —SiR n L 3-n ] 3 ... (1D)
　方法（５）：
　出発物質として方法（１）において得られた化合物（１１）を用いる。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＨ　・・・（１１） Method (5):
The compound (11) obtained in method (1) is used as starting material.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (11)
　塩基性化合物の存在下、化合物（１１）に方法（４）において得られた化合物（２０）を反応させて、化合物（１７Ｅ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＨ２－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｅ） In the presence of a basic compound, compound (11) is reacted with compound (20) obtained in method (4) to give compound (17E).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OCH 2 —C (CH 2 CH═CH 2 ) 3 (17E)
　化合物（１７Ｅ）と化合物（Ｓ）とを、化合物（１７Ｅ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｅ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＨ２－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｅ） The compound (17E) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17E) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1E) is obtained.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OCH 2 —C [CH 2 CH 2 CH 2 —SiR n L 3-n ] 3 ... (1E )
　方法（６）：
　出発物質として国際公開第２０１３／１２１９８４号に記載の方法で得られた化合物（１５Ｃ）を用いる。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－ＣＨ２ＯＨ　・・・（１５Ｃ） Method (6):
The compound (15C) obtained by the method described in International Publication No. 2013/121984 is used as a starting material.
R f1 —O— (R F1 O) x —Q 32 —CH 2 OH (15C)
　塩基性化合物の存在下、化合物（１５Ｃ）に方法（４）において得られた化合物（２０）を反応させて、化合物（１７Ｆ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－ＣＨ２ＯＣＨ２－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｆ） In the presence of a basic compound, compound (15C) is reacted with compound (20) obtained in method (4) to give compound (17F).
R f1 —O— (R F1 O) x —Q 32 —CH 2 OCH 2 —C (CH 2 CH═CH 2 ) 3 (17F)
　化合物（１７Ｆ）と化合物（Ｓ）とを、化合物（１７Ｆ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｆ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－ＣＨ２ＯＣＨ２－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｆ） The compound (17F) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17F) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1F).
R f1 —O— (R F1 O) x —Q 32 —CH 2 OCH 2 —C [CH 2 CH 2 CH 2 —SiR n L 3-n ] 3 ... (1F)
　方法（１１）：
　出発物質として方法（１）において得られた化合物（１４）を用いる。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－Ｃ（Ｏ）ＯＲ１０　・・・（１４） Method (11):
The compound (14) obtained in method (1) is used as a starting material.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —C (O) OR 10 (14)
　化合物（１４）にＨ２Ｎ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３を反応させて、化合物（１７Ｇ）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｇ） The compound (14) is reacted with H 2 N—R 34 —C (CH 2 CH═CH 2 ) 3 to obtain the compound (17G).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —C (O) NH—R 34 —C (CH 2 CH═CH 2 ) 3.・ (17G)
　化合物（１７Ｇ）と化合物（Ｓ）とを、化合物（１７Ｇ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｇ）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｇ） The compound (17G) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17G) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1G) is obtained.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —C (O) NH—R 34 —C [CH 2 CH 2 CH 2 —SiR n L 3-n ] 3 ... (1G)
　方法（１２）：
　出発物質として方（１）において得られた化合物（１１）を用いる。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＨ　・・・（１１） Method (12):
The compound (11) obtained in method (1) is used as starting material.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (11)
　Ｊ．Ｏｒｇ．Ｃｈｅｍ．，第６４巻，１９９９年，ｐ．２５６４－２５６６に記載の方法にしたがい、化合物（１１）を酸化して、化合物（１３Ｈ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－Ｃ（Ｏ）ＯＨ　・・・（１３Ｈ） J. et al. Org. Chem. 64, 1999, p. In accordance with the method described in 2564-2566, compound (11) is oxidized to give compound (13H).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —C (O) OH (13H)
　化合物（１３Ｈ）にＲ１０ＯＨを作用させることによって、化合物（１４Ｈ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－Ｃ（Ｏ）ＯＲ１０　・・・（１４Ｈ） Compound (14H) is obtained by allowing R 10 OH to act on compound (13H).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —C (O) OR 10 (14H)
　化合物（１４Ｈ）にＨ２Ｎ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３を反応させて、化合物（１７Ｈ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｈ） Compound (14H) is reacted with H 2 N—R 34 —C (CH 2 CH═CH 2 ) 3 to obtain compound (17H).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —C (O) NH—R 34 —C (CH 2 CH═CH 2 ) 3 (17H)
　化合物（１７Ｈ）と化合物（Ｓ）とを、化合物（１７Ｈ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｈ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｈ） The compound (17H) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (17H). 1H).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —C (O) NH—R 34 —C [CH 2 CH 2 CH 2 —SiR n L 3-n ] 3. .. (1H)
　方法（１３）：
　出発物質として国際公開第２０１３／１２１９８４号に記載の方法で得られた化合物（１４Ｉ）を用いる。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－Ｃ（Ｏ）ＯＲ１０　・・・（１４Ｉ）
　ただし、ｘは、１以上の整数である。 Method (13):
The compound (14I) obtained by the method described in International Publication No. 2013/121984 is used as a starting material.
R f1 -O- (R F1 O) x -Q 32 -C (O) OR 10 (14I)
However, x is an integer of 1 or more.
　化合物（１４Ｉ）にＨ２Ｎ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３を反応させて、化合物（１７Ｉ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｉ） Compound (14I) is reacted with H 2 N—R 34 —C (CH 2 CH═CH 2 ) 3 to obtain compound (17I).
R f1 —O— (R F1 O) x —Q 32 —C (O) NH—R 34 —C (CH 2 CH═CH 2 ) 3 ... (17I)
　化合物（１７Ｉ）と化合物（Ｓ）とを、化合物（１７Ｉ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｉ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｑ３２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｉ） The compound (17I) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17I) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1I) is obtained.
R f1 —O— (R F1 O) x —Q 32 —C (O) NH—R 34 —C [CH 2 CH 2 CH 2 —SiR n L 3-n ] 3 ... (1I)
　方法（１４）：
　ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＯＣＨ３とＨ２Ｎ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３とを反応させて、化合物（３０）を得る。
　ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（３０） Method (14):
CF 2 ═CFOCF 2 CF 2 CF 2 —C (O) OCH 3 and H 2 N—R 34 —C (CH 2 CH═CH 2 ) 3 are reacted to obtain compound (30).
CF 2 = CFOCF 2 CF 2 CF 2 —C (O) NH—R 34 —C (CH 2 CH═CH 2 ) 3 (30)
　出発物質として方法（１）において得られた化合物（１５）を用いる。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＨ　・・・（１５） The compound (15) obtained in method (1) is used as starting material.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OH (15)
　塩基性化合物の存在下、化合物（１５）に化合物（３０）を反応させて、化合物（１７Ｊ）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｊ） Compound (15) is reacted with compound (30) in the presence of a basic compound to give compound (17J).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R 34 —C ( CH 2 CH═CH 2 ) 3 (17J)
　化合物（１７Ｊ）と化合物（Ｓ）とを、化合物（１７Ｊ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｊ）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｊ） The compound (17J) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (17J). 1J).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R 34 —C [ CH 2 CH 2 CH 2 —SiR n L 3-n ] 3 (1J)
　方法（１５）：
　出発物質として方法（１）において得られた化合物（１１）を用いる。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＨ　・・・（１１） Method (15):
The compound (11) obtained in method (1) is used as starting material.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OH (11)
　塩基性化合物の存在下、化合物（１１）に方法（１４）において得られた化合物（３０）を反応させて、化合物（１７Ｋ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｋ） Compound (17) is obtained by reacting compound (11) with compound (30) obtained in method (14) in the presence of a basic compound.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R 34 —C (CH 2 CH═CH 2 3 ... (17K)
　化合物（１７Ｋ）と化合物（Ｓ）とを、化合物（１７Ｋ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｋ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｋ） The compound (17K) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (17K). 1K).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R 34 —C [CH 2 CH 2 CH 2 -SiR n L 3-n] 3 ··· (1K)
　方法（１６）：
　出発物質として国際公開第２０１３／１２１９８４号に記載の方法で得られた化合物（１５Ｃ）を用いる。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－ＲＦＣＨ２ＯＨ　・・・（１５Ｃ） Method (16):
The compound (15C) obtained by the method described in International Publication No. 2013/121984 is used as a starting material.
R f1 —O— (R F1 O) x —R F CH 2 OH (15C)
　塩基性化合物の存在下、化合物（１５Ｃ）に方法（１４）において得られた化合物（３０）を反応させて、化合物（１７Ｌ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－ＲＦＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｌ） In the presence of a basic compound, compound (15C) is reacted with compound (30) obtained in method (14) to give compound (17L).
R f1 —O— (R F1 O) x —R F CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R 34 —C (CH 2 CH═CH 2 ) 3 (17L)
　化合物（１７Ｌ）と化合物（Ｓ）とを、化合物（１７Ｌ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（１Ｌ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－ＲＦＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒ３４－Ｃ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］３　・・・（１Ｌ） The compound (17L) and the compound (S) are subjected to a hydrosilylation reaction with respect to the compound (17L) in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent to obtain a compound ( 1L).
R f1 —O— (R F1 O) x —R F CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R 34 —C [CH 2 CH 2 CH 2 —SiR n L 3-n ] 3 ... (1L)
　「化合物（Ａ１２）の製造方法」
　化合物（Ａ１２）の製造方法としては、たとえば下記の方法（２１）～（２３）が挙げられる。 “Production Method of Compound (A12)”
Examples of the method for producing compound (A12) include the following methods (21) to (23).
　方法（２１）：
　出発物質として市販の化合物（４０）を用いる。
　ＨＯ－ＣＨ２－（ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＨ　・・・（４０） Method (21):
Commercially available compound (40) is used as starting material.
HO—CH 2 — (CF 2 O) (R F1 O) x —CF 2 —CH 2 —OH (40)
　塩基性化合物の存在下、化合物（４０）にＲｆ１－Ｏ－ＣＦ＝ＣＦ２を反応させて、化合物（４１）、化合物（３Ａ’）および未反応の化合物（４０）の混合物を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＨ　・・・（４１）
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＣＦ２ＣＨＦ－Ｏ－Ｒｆ１　・・・（３Ａ’） In the presence of the basic compound, the compound (40) is reacted with R f1 —O—CF═CF 2 to obtain a mixture of the compound (41), the compound (3A ′) and the unreacted compound (40).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (41)
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OCF 2 CHF—O—R f1 (3A ′)
　混合物から化合物（４１）を単離し、化合物（４１）とＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＦとのエステル化反応によって、化合物（４２）を得る。該エステル化反応は、化合物（４１）と、他の酸フロリド、酸クロリド、酸ブロミド、酸無水物等との反応であってもよい。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＣＯＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３　・・・（４２） Compound (41) is isolated from the mixture, and compound (42) is obtained by esterification reaction of compound (41) and CF 3 CF 2 CF 2 OCF (CF 3 ) COF. The esterification reaction may be a reaction between the compound (41) and another acid fluoride, acid chloride, acid bromide, acid anhydride or the like.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OCOCF (CF 3 ) OCF 2 CF 2 CF 3 (42)
　フッ素ガスを用いて化合物（４２）の水素原子をフッ素原子に置換することによって、化合物（４３）を得る。該フッ素化工程は、たとえば、国際公開第２０００／５６６９４号に記載の方法等にしたがって実施できる。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ（ＣＦ２ＣＦ２Ｏ）－ＣＯＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３　・・・（４３） A compound (43) is obtained by substituting the fluorine atom for the hydrogen atom of the compound (42) using fluorine gas. The fluorination step can be performed, for example, according to the method described in International Publication No. 2000/56694.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x (CF 2 CF 2 O) —COCF (CF 3 ) OCF 2 CF 2 CF 3 (43)
　化合物（４３）にアルコール（メタノール、エタノール、１－プロパノール、２－プロパノール等。以下、ＲＯＨと記す。Ｒはアルキル基である。）を作用させることによって、化合物（４４）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＯＯＲ　・・・（４４） Compound (44) is obtained by reacting compound (43) with alcohol (methanol, ethanol, 1-propanol, 2-propanol, etc., hereinafter referred to as ROH, R is an alkyl group).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —COOR (44)
　化合物（４４）を、還元剤（水素化ホウ素ナトリウム、水素化リチウムアルミニウム等）を用いて水素還元することによって、下式（４５）で表される化合物（４５）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＨ　・・・（４５） The compound (44) represented by the following formula (45) is obtained by hydrogen reduction of the compound (44) using a reducing agent (sodium borohydride, lithium aluminum hydride, etc.).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OH (45)
　塩基性化合物の存在下、化合物（４５）にＣＦ３ＳＯ２Ｃｌを反応させて、化合物（４６）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＳＯ２ＣＦ３　・・・（４６） Compound (45) is reacted with CF 3 SO 2 Cl in the presence of a basic compound to give compound (46).
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 OSO 2 CF 3 (46)
　塩基性化合物の存在下、化合物（４６）にＨＮ（ＣＨ２ＣＨ＝ＣＨ２）２を反応させて、化合物（４７）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－Ｎ（ＣＨ２ＣＨ＝ＣＨ２）２　・・・（４７） Compound (47) is obtained by reacting compound (46) with HN (CH 2 CH═CH 2 ) 2 in the presence of a basic compound.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 —N (CH 2 CH═CH 2 ) 2 (47)
　化合物（４７）と化合物（Ｓ）とを、化合物（４７）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、化合物（４Ａ）を得る。
　Ｒｆ１－Ｏ－（ＣＦ２ＣＦ２Ｏ）（ＣＦ２ＣＦ２Ｏ）（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－Ｎ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］２　・・・（４Ａ） The compound (47) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (47). 4A) is obtained.
R f1 —O— (CF 2 CF 2 O) (CF 2 CF 2 O) (R F1 O) x —CF 2 —CH 2 —N [CH 2 CH 2 CH 2 —SiR n L 3-n ] 2. .. (4A)
　方法（２２）：
　出発物質として方法（２１）において得られた化合物（４１）を用いる。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－ＯＨ　・・・（４１） Method (22):
The compound (41) obtained in method (21) is used as starting material.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —OH (41)
　塩基性化合物の存在下、化合物（４１）にＣＦ３ＳＯ２Ｃｌを反応させて、化合物（４６Ｂ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２ＯＳＯ２ＣＦ３　・・・（４６Ｂ） In the presence of a basic compound, compound (41) is reacted with CF 3 SO 2 Cl to obtain compound (46B).
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 OSO 2 CF 3 (46B)
　塩基性化合物の存在下、化合物（４６Ｂ）にＨＮ（ＣＨ２ＣＨ＝ＣＨ２）２を反応させて、化合物（４７Ｂ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－Ｎ（ＣＨ２ＣＨ＝ＣＨ２）２　・・・（４７Ｂ） Compound (47B) is obtained by reacting compound (46B) with HN (CH 2 CH═CH 2 ) 2 in the presence of a basic compound.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —N (CH 2 CH═CH 2 ) 2 (47B)
　化合物（４７Ｂ）と化合物（Ｓ）とを、化合物（４７Ｂ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、下式（４Ｂ）で表される化合物（４Ｂ）を得る。
　Ｒｆ１－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－（ＲＦ１Ｏ）ｘ－ＣＦ２－ＣＨ２－Ｎ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］２　・・・（４Ｂ） The compound (47B) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (47B). The compound (4B) represented by (4B) is obtained.
R f1 —O—CHFCF 2 OCH 2 CF 2 O— (R F1 O) x —CF 2 —CH 2 —N [CH 2 CH 2 CH 2 —SiR n L 3-n ] 2 (4B)
　方法（２３）：
　出発物質として国際公開第２０１３／１２１９８４号に記載の方法等の公知の方法で得られた化合物（４５Ｃ）を用いる。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｒ４２－ＣＨ２ＯＨ　・・・（４５Ｃ） Method (23):
As a starting material, a compound (45C) obtained by a known method such as the method described in International Publication No. 2013/121984 is used.
R f1 —O— (R F1 O) x —R 42 —CH 2 OH (45C)
　塩基性化合物の存在下、化合物（４５Ｃ）にＣＦ３ＳＯ２Ｃｌを反応させて、化合物（１６Ｃ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｒ４２－ＣＨ２ＯＳＯ２ＣＦ３　・・・（４６Ｃ） Compound (16C) is obtained by reacting compound (45C) with CF 3 SO 2 Cl in the presence of a basic compound.
R f1 —O— (R F1 O) x —R 42 —CH 2 OSO 2 CF 3 (46C)
　塩基性化合物の存在下、化合物（４６Ｃ）にＨＮ（ＣＨ２ＣＨ＝ＣＨ２）２を反応させて、下式（４７Ｃ）で表される化合物（４７Ｃ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｒ４２－ＣＨ２－Ｎ（ＣＨ２ＣＨ＝ＣＨ２）２　・・・（４７Ｃ） In the presence of a basic compound, compound (46C) is reacted with HN (CH 2 CH═CH 2 ) 2 to obtain compound (47C) represented by the following formula (47C).
R f1 —O— (R F1 O) x —R 42 —CH 2 —N (CH 2 CH═CH 2 ) 2 (47C)
　化合物（４７Ｃ）と化合物（Ｓ）とを、化合物（４７Ｃ）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応して、下式（４Ｃ）で表される化合物（４Ｃ）を得る。
　Ｒｆ１－Ｏ－（ＲＦ１Ｏ）ｘ－Ｒ４２－ＣＨ２－Ｎ［ＣＨ２ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ］２　・・・（４Ｃ） The compound (47C) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (47C). The compound (4C) represented by (4C) is obtained.
R f1 —O— (R F1 O) x —R 42 —CH 2 —N [CH 2 CH 2 CH 2 —SiR n L 3-n ] 2 (4C)
　「化合物（Ａ１３）の製造方法」
　化合物（Ａ１３）の製造方法としては、たとえば下記の方法が挙げられる。
　塩基性化合物の存在下、化合物（２）と化合物（３）とを反応させて粗生成物を得る。
　粗生成物は、ｅとｆとの比が異なる複数種の化合物（４）を含む。粗生成物から公知の手段（カラム精製等）によってｅとｆとの比が所望の比である化合物（４）を分取する。
　Ｚ３（ＯＨ）ｅ＋ｆ　・・・（２）
　Ｘ－Ｒ２１－ＣＨ＝ＣＨ２　・・・（３）
　［ＨＯ－］ｅＺ３［－Ｏ－Ｒ５４－ＣＨ＝ＣＨ２］ｆ　・・・（４）
　ただし、Ｘは、ハロゲン原子であり、Ｒ５４は、前記式（Ａ１３）のＲ５３よりも炭素数が２個少ないアルキレン基である。 “Production Method of Compound (A13)”
As a manufacturing method of a compound (A13), the following method is mentioned, for example.
In the presence of a basic compound, the compound (2) and the compound (3) are reacted to obtain a crude product.
The crude product contains a plurality of types of compounds (4) having different ratios of e and f. The compound (4) in which the ratio of e to f is a desired ratio is separated from the crude product by a known means (column purification or the like).
Z 3 (OH) e + f (2)
X—R 21 —CH═CH 2 (3)
[HO—] e Z 3 [—O—R 54 —CH═CH 2 ] f (4)
However, X is a halogen atom, and R 54 is an alkylene group having 2 fewer carbon atoms than R 53 in the formula (A13).
　化合物（４）と無水トリフルオロメタンスルホン酸とを２，６－ルチジン等の塩基の存在下に反応させて化合物（５）を得る。
　［Ｆ３Ｃ－ＳＯ２－Ｏ－］ｅＺ３［－Ｏ－Ｒ５４－ＣＨ＝ＣＨ２］ｆ　・・・（５） Compound (5) is obtained by reacting compound (4) with trifluoromethanesulfonic anhydride in the presence of a base such as 2,6-lutidine.
[F 3 C—SO 2 —O—] e Z 3 [—O—R 54 —CH═CH 2 ] f (5)
　塩基の存在下、化合物（５）と化合物（６）とを反応させて化合物（７）を得る。
　Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－Ｒ５１－Ｒ５２－ＯＨ　・・・（６）
　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－Ｒ５１－Ｒ５２－Ｏ－］ｅＺ３［－Ｏ－Ｒ５４－ＣＨ＝ＣＨ２］ｆ　・・・（７） Compound (7) is obtained by reacting compound (5) with compound (6) in the presence of a base.
R f1 -OQR fe -R 51 -R 52 -OH (6)
[R f1 -OQR fe -R 51 -R 52 -O-] e Z 3 [-O-R 54 -CH = CH 2 ] f (7)
　化合物（７）と化合物（Ｓ）とを、化合物（７）に対して遷移金属換算で３００～４，０００ｐｐｍの遷移金属化合物および必要に応じて溶媒の存在下にヒドロシリル化反応させて、化合物（Ａ１３）を得る。
　［Ｒｆ１－Ｏ－Ｒｆｅ－Ｒ５１－Ｒ５２－Ｏ－］ｅＺ３［－Ｏ－Ｒ５３－ＳｉＲｎＬ３－ｎ］ｆ　・・・（Ａ１３） The compound (7) and the compound (S) are subjected to a hydrosilylation reaction in the presence of 300 to 4,000 ppm of a transition metal compound in terms of transition metal and, if necessary, a solvent with respect to the compound (7). A13) is obtained.
[R f1 —O—R fe —R 51 —R 52 —O—] e Z 3 [—O—R 53 —SiR n L 3-n ] f (A13)
　ｅ＋ｆが３である化合物（２）としては、グリセリン、トリメチロールエタン、トリメチロールプロパン、１，２，６－ヘキサントリオール等が挙げられる。
　ｅ＋ｆが４である化合物（２）としては、ジグリセリン、ペンタエリスリトール、ジトリメチロールプロパン等が挙げられる。
　ｅ＋ｆが６である化合物（２）としては、ジペンタエリスリトール、ソルビトール、マンニトール、ズルシトール等が挙げられる。
　化合物（３）としては、臭化アリル、５－ブロモ－１－ペンテン等が挙げられる。
　化合物（６）は、たとえば、国際公開第２０１３／１２１９８４号、国際公開第２０１４／１６３００４号、国際公開第２０１５／０８７９０２号等に記載の方法によって製造できる。
　化合物（Ｓ）としては、トリメトキシシラン、トリエトキシシラン、メチルジメトキシシラン、トリクロロシラン等が挙げられる。 Examples of the compound (2) in which e + f is 3 include glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol and the like.
Examples of the compound (2) in which e + f is 4 include diglycerin, pentaerythritol, ditrimethylolpropane, and the like.
Examples of the compound (2) in which e + f is 6 include dipentaerythritol, sorbitol, mannitol, dulcitol and the like.
Examples of the compound (3) include allyl bromide and 5-bromo-1-pentene.
Compound (6) can be produced, for example, by the method described in International Publication No. 2013/121984, International Publication No. 2014/163004, International Publication No. 2015/088792.
Examples of the compound (S) include trimethoxysilane, triethoxysilane, methyldimethoxysilane, and trichlorosilane.
　化合物（Ａ１３）の合成フローの一例を示す。本合成フローにおいて、化合物（２）は化合物（２－１）（ジペンタエリスリトール）であり、化合物（３）は化合物（３－１）（臭化アリル）であり、化合物（６）は国際公開第２０１５／０８７９０２号の製造例６に記載の方法によって得られた化合物（６－１）であり、化合物（８）は化合物（８－１）（トリメトキシシラン）である。化合物（６－１）におけるＷ－Ｒ５１はＣＦ３ＣＦ２ＣＦ２Ｏ｛（ＣＦ２Ｏ）ｍ２１（ＣＦ２ＣＦ２Ｏ）ｍ２２｝ＣＦ２である。
　ＣＦ３ＣＦ２ＣＦ２Ｏ｛（ＣＦ２Ｏ）ｍ２１（ＣＦ２ＣＦ２Ｏ）ｍ２２｝ＣＦ２－ＣＨ２－ＯＨ　・・・（６－１） An example of the synthesis flow of a compound (A13) is shown. In this synthesis flow, compound (2) is compound (2-1) (dipentaerythritol), compound (3) is compound (3-1) (allyl bromide), and compound (6) is published internationally. The compound (6-1) obtained by the method described in Production Example 6 of No. 2015/088702, and the compound (8) is the compound (8-1) (trimethoxysilane). W-R 51 in the compound (6-1) is CF 3 CF 2 CF 2 O { (CF 2 O) m21 (CF 2 CF 2 O) m22} CF 2.
CF 3 CF 2 CF 2 O { (CF 2 O) m21 (CF 2 CF 2 O) m22} CF 2 -CH 2 -OH ··· (6-1)
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　化合物（２）、化合物（３）、化合物（６）および化合物（８）を適宜選択し、化合物（４）におけるｅとｆとの比を適宜選択して各反応を実施することによって所望の化合物（Ａ１３）を製造できる。 The compound (2), the compound (3), the compound (6) and the compound (8) are appropriately selected, and the desired compound is selected by appropriately selecting the ratio of e to f in the compound (4) and carrying out each reaction. (A13) can be manufactured.
（２）第２実施形態例
　第２実施形態例の含フッ素エーテル組成物の製造方法は、前記化合物（Ｂ）と、前記化合物（Ｓ）とを、化合物（Ｂ）に対する遷移金属化合物の質量割合が遷移金属換算で１ｐｐｍ以上３００ｐｐｍ未満の遷移金属化合物の存在下に反応（ヒドロシリル化反応）を行って化合物（ＡＸ）を生成させ、次いで、化合物（ＡＸ）に対する遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍとなるように、反応生成物に遷移金属化合物を添加する、方法である。ヒドロシリル化反応は、溶媒の存在下で行ってもよいし、非存在下で行ってもよい。
　得られる含フッ素エーテル組成物は、反応により生成する化合物（ＡＨ）と遷移金属化合物とを含み、化合物（ＡＨ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍである、組成物である。 (2) Second Embodiment Example The method for producing a fluorinated ether composition according to the second embodiment is characterized in that the compound (B) and the compound (S) are mixed in a mass ratio of the transition metal compound to the compound (B). Is produced in the presence of a transition metal compound having a transition metal equivalent of 1 ppm or more and less than 300 ppm to produce a compound (AX), and the mass ratio of the transition metal compound to the compound (AX) is then a transition metal. In this method, a transition metal compound is added to the reaction product so as to be 300 to 4,000 ppm in terms of conversion. The hydrosilylation reaction may be performed in the presence or absence of a solvent.
The resulting fluorine-containing ether composition contains a compound (AH) produced by the reaction and a transition metal compound, and the mass ratio of the transition metal compound to the compound (AH) is 300 to 4,000 ppm in terms of transition metal. It is a composition.
　ヒドロシリル化反応に使用する遷移金属化合物の使用量が遷移金属換算で、第１実施形態例では３００～４，０００ｐｐｍであるのに対し、第２実施形態例では１ｐｐｍ以上３００ｐｐｍ未満である点、および生成した化合物（ＡＸ）に対して、第１実施形態例では遷移金属化合物を添加する必要がないのに対し、第２に実施形態例では特定量の遷移金属化合物を添加する点以外は、第１実施形態例と第２実施形態例は同じである。 The amount of the transition metal compound used in the hydrosilylation reaction is 300 to 4,000 ppm in terms of transition metal in the first embodiment, whereas it is 1 ppm or more and less than 300 ppm in the second embodiment, and In contrast to the generated compound (AX), in the first embodiment, it is not necessary to add a transition metal compound, whereas in the second embodiment, the second embodiment is the same except that a specific amount of the transition metal compound is added. The first embodiment and the second embodiment are the same.
　生成した化合物（ＡＸ）に対する遷移金属化合物の質量割合が前記範囲内となるように化合物（ＡＸ）に遷移金属化合物を添加することで、基材の透明性を損なうことなく、表面層の耐久性を向上できる。生成した化合物（ＡＸ）に対する遷移金属化合物の添加量は、化合物（ＡＸ）に対する遷移金属化合物の質量割合が遷移金属換算で４００～２，０００ｐｐｍとなる量が好ましく、５００～１，０００ｐｐｍとなる量が特に好ましい。 By adding the transition metal compound to the compound (AX) so that the mass ratio of the transition metal compound to the generated compound (AX) is within the above range, the durability of the surface layer is maintained without impairing the transparency of the substrate. Can be improved. The amount of the transition metal compound added to the produced compound (AX) is preferably such that the mass ratio of the transition metal compound to the compound (AX) is 400 to 2,000 ppm in terms of transition metal, and 500 to 1,000 ppm. Is particularly preferred.
　第２実施形態例において、ヒドロシリル化反応に使用する遷移金属化合物と、生成した化合物（ＡＸ）に添加する遷移金属化合物とは、同じ種類であってもよいし、異なる種類であってもよいが、同じ種類が好ましい。 In the second embodiment, the transition metal compound used for the hydrosilylation reaction and the transition metal compound added to the generated compound (AX) may be the same type or different types. The same type is preferred.
〔コーティング液〕
　本発明の含フッ素エーテル組成物は、液状媒体に溶解または分散してコーティング液として用いてもよい。すなわち、コーティング液は、本組成物と液状媒体とを含む。 [Coating solution]
The fluorine-containing ether composition of the present invention may be dissolved or dispersed in a liquid medium and used as a coating liquid. That is, the coating liquid contains the present composition and a liquid medium.
　液状媒体としては、有機溶媒が好ましい。有機溶媒は、ヒドロシリル化反応の際に用いる溶媒が挙げられる。
　ヒドロシリル化反応の際に溶媒を用いる場合、ヒドロシリル化反応の際に溶媒とコーティング液に含まれる液状媒体とは同じ種類であっても異なる種類であってもよい。
　本組成物の含有量は、コーティング液の総質量に対し、０．００１～３０質量％であることが好ましく、０．１～２０質量％が特に好ましい。
　液状媒体の含有量は、コーティング液の総質量に対し、７０～９９．９９９質量％であることが好ましく、８０～９９．９質量％が特に好ましい。 As the liquid medium, an organic solvent is preferable. Examples of the organic solvent include a solvent used in the hydrosilylation reaction.
When a solvent is used during the hydrosilylation reaction, the solvent and the liquid medium contained in the coating liquid during the hydrosilylation reaction may be the same type or different types.
The content of the present composition is preferably 0.001 to 30% by mass, particularly preferably 0.1 to 20% by mass, based on the total mass of the coating liquid.
The content of the liquid medium is preferably 70 to 99.999% by mass, particularly preferably 80 to 99.9% by mass, based on the total mass of the coating liquid.
　コーティング液の固形分濃度は、コーティング液の総質量に対し、０．００１～１０質量％が好ましく、０．０１～１質量％が特に好ましい。
　コーティング液の固形分濃度は、加熱前のコーティング液の質量と、１２０℃の対流式乾燥機にて４時間加熱した後の質量とから算出する値である。
　本組成物の濃度は、固形分濃度と、本組成物および溶媒等の仕込み量とから算出可能である。 The solid concentration of the coating solution is preferably 0.001 to 10% by mass, particularly preferably 0.01 to 1% by mass, based on the total mass of the coating solution.
The solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120 ° C.
The concentration of the present composition can be calculated from the solid content concentration and the charged amounts of the present composition and solvent.
〔物品〕
　物品は、本組成物から形成された表面層を基材の表面に有する。 [Goods]
The article has a surface layer formed from the composition on the surface of the substrate.
（表面層）
　本組成物においては、化合物（Ａ）中の基（Ｉ）におけるＬが加水分解性基である場合には、基（Ｉ）が加水分解反応することによってシラノール基（Ｓｉ－ＯＨ）が形成され、該シラノール基は分子間で反応してＳｉ－Ｏ－Ｓｉ結合が形成され、または該シラノール基が基材の表面の水酸基（基材－ＯＨ）と脱水縮合反応して化学結合（基材－Ｏ－Ｓｉ）が形成される。したがって、表面層は、化合物（Ａ）を、化合物（Ａ）の基（Ｉ）の一部または全部が加水分解反応した状態で含む。基（Ｉ）におけるＬが水酸基である場合には、加水分解反応を経ずに上記反応が進む。 (Surface layer)
In this composition, when L in the group (I) in the compound (A) is a hydrolyzable group, a silanol group (Si—OH) is formed by the hydrolysis reaction of the group (I). The silanol group reacts between molecules to form a Si—O—Si bond, or the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (substrate—OH) on the surface of the substrate to form a chemical bond (substrate— O—Si) is formed. Therefore, the surface layer contains the compound (A) in a state where a part or all of the group (I) of the compound (A) is hydrolyzed. When L in the group (I) is a hydroxyl group, the above reaction proceeds without undergoing a hydrolysis reaction.
　表面層の厚さは、１～１００ｎｍが好ましく、１～５０ｎｍが特に好ましい。表面層の厚さが前記範囲の下限値以上であれば、表面処理による効果が充分に得られやすい。表面層の厚さが前記範囲の上限値以下であれば、利用効率が高い。表面層の厚さは、薄膜解析用Ｘ線回折計（ＲＩＧＡＫＵ社製、ＡＴＸ－Ｇ）を用いて、Ｘ線反射率法によって反射Ｘ線の干渉パターンを得て、該干渉パターンの振動周期から算出できる。 The thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the surface layer is not less than the lower limit of the above range, the effect of the surface treatment can be sufficiently obtained. If the thickness of the surface layer is not more than the upper limit of the above range, the utilization efficiency is high. The thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by an X-ray reflectivity method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G). It can be calculated.
（基材）
　基材は、耐摩擦性、指紋汚れ除去性等が必要とされる種々の物品（光学レンズ、タッチパネル、ディスプレイ、光記録媒体等）の本体部分、または該物品の表面を構成する部材である。
　基材としては、潤滑性や撥水撥油性の付与が求められている基材であれば特に限定されない。基材の表面の材料としては、金属、樹脂、ガラス、サファイア、セラミック、石、および、これらの複合材料が挙げられる。ガラスは化学強化されていてもよい。基材の表面にはＳｉＯ２膜等の下地膜が形成されていてもよい。
　基材としては、光学レンズ、タッチパネル用基材、ディスプレイ用基材および光記録媒体用基材が好適であり、タッチパネル用基材が特に好適である。タッチパネル用基材は、透光性を有する。「透光性を有する」とは、ＪＩＳ　Ｒ３１０６：１９９８（ＩＳＯ　９０５０：１９９０）に準じた垂直入射型可視光透過率が２５％以上であることを意味する。
　光学レンズ、タッチパネル、ディスプレイおよび光記録媒体における基材の表面の材料としては、ガラスおよび透明樹脂が好ましい。 (Base material)
The base material is a main body part of various articles (such as an optical lens, a touch panel, a display, and an optical recording medium) that require friction resistance and fingerprint stain removability, or a member constituting the surface of the article.
The substrate is not particularly limited as long as it is required to impart lubricity and water / oil repellency. Examples of the material for the surface of the substrate include metal, resin, glass, sapphire, ceramic, stone, and a composite material thereof. The glass may be chemically strengthened. A base film such as a SiO 2 film may be formed on the surface of the substrate.
As the substrate, an optical lens, a substrate for touch panel, a substrate for display, and a substrate for optical recording medium are suitable, and a substrate for touch panel is particularly suitable. The base material for touch panels has translucency. “Having translucency” means that a normal incidence visible light transmittance in accordance with JIS R3106: 1998 (ISO 9050: 1990) is 25% or more.
As a material for the surface of the substrate in the optical lens, touch panel, display, and optical recording medium, glass and transparent resin are preferable.
（物品の製造方法）
　物品は、たとえば、下記の方法で製造できる。
　・本組成物を用いたドライコーティング法によって基材の表面を処理して、物品を得る方法。
　・ウェットコーティング法によって本コーティング液を基材の表面に塗布し、乾燥させて、物品を得る方法。 (Product manufacturing method)
The article can be manufactured, for example, by the following method.
A method of obtaining an article by treating the surface of a substrate by a dry coating method using the present composition.
A method of obtaining an article by applying the present coating solution to the surface of a substrate by a wet coating method and drying it.
　＜ドライコーティング法＞
　本組成物は、ドライコーティング法にそのまま用いることができる。本組成物は、ドライコーティング法によって密着性に優れた表面層を形成するのに好適である。
　ドライコーティング法としては、真空蒸着法、ＣＶＤ法、スパッタリング法等が挙げられる。化合物（Ａ）の分解を抑える点、および装置の簡便さの点から、真空蒸着法が特に好ましい。 <Dry coating method>
The present composition can be used as it is in a dry coating method. This composition is suitable for forming a surface layer having excellent adhesion by a dry coating method.
Examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method. The vacuum deposition method is particularly preferable from the viewpoint of suppressing the decomposition of the compound (A) and the simplicity of the apparatus.
　真空蒸着の際の温度は、２０～３００℃が好ましく、３０～２００℃が特に好ましい。
　真空蒸着の際の圧力は、１×１０－１Ｐａ以下が好ましく、１×１０－２Ｐａ以下が特に好ましい。 The temperature during vacuum deposition is preferably 20 to 300 ° C, particularly preferably 30 to 200 ° C.
The pressure during vacuum deposition is preferably 1 × 10 −1 Pa or less, particularly preferably 1 × 10 −2 Pa or less.
　＜ウェットコーティング法＞
　ウェットコーティング法としては、スピンコート法、ワイプコート法、スプレーコート法、スキージーコート法、ディップコート法、ダイコート法、インクジェット法、フローコート法、ロールコート法、キャスト法、ラングミュア・ブロジェット法、グラビアコート法等が挙げられる。 <Wet coating method>
Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, ink jet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. Examples thereof include a coating method.
　＜後処理＞
　表面層の耐摩擦性を向上させるために、必要に応じて、化合物（Ａ）と基材との反応を促進するための操作を行ってもよい。該操作としては、加熱、加湿、光照射等が挙げられる。
　たとえば、水分を有する大気中で表面層が形成された基材を加熱して、加水分解性シリル基のシラノール基への加水分解反応、基材の表面の水酸基等とシラノール基との反応、シラノール基の縮合反応によるシロキサン結合の生成、等の反応を促進できる。
　表面処理後、表面層中の化合物であって他の化合物や基材と化学結合していない化合物は、必要に応じて除去してもよい。具体的な方法としては、たとえば、表面層に溶媒をかけ流す方法、溶媒をしみ込ませた布でふき取る方法等が挙げられる。 <Post-processing>
In order to improve the friction resistance of the surface layer, an operation for promoting the reaction between the compound (A) and the substrate may be performed as necessary. Examples of the operation include heating, humidification, and light irradiation.
For example, by heating a substrate on which a surface layer is formed in an atmosphere having moisture, hydrolysis reaction of hydrolyzable silyl groups to silanol groups, reaction of hydroxyl groups on the substrate surface with silanol groups, silanols, Reactions such as formation of siloxane bonds by group condensation reactions can be promoted.
After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific methods include, for example, a method of pouring a solvent over the surface layer and a method of wiping with a cloth soaked with a solvent.
〔作用効果〕
　本組成物および本組成物を含むコーティング液にあっては、化合物（Ａ）および特定量の遷移金属化合物を含むため、耐久性に優れる表面層を形成できる。すなわち、本組成物または本組成物を含むコーティング液を用いて基材の表面に表面層が形成されることによって、優れた初期の撥水撥油性等の特性が付与されるとともに、該表面が繰り返し摩擦されてもその特性が低下しにくい優れた耐久性が得られる。この理由としては、以下のように考えられる。すなわち、本組成物は化合物（Ａ）に対して遷移金属換算で３００ｐｐｍ以上の遷移金属化合物を含むため、化合物（Ａ）中の加水分解性シリル基のシラノール基への加水分解反応、および該シラノール基と基材の表面の水酸基（基材－ＯＨ）との脱水縮合反応が充分に進行する。その結果、基材の表面の水酸基とシラノール基との化学結合（基材－Ｏ－Ｓｉ）の数が増える。基材の表面の水酸基とシラノール基との化学結合の数が増えることが、耐久性の向上に寄与すると考えられる。 [Function and effect]
Since the present composition and the coating liquid containing the present composition contain the compound (A) and a specific amount of the transition metal compound, a surface layer having excellent durability can be formed. That is, by forming a surface layer on the surface of the substrate using the present composition or a coating liquid containing the present composition, excellent properties such as initial water and oil repellency are imparted, and Even if it is repeatedly rubbed, it is possible to obtain excellent durability in which the characteristics are not easily lowered. The reason is considered as follows. That is, since the present composition contains 300 ppm or more of a transition metal compound in terms of transition metal with respect to the compound (A), the hydrolysis reaction of the hydrolyzable silyl group in the compound (A) to a silanol group, and the silanol The dehydration condensation reaction between the group and the hydroxyl group on the surface of the base material (base material—OH) proceeds sufficiently. As a result, the number of chemical bonds (base material—O—Si) between the hydroxyl group and the silanol group on the surface of the base material increases. An increase in the number of chemical bonds between the hydroxyl groups and silanol groups on the surface of the substrate is considered to contribute to the improvement of durability.
　このように、本組成物より形成される表面層は、表面が繰り返し摩擦されても撥水撥油性が低下しにくいことから、基材の表面の指紋汚れを容易に除去できる性能（指紋汚れ除去性）が得られる。
　一方、本発明者は、遷移金属化合物の質量割合が化合物（Ａ）に対して遷移金属換算で４，０００ｐｐｍを超えると、基材が着色することを見出した。よって、化合物（Ａ）に対する遷移金属化合物の質量割合を遷移金属換算で４，０００ｐｐｍ以下とした。 As described above, the surface layer formed from this composition is less likely to deteriorate the water and oil repellency even if the surface is repeatedly rubbed, so that it can easily remove fingerprint stains on the surface of the substrate (removal of fingerprint stains). Property).
On the other hand, this inventor discovered that a base material will color when the mass ratio of a transition metal compound exceeds 4,000 ppm in conversion of a transition metal with respect to a compound (A). Therefore, the mass ratio of the transition metal compound to the compound (A) is set to 4,000 ppm or less in terms of transition metal.
　なお、化合物（Ａ）に対する遷移金属化合物の質量割合が少ない場合、具体的には遷移金属換算で１０ｐｐｍ以下の場合、表面層の耐久性は劣るものの、化合物（Ａ）を含む含フッ素エーテル組成物の貯蔵安定性が高まる傾向にある。そのため、表面層の耐久性よりも組成物の貯蔵安定性を重視する場合は、化合物（Ａ）に対する遷移金属化合物の質量割合を遷移金属換算で１０ｐｐｍ以下とすることが好ましい。 In addition, when the mass ratio of the transition metal compound to the compound (A) is small, specifically, when it is 10 ppm or less in terms of transition metal, the durability of the surface layer is inferior, but the fluorine-containing ether composition containing the compound (A) There is a tendency for the storage stability of to increase. Therefore, when the storage stability of the composition is more important than the durability of the surface layer, the mass ratio of the transition metal compound to the compound (A) is preferably 10 ppm or less in terms of transition metal.
　化合物（Ａ）に対する遷移金属化合物の質量割合を遷移金属換算で１０ｐｐｍ以下とするには、たとえば、ヒドロシリル化反応において、遷移金属化合物の使用量を化合物（Ｂ）に対して遷移金属換算で０．１～１０ｐｐｍとすればよい。また、遷移金属換算で１０ｐｐｍを超える遷移金属化合物を用いてヒドロシリル化反応を行った場合には、反応後に活性炭処理、分子蒸留等の後処理を行うことで遷移金属化合物を除去し、化合物（Ａ）に対する遷移金属化合物の質量割合を遷移金属換算で１０ｐｐｍ以下に調整してもよい。ただし、活性炭処理の場合、使用する活性炭に含まれる水が化合物（ＡＸ）に持ち込まれるため、該水を除去する手間がかかることがある。そのため、遷移金属換算で０．１～１０ｐｐｍの遷移金属化合物を用いてヒドロシリル化反応を行う方法が好ましい。 In order to set the mass ratio of the transition metal compound to the compound (A) to 10 ppm or less in terms of transition metal, for example, in the hydrosilylation reaction, the amount of the transition metal compound used is 0. It may be 1 to 10 ppm. In addition, when the hydrosilylation reaction is performed using a transition metal compound in excess of 10 ppm in terms of transition metal, the transition metal compound is removed by performing post-treatment such as activated carbon treatment and molecular distillation after the reaction, and the compound (A ) May be adjusted to 10 ppm or less in terms of transition metal. However, in the case of activated carbon treatment, since the water contained in the activated carbon to be used is brought into the compound (AX), it may take time to remove the water. Therefore, a method in which a hydrosilylation reaction is performed using 0.1 to 10 ppm of a transition metal compound in terms of transition metal is preferable.
　以下、実施例によって本発明を詳細に説明するが、本発明はこれらに限定されない。以下、「％」は特に断りのない限り「質量％」である。
　例１～５は実施例であり、例６～８は比較例である。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Hereinafter, “%” is “% by mass” unless otherwise specified.
Examples 1 to 5 are examples, and examples 6 to 8 are comparative examples.
〔評価〕
　（数平均分子量）
　含フッ素エーテル化合物の数平均分子量は、１Ｈ－ＮＭＲおよび１９Ｆ－ＮＭＲによって、末端基を基準にしてオキシペルフルオロアルキレン基の数（平均値）を求めることによって算出した。末端基は、たとえば基（Ｉ）または基（ＩＩ）である。 [Evaluation]
(Number average molecular weight)
The number average molecular weight of the fluorinated ether compound was calculated by determining the number (average value) of oxyperfluoroalkylene groups based on the terminal groups by 1 H-NMR and 19 F-NMR. The terminal group is, for example, group (I) or group (II).
　（耐久性）
　表面層について、ＪＩＳ　Ｌ０８４９：２０１３（ＩＳＯ　１０５－Ｘ１２：２００１）に準拠して往復式トラバース試験機（ケイエヌテー社製）を用い、スチールウールボンスター（♯００００）を荷重０．５ｋｇ／ｃｍ２、速度：３２０ｃｍ／分で往復させた。５００回往復させる毎に水接触角を測定して、水接触角１００°以上が維持される上限の回数（接触角１００°以上の維持回数）を求めた。この回数が多いほど、表面層が摩擦によって損なわれにくく、耐久性に優れる。 (durability)
For the surface layer, a reciprocating traverse tester (manufactured by KE NTE) was used in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), a steel wool bonster (# 0000) was loaded at a rate of 0.5 kg / cm 2 , and the speed : Reciprocating at 320 cm / min. The water contact angle was measured every 500 reciprocations, and the upper limit number of times that the water contact angle of 100 ° or more was maintained (the number of maintenance times of the contact angle of 100 ° or more) was determined. As the number of times increases, the surface layer is less likely to be damaged by friction, and the durability is excellent.
　（基材の着色（外観評価））
　表面層が形成された基材の外観（色）を目視により観察した。 (Coloring of substrate (appearance evaluation))
The appearance (color) of the substrate on which the surface layer was formed was visually observed.
〔例１〕
　国際公開第２０１４／１６３００４号の例１－２に記載の方法にしたがい、化合物（５１）を得た。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２ＣＨ＝ＣＨ２　・・・（５１）
　単位数ｍ１１の平均値：２１、単位数ｍ１２の平均値：２０、化合物（５１）の数平均分子量：４，２００。 [Example 1]
The compound (51) was obtained according to the method described in Example 1-2 of International Publication No. 2014/163004.
CF 3 CF 2 CF 2 —O—CHFCF 2 OCH 2 CF 2 O — {(CF 2 O) m11 (CF 2 CF 2 O) m12 } —CF 2 —CH 2 —O—CH 2 CH═CH 2.・ (51)
Average value of unit number m11: 21, Average value of unit number m12: 20, Number average molecular weight of compound (51): 4,200.
　１００ｍＬのテトラフルオロエチレン－ペルフルオロ（アルコキシビニルエーテル）共重合体（ＰＦＡ）製ナスフラスコに、化合物（５１）の２５．０ｇ、白金／ １，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のキシレン溶液（白金含有量：２％）の０．６０２５ｇ（化合物（５１）に対する白金の使用量が４８２ｐｐｍに相当）、ＨＳｉ（ＯＣＨ３）３の２．８４ｇおよびＡＣ－２０００の１２．５ｇを入れ、７０℃で１０時間撹拌し、ヒドロシリル化反応を行った。反応終了後、溶媒等を減圧蒸留し、化合物（５２－１）および化合物（５２－２）を合計で２４．５ｇ（収率９５．３％）と、白金との組成物を得た。化合物（５２－１）と化合物（５２－２）のモル比は、ＮＭＲより８３：１７であった。また、化合物（Ａ）に相当する化合物（５２－１）に対する白金の質量割合は４００ｐｐｍであった。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２ＣＨ２ＣＨ２－Ｓｉ－（ＯＣＨ３）３　・・・（５２－１）
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＨＦＣＦ２ＯＣＨ２ＣＦ２Ｏ－｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝－ＣＦ２－ＣＨ２－Ｏ－ＣＨ＝ＣＨＣＨ３　・・・（５２－２） In a 100 mL tetrafluoroethylene-perfluoro (alkoxyvinyl ether) copolymer (PFA) eggplant flask, 25.0 g of the compound (51), platinum / 1,3-divinyl-1,1,3,3-tetramethyldi 0.6025 g of a xylene solution of a siloxane complex (platinum content: 2%) (the amount of platinum used relative to compound (51) corresponds to 482 ppm), 2.84 g of HSi (OCH 3 ) 3 and 12. 5 g was added and stirred at 70 ° C. for 10 hours to carry out a hydrosilylation reaction. After completion of the reaction, the solvent and the like were distilled under reduced pressure to obtain a composition of 24.5 g (yield: 95.3%) of the compound (52-1) and the compound (52-2) and platinum. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. In addition, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 400 ppm.
CF 3 CF 2 CF 2 —O—CHFCF 2 OCH 2 CF 2 O — {(CF 2 O) m11 (CF 2 CF 2 O) m12 } —CF 2 —CH 2 —O—CH 2 CH 2 CH 2 —Si -(OCH 3 ) 3 (52-1)
CF 3 CF 2 CF 2 —O—CHFCF 2 OCH 2 CF 2 O — {(CF 2 O) m 11 (CF 2 CF 2 O) m 12 } —CF 2 —CH 2 —O—CH═CHCH 3. 52-2)
　化合物（５２－１）のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（３００．４ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＴＭＳ）　δ（ｐｐｍ）：０．７（２Ｈ）、１．７（２Ｈ）、３．６（１１Ｈ）、３．８（２Ｈ）、４．２（２Ｈ）、５．８～６．０（１Ｈ）。
　１９Ｆ－ＮＭＲ（２８２．７ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）　δ（ｐｐｍ）：－５２．３～－５５．７（４２Ｆ）、－７８．２（１Ｆ）、－７８．７（１Ｆ）、－８０．３（１Ｆ）、－８０．７（１Ｆ）、－８２．２（３Ｆ）、－８５．４～－８８．２（２Ｆ）、－８９．４～－９１．１（８２Ｆ）、－１３０．５（２Ｆ）、－１４５．１（１Ｆ）。
　単位数ｍ１１の平均値：２１、単位数ｍ１２の平均値：２０、化合物（５２－１）の数平均分子量：４，３００。 NMR spectrum of compound (52-1);
1 H-NMR (300.4 MHz, solvent: CDCl 3 , standard: TMS) δ (ppm): 0.7 (2H), 1.7 (2H), 3.6 (11H), 3.8 (2H) 4.2 (2H), 5.8-6.0 (1H).
19 F-NMR (282.7 MHz, solvent: CDCl 3 , reference: CFCl 3 ) δ (ppm): −52.3 to −55.7 (42F), −78.2 (1F), −78.7 ( 1F), -80.3 (1F), -80.7 (1F), -82.2 (3F), -85.4 to -88.2 (2F), -89.4 to -91.1 ( 82F), -130.5 (2F), -145.1 (1F).
Average value of number of units m11: 21, Average value of number of units m12: 20, Number average molecular weight of compound (52-1): 4,300.
　化合物（５２－２）のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（３００．４ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＴＭＳ）　δ（ｐｐｍ）：１．６（３Ｈ）、４．０（２Ｈ）、４．２（２Ｈ）、４．５～５．０（１Ｈ）、５．８～６．２（２Ｈ）。
　１９Ｆ－ＮＭＲ（２８２．７ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）　δ（ｐｐｍ）：－５２．３～－５５．７（４２Ｆ）、－７８．１（１Ｆ）、－７８．７（１Ｆ）、－８０．２（１Ｆ）、－８０．７（１Ｆ）、－８２．２（３Ｆ）、－８５．４～－８８．２（２Ｆ）、－８９．４～－９１．１（８２Ｆ）、－１３０．５（２Ｆ）、－１４５．１（１Ｆ）。
　単位数ｍ１１の平均値：２１、単位数ｍ１２の平均値：２０、化合物（５２－２）の数平均分子量：４，２００。 NMR spectrum of compound (52-2);
1 H-NMR (300.4 MHz, solvent: CDCl 3 , standard: TMS) δ (ppm): 1.6 (3H), 4.0 (2H), 4.2 (2H), 4.5-5. 0 (1H), 5.8 to 6.2 (2H).
19 F-NMR (282.7 MHz, solvent: CDCl 3 , standard: CFCl 3 ) δ (ppm): −52.3 to −55.7 (42F), −78.1 (1F), −78.7 ( 1F), -80.2 (1F), -80.7 (1F), -82.2 (3F), -85.4 to -88.2 (2F), -89.4 to -91.1 ( 82F), -130.5 (2F), -145.1 (1F).
Average value of number of units m11: 21, Average value of number of units m12: 20, Number average molecular weight of compound (52-2): 4,200.
　化合物（５２－１）と化合物（５２－２）と白金との組成物を用いて、下記のウェットコーティング法により、基材の表面処理を行い、例１の物品を得た。基材としては化学強化ガラスを用いた。得られた物品について、耐久性および基材の着色を評価した。結果を表１に示す。 Using the composition of compound (52-1), compound (52-2) and platinum, the substrate was surface-treated by the following wet coating method to obtain the article of Example 1. Chemically tempered glass was used as the substrate. The obtained article was evaluated for durability and coloring of the substrate. The results are shown in Table 1.
　＜ウェットコーティング法＞
　得られた組成物と、液状媒体としてのＣ４Ｆ９ＯＣ２Ｈ５（３Ｍ社製、ノベック（登録商標）７２００）とを混合して、固形分濃度２０％のコーティング液を調製した。コーティング液に基材をディッピングし、３０分間放置後、基材を引き上げた（ディップコート法）。塗膜を２００℃で３０分間乾燥させ、ジクロロペンタフルオロプロパン（旭硝子社製、ＡＫ－２２５）にて洗浄することによって、基材の表面に表面層を有する物品を得た。 <Wet coating method>
The obtained composition was mixed with C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200) as a liquid medium to prepare a coating solution having a solid content concentration of 20%. The substrate was dipped in the coating solution, and after standing for 30 minutes, the substrate was pulled up (dip coating method). The coating film was dried at 200 ° C. for 30 minutes and washed with dichloropentafluoropropane (Asahi Glass Co., Ltd., AK-225) to obtain an article having a surface layer on the surface of the substrate.
〔例２〕
　ヒドロシリル化反応において、白金／ １，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のキシレン溶液（白金含有量：２％）の使用量を１．５０６２５ｇ（化合物（５１）に対する白金の使用量が１，２０５ｐｐｍに相当）に変更した以外は、例１と同様にして化合物（５２－１）および化合物（５２－２）と、白金との組成物を得た。化合物（５２－１）と化合物（５２－２）のモル比は、ＮＭＲより８３：１７であった。また、化合物（Ａ）に相当する化合物（５２－１）に対する白金の質量割合は１，０００ｐｐｍであった。
　得られた組成物を用いた以外は、例１と同様にして物品を製造し、耐久性および基材の着色を評価した。結果を表１に示す。 [Example 2]
In the hydrosilylation reaction, the amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) used was 1.50625 g (based on compound (51)). Except that the amount of platinum used was changed to equivalent to 1,205 ppm, a composition of compound (52-1) and compound (52-2) and platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. Further, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 1,000 ppm.
An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
〔例３〕
　ヒドロシリル化反応において、白金／ １，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のキシレン溶液（白金含有量：２％）の使用量を３．０１２５ｇ（化合物（５１）に対する白金の使用量が２，４１０ｐｐｍに相当）に変更した以外は、例１と同様にして化合物（５２－１）および化合物（５２－２）と、白金との組成物を得た。化合物（５２－１）と化合物（５２－２）のモル比は、ＮＭＲより８３：１７であった。また、化合物（Ａ）に相当する化合物（５２－１）に対する白金の質量割合は２，０００ｐｐｍであった。
　得られた組成物を用いた以外は、例１と同様にして物品を製造し、耐久性および基材の着色を評価した。結果を表１に示す。 [Example 3]
In the hydrosilylation reaction, a platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) was used in an amount of 3.0125 g (based on compound (51)). Except that the amount of platinum used was changed to equivalent to 2,410 ppm, a composition of compound (52-1) and compound (52-2) with platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. Further, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 2,000 ppm.
An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
〔例４〕
　国際公開第２０１３／１２１９８４号の実施例６に記載の方法にしたがい、化合物（１４Ｉ－１）を得た。
　ＣＦ３－Ｏ－（ＣＦ２ＣＦ２Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｘ３（ＣＦ２ＣＦ２Ｏ）－ＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＯＣＨ３　・・・（１４Ｉ－１）
　単位数ｘ３の平均値：１３、化合物（１４Ｉ－１）の数平均分子量：４，７００。 [Example 4]
The compound (14I-1) was obtained according to the method described in Example 6 of WO2013 / 121984.
CF 3 -O- (CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) x3 (CF 2 CF 2 O) -CF 2 CF 2 CF 2 -C (O) OCH 3 ··· (14I- 1)
Average value of number of units × 3: 13, number average molecular weight of compound (14I-1): 4,700.
　５０ｍＬのナスフラスコに、化合物（１４Ｉ－１）の９．０ｇおよびＨ２Ｎ－ＣＨ２－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３の０．４５ｇを入れ、１２時間撹拌した。ＮＭＲから、化合物（１４Ｉ－１）がすべて化合物（１７Ｉ－１）に変換していることを確認した。また、副生物であるメタノールが生成していた。得られた溶液をＡＥ－３０００の９．０ｇで希釈し、シリカゲルカラムクロマトグラフィ（展開溶媒：ＡＥ－３０００）で精製し、化合物（１７Ｉ－１）の７．６ｇ（収率８４％）を得た。
　ＣＦ３－Ｏ－（ＣＦ２ＣＦ２Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｘ３（ＣＦ２ＣＦ２Ｏ）－ＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　・・・（１７Ｉ－１）
　単位数ｘ３の平均値：１３、化合物（１７Ｉ－１）の数平均分子量：４，８００。 In a 50 mL eggplant flask, 9.0 g of compound (14I-1) and 0.45 g of H 2 N—CH 2 —C (CH 2 CH═CH 2 ) 3 were added and stirred for 12 hours. From NMR, it was confirmed that all of the compound (14I-1) was converted to the compound (17I-1). In addition, by-product methanol was generated. The resulting solution was diluted with 9.0 g of AE-3000 and purified by silica gel column chromatography (developing solvent: AE-3000) to obtain 7.6 g (yield 84%) of compound (17I-1). .
CF 3 —O— (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) x3 (CF 2 CF 2 O) —CF 2 CF 2 CF 2 —C (O) NH—CH 2 —C (CH 2 CH = CH 2 ) 3 (17I-1)
Average value of number of units × 3: 13, number average molecular weight of compound (17I-1): 4,800.
　１０ｍＬのＰＦＡ製サンプル管に、化合物（１７Ｉ－１）の６．０ｇ、白金／１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のキシレン溶液（白金含有量：２％）の０．１５ｇ（化合物（１７Ｉ－１）に対する白金の質量割合が５００ｐｐｍに相当）、ＨＳｉ（ＯＣＨ３）３の０．７８ｇ、ジメチルスルホキシドの０．０２ｇ、１，３―ビス（トリフルオロメチル）ベンゼン（東京化成工業社製）の０．４９ｇを入れ、４０℃で１０時間撹拌した。反応終了後、溶媒等を減圧留去し、化合物（１Ｉ－１）の６．７ｇ（収率１００％）と、白金との組成物を得た。化合物（Ａ）に相当する化合物（１Ｉ－１）に対する白金の質量割合は５００ｐｐｍであった。
　ＣＦ３－Ｏ－（ＣＦ２ＣＦ２Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｘ３（ＣＦ２ＣＦ２Ｏ）－ＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－Ｃ［ＣＨ２ＣＨ２ＣＨ２－Ｓｉ（ＯＣＨ３）３］３　・・・（１Ｉ－１） In a 10 mL PFA sample tube, 6.0 g of the compound (17I-1) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2% ) 0.15 g (corresponding to the mass ratio of platinum to the compound (17I-1) of 500 ppm), HSi (OCH 3 ) 3 0.78 g, dimethyl sulfoxide 0.02 g, 1,3-bis (trifluoromethyl) ) 0.49 g of benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 40 ° C. for 10 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure to obtain a composition of 6.7 g (yield 100%) of compound (1I-1) and platinum. The mass ratio of platinum to the compound (1I-1) corresponding to the compound (A) was 500 ppm.
CF 3 —O— (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) x3 (CF 2 CF 2 O) —CF 2 CF 2 CF 2 —C (O) NH—CH 2 —C [CH 2 CH 2 CH 2 —Si (OCH 3 ) 3 ] 3 ... (1I-1)
　化合物（１Ｉ－１）のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（３００．４ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＴＭＳ）　δ（ｐｐｍ）：０．７５（６Ｈ）、１．３～１．６（１２Ｈ）、３．４（２Ｈ）、３．７（２７Ｈ）。
　１９Ｆ－ＮＭＲ（２８２．７ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）　δ（ｐｐｍ）：－５５．２（３Ｆ）、－８２．１（５４Ｆ）、－８８．１（５４Ｆ）、－９０．２（２Ｆ）、－１１９．６（２Ｆ）、－１２５．４（５２Ｆ）、－１２６．２（２Ｆ）。
　単位数ｘ３の平均値：１３、化合物（１Ｉ－１）の数平均分子量：５，４００。 NMR spectrum of compound (1I-1);
1 H-NMR (300.4 MHz, solvent: CDCl 3 , standard: TMS) δ (ppm): 0.75 (6H), 1.3 to 1.6 (12H), 3.4 (2H), 3. 7 (27H).
19 F-NMR (282.7 MHz, solvent: CDCl 3 , reference: CFCl 3 ) δ (ppm): −55.2 (3F), −82.1 (54F), −88.1 (54F), −90 .2 (2F), -119.6 (2F), -125.4 (52F), -126.2 (2F).
Average value of number of units × 3: 13, number average molecular weight of compound (1I-1): 5,400.
　得られた組成物を用いた以外は、例１と同様にして物品を製造し、耐久性および基材の着色を評価した。結果を表１に示す。 Articles were produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
〔例５〕
　特開２０１５－１９９９０６号公報の合成例１に記載の方法にしたがい、化合物（６２）を得た。
　ＣＦ３－Ｏ－｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝－ＣＦ２－Ｃ（ＯＨ）［－ＣＨ２ＣＨ＝ＣＨ２］２　・・・（６２）
　ただし、ｍ１１：ｍ１２＝４７：５３であり、ｍ１１＋ｍ１２≒４３である。 [Example 5]
The compound (62) was obtained according to the method described in Synthesis Example 1 of JP-A-2015-199906.
CF 3 —O — {(CF 2 O) m11 (CF 2 CF 2 O) m12 } —CF 2 —C (OH) [— CH 2 CH═CH 2 ] 2 (62)
However, m11: m12 = 47: 53 and m11 + m12≈43.
　反応容器に、化合物（６２）の２００ｇ（２．６×１０－２ｍｏｌ）、１，３－ビストリフルオロメチルベンゼンの２００ｇ、ＨＳｉ（ＯＣＨ３）３の１２．７ｇ（１．１×１０－１ｍｏｌ）、および塩化白金酸／ビニルシロキサン錯体のトルエン溶液（白金含有量：０．５％）の８０ｇ（化合物（６２）に対する白金の質量割合が２，０００ｐｐｍに相当）を混合し、８０℃で４０時間熟成させた。その後、溶媒および未反応物を減圧留去し、化合物（６３）の２０１ｇと、塩化白金酸との組成物を得た。化合物（Ａ）に相当する化合物（６３）に対する白金の質量割合は２，０００ｐｐｍであった。
　ＣＦ３－Ｏ－｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝－ＣＦ２－Ｃ（ＯＨ）［－ＣＨ２ＣＨ２ＣＨ２－Ｓｉ（ＯＣＨ３）３］２　・・・（６３）
　ただし、ｍ１１：ｍ１２＝４７：５３であり、ｍ１１＋ｍ１２≒４３である。 In a reaction vessel, 200 g (2.6 × 10 −2 mol) of compound (62), 200 g of 1,3-bistrifluoromethylbenzene, 12.7 g (1.1 × 10 −1 ) of HSi (OCH 3 ) 3 were added. mol) and 80 g of a chloroplatinic acid / vinylsiloxane complex toluene solution (platinum content: 0.5%) (the platinum mass ratio to the compound (62) is equivalent to 2,000 ppm) at 80 ° C. Aged for 40 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain a composition of 201 g of compound (63) and chloroplatinic acid. The mass ratio of platinum to the compound (63) corresponding to the compound (A) was 2,000 ppm.
CF 3 —O — {(CF 2 O) m 11 (CF 2 CF 2 O) m 12 } —CF 2 —C (OH) [— CH 2 CH 2 CH 2 —Si (OCH 3 ) 3 ] 2. 63)
However, m11: m12 = 47: 53 and m11 + m12≈43.
　化合物（６３）のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（３００．４ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＴＭＳ）　δ（ｐｐｍ）：０．２～２．２（１２Ｈ）、３．０～３．５（１８Ｈ）。 NMR spectrum of compound (63);
1 H-NMR (300.4 MHz, solvent: CDCl 3 , standard: TMS) δ (ppm): 0.2 to 2.2 (12H), 3.0 to 3.5 (18H).
　得られた組成物を用いた以外は、例１と同様にして物品を製造し、耐久性および基材の着色を評価した。結果を表１に示す。 Articles were produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
〔例６〕
　ヒドロシリル化反応において、白金／ １，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のキシレン溶液（白金含有量：２％）の使用量を７．５３１２５ｇ（化合物（５１）に対する白金の使用量が６，０２５ｐｐｍに相当）に変更した以外は、例１と同様にして化合物（５２－１）および化合物（５２－２）と、白金との組成物を得た。化合物（５２－１）と化合物（５２－２）のモル比は、ＮＭＲより８３：１７であった。また、化合物（Ａ）に相当する化合物（５２－１）に対する白金の質量割合は５，０００ｐｐｍであった。
　得られた組成物を用いた以外は、例１と同様にして物品を製造し、耐久性および基材の着色を評価した。結果を表１に示す。 [Example 6]
In the hydrosilylation reaction, the amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) used was 7.53125 g (based on compound (51)). Except that the amount of platinum used was changed to 6,025 ppm), a composition of compound (52-1) and compound (52-2) and platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. In addition, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 5,000 ppm.
An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
〔例７〕
　ヒドロシリル化反応において、白金／ １，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のキシレン溶液（白金含有量：２％）の使用量を０．１５０６２５ｇ（化合物（５１）に対する白金の使用量が１２０．５ｐｐｍに相当）に変更した以外は、例１と同様にして化合物（５２－１）および化合物（５２－２）と、白金との組成物を得た。化合物（５２－１）と化合物（５２－２）のモル比は、ＮＭＲより８３：１７であった。また、化合物（Ａ）に相当する化合物（５２－１）に対する白金の質量割合は１００ｐｐｍであった。
　得られた組成物を用いた以外は、例１と同様にして物品を製造し、耐久性および基材の着色を評価した。結果を表１に示す。 [Example 7]
In the hydrosilylation reaction, the amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) used was 0.150625 g (based on compound (51)). Except that the amount of platinum used was changed to 120.5 ppm, a composition of compound (52-1) and compound (52-2) and platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. Further, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 100 ppm.
An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
〔例８〕
　ヒドロシリル化反応において、白金／ １，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のキシレン溶液（白金含有量：２％）の使用量を０．００７５３１２５ｇ（化合物（５１）に対する白金の使用量が６．０２５ｐｐｍに相当）に変更した以外は、例１と同様にして化合物（５２－１）および化合物（５２－２）と、白金との組成物を得た。化合物（５２－１）と化合物（５２－２）のモル比は、ＮＭＲより８３：１７であった。また、化合物（Ａ）に相当する化合物（５２－１）に対する白金の質量割合は５ｐｐｍであった。
　得られた組成物を用いた以外は、例１と同様にして物品を製造し、耐久性および基材の着色を評価した。結果を表１に示す。 [Example 8]
In the hydrosilylation reaction, the amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2%) used was 0.00753125 g (based on compound (51)). Except that the amount of platinum used was changed to 6.025 ppm, a composition of compound (52-1) and compound (52-2) and platinum was obtained in the same manner as in Example 1. The molar ratio of compound (52-1) to compound (52-2) was 83:17 from NMR. Further, the mass ratio of platinum to the compound (52-1) corresponding to the compound (A) was 5 ppm.
An article was produced in the same manner as in Example 1 except that the obtained composition was used, and durability and coloring of the substrate were evaluated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　化合物（Ａ）に対する白金の質量割合が３００～４，０００ｐｐｍである例１～５の組成物は、化合物（Ａ）に対する白金の質量割合が１００ｐｐｍ以下である例７、８の組成物に比べて、耐久性に優れる表面層を形成できた。
　また、例１～５の組成物は、化合物（Ａ）に対する白金の質量割合が５，０００ｐｐｍである例６の組成物に比べて、基材の透明性を妨げることなく耐久性に優れる表面層を形成できた。
　なお、例８の組成物を６０℃、９０％ＲＨの条件下で２か月間保存したところ、濁り、分離、沈殿、固化のいずれも発生せず、透明性を維持しており、貯蔵安定性に優れていた。 The compositions of Examples 1 to 5 in which the mass ratio of platinum to the compound (A) is 300 to 4,000 ppm are compared with the compositions of Examples 7 and 8 in which the mass ratio of platinum to the compound (A) is 100 ppm or less. A surface layer having excellent durability could be formed.
In addition, the compositions of Examples 1 to 5 are surface layers excellent in durability without hindering the transparency of the substrate as compared with the composition of Example 6 in which the mass ratio of platinum to the compound (A) is 5,000 ppm. Could be formed.
In addition, when the composition of Example 8 was stored at 60 ° C. and 90% RH for 2 months, no turbidity, separation, precipitation, or solidification occurred, and transparency was maintained and storage stability was maintained. It was excellent.
　本組成物および本組成物を含むコーティング液は、撥水撥油性の付与が求められている各種の用途に用いることができる。たとえばタッチパネル等の表示入力装置；透明なガラス製または透明なプラスチック製（アクリル、ポリカーボネート等）部材の表面保護コート、キッチン用防汚コート；電子機器、熱交換器、電池等の撥水防湿コートや防汚コート、トイレタリー用防汚コート；導通しながら撥液が必要な部材へのコート；熱交換機の撥水・防水・滑水コート；振動ふるいやシリンダ内部等の表面低摩擦コート等に用いることができる。より具体的な使用例としては、ディスプレイの前面保護板、反射防止板、偏光板、アンチグレア板、あるいはそれらの表面に反射防止膜処理を施したもの、携帯電話、携帯情報端末等の機器のタッチパネルシートやタッチパネルディスプレイ等人の指あるいは手のひらで画面上の操作を行う表示入力装置を有する各種機器、トイレ、風呂、洗面所、キッチン等の水周りの装飾建材、配線板用防水コーティング熱交換機の撥水・防水コート、太陽電池の撥水コート、プリント配線板の防水・撥水コート、電子機器筐体や電子部品用の防水・撥水コート、送電線の絶縁性向上コート、各種フィルタの防水・撥水コート、電波吸収材や吸音材の防水性コート、風呂、厨房機器、トイレタリー用防汚コート、熱交換機の撥水・防水・滑水コート、振動ふるいやシリンダ内部等の表面低摩擦コート、機械部品、真空機器部品、ベアリング部品、自動車部品、工具等の表面保護コート等が挙げられる。
　なお、２０１７年０３月２７日に出願された日本特許出願２０１７－０６０９４９号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The composition and the coating liquid containing the composition can be used for various applications that are required to impart water and oil repellency. For example, display input devices such as touch panels; surface protective coatings made of transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members, antifouling coatings for kitchens; water and moisture repellent coatings for electronic devices, heat exchangers, batteries, etc. Antifouling coating, antifouling coating for toiletries; coating on materials that require liquid repellency while conducting; water-repellent / waterproof / sliding coating for heat exchangers; use on vibration screens, low friction surfaces on the inside of cylinders, etc. Can do. More specific examples of use include a front protective plate of a display, an antireflection plate, a polarizing plate, an antiglare plate, or an antireflection coating on the surface thereof, a touch panel of a device such as a mobile phone or a portable information terminal. Various devices with display input devices that operate on the screen with human fingers or palms such as sheets and touch panel displays, decorative building materials around water such as toilets, baths, washrooms, and kitchens, waterproof coating heat exchangers for wiring boards Water / water-proof coating, water-repellent coating for solar cells, waterproof / water-repellent coating for printed wiring boards, waterproof / water-repellent coating for electronic equipment casings and electronic parts, insulation improvement coating for power transmission lines, various filters Water repellent coat, waterproof coat of radio wave absorber and sound absorbing material, bath, kitchen equipment, antifouling coat for toiletries, water repellent / waterproof / slidable coat of heat exchanger, vibration Low surface friction coating Rui and the cylinder interior and the like, mechanical parts, vacuum equipment parts, bearing parts, automobile parts, surface protection coating such as a tool and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-060949 filed on Mar. 27, 2017 are hereby incorporated by reference as the disclosure of the specification of the present invention. It is.

Claims (13)

  1. 　ポリ（オキシペルフルオロアルキレン）鎖および下式（Ｉ）で表される基を有する化合物（Ａ）と、遷移金属化合物とを含む含フッ素エーテル組成物であって、
    　前記化合物（Ａ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍであることを特徴とする含フッ素エーテル組成物。
    　－ＳｉＲｎＬ３－ｎ　・・・（Ｉ）
    　ただし、Ｌは水酸基または加水分解性基であり、
    　Ｒは水素原子または１価の炭化水素基であり、
    　ｎは０～２の整数であり、
    　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
    　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。     A fluorine-containing ether composition comprising a compound (A) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (I), and a transition metal compound,
    A fluorine-containing ether composition, wherein a mass ratio of the transition metal compound to the compound (A) is 300 to 4,000 ppm in terms of transition metal.
    -SiR n L 3-n (I)
    However, L is a hydroxyl group or a hydrolysable group,
    R is a hydrogen atom or a monovalent hydrocarbon group,
    n is an integer from 0 to 2,
    when n is 0 or 1, (3-n) L's may be the same or different;
    When n is 2, n R may be the same or different.
  2. 　前記化合物（Ａ）が、下式（Ａ１）で表される化合物である、請求項１に記載の含フッ素エーテル組成物。
    　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］ａＺ１［－ＳｉＲｎＬ３－ｎ］ｂ　・・・（Ａ１）
    　ただし、Ｌ、Ｒおよびｎはそれぞれ前記と同義であり、
    　Ｒｆ１は、ペルフルオロアルキル基であり、
    　Ｑは、単結合、１個以上の水素原子を含むオキシフルオロアルキレン基、または該オキシフルオロアルキレン基の２～５個が結合してなるポリオキシフルオロアルキレン基であり、該基を構成するオキシフルオロアルキレン基は全てが同一であっても異なっていてもよく、
    　Ｒｆｅは、前記ポリ（オキシペルフルオロアルキレン）鎖であり、
    　Ｚ１は、（ａ＋ｂ）価の連結基であり、
    　ａは、１以上の整数であり、
    　ｂは、１以上の整数であり、
    　ａが２以上のときａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は、同一であっても異なっていてもよく、
    　ｂが２以上のときｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。     The fluorine-containing ether composition according to claim 1, wherein the compound (A) is a compound represented by the following formula (A1).
    [R f1 -OQR fe- ] a Z 1 [-SiR n L 3-n ] b (A1)
    However, L, R, and n are respectively synonymous with the above,
    R f1 is a perfluoroalkyl group;
    Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups. The alkylene groups may all be the same or different,
    R fe is the poly (oxyperfluoroalkylene) chain,
    Z 1 is a (a + b) -valent linking group,
    a is an integer of 1 or more,
    b is an integer of 1 or more,
    When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different,
    When b is 2 or more, b [-SiR n L 3-n ] may be the same or different.
  3. 　前記ポリ（オキシペルフルオロアルキレン）鎖が、｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２Ｏ）ｍ１２｝、｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１２｝、｛（ＣＦ２Ｏ）ｍ１１（ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１２｝または（ＣＦ２ＣＦ２Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｍ１５である（ただし、ｍ１１は１以上の整数であり、ｍ１２は１以上の整数であって（ｍ１１＋ｍ１２）は２～２００の整数であり、ｍ１５は１～１００の整数である。）、請求項１または２に記載の含フッ素エーテル組成物。 The poly ( oxyperfluoroalkylene ) chain has {(CF 2 O) m11 (CF 2 CF 2 O) m12 }, {(CF 2 O) m11 (CF 2 CF 2 CF 2 O) m12 }, {(CF 2 O) m11 (CF 2 CF 2 CF 2 CF 2 O) m12 } or (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) m15 (where m11 is an integer of 1 or more, m12 3. The fluorine-containing ether composition according to claim 1, wherein is an integer of 1 or more, (m11 + m12) is an integer of 2 to 200, and m15 is an integer of 1 to 100).
  4. 　前記ａが１～３の整数であって、ａが２または３の場合ａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は同一であり、前記ｂが２～５の整数であって、ｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一である、請求項３に記載の含フッ素エーテル組成物。 When a is an integer of 1 to 3 and a is 2 or 3, a number of [R f1 —OQR fe —] is the same, and b is an integer of 2 to 5. The b [-SiR n L 3-n ] are the same, and the fluorine-containing ether composition according to claim 3.
  5. 　前記化合物（Ａ）の数平均分子量（Ｍｎ）が、２，０００～２０，０００である、請求項１～４のいずれか一項に記載の含フッ素エーテル化合物。 The fluorine-containing ether compound according to any one of claims 1 to 4, wherein the compound (A) has a number average molecular weight (Mn) of 2,000 to 20,000.
  6. 　前記遷移金属化合物が、ヒドロシリル化反応の触媒として作用する遷移金属化合物である、請求項１～５のいずれか一項に記載の含フッ素エーテル組成物。 The fluorine-containing ether composition according to any one of claims 1 to 5, wherein the transition metal compound is a transition metal compound that acts as a catalyst for a hydrosilylation reaction.
  7. 　前記遷移金属化合物が白金化合物である、請求項１～６のいずれか一項に記載の含フッ素エーテル組成物。 The fluorine-containing ether composition according to any one of claims 1 to 6, wherein the transition metal compound is a platinum compound.
  8. 　請求項１～７のいずれか一項に記載の含フッ素エーテル組成物と、液状媒体とを含むことを特徴とするコーティング液。 A coating liquid comprising the fluorinated ether composition according to any one of claims 1 to 7 and a liquid medium.
  9. 　請求項１～７のいずれか一項に記載の含フッ素エーテル組成物から形成された表面層を有することを特徴とする物品。 An article having a surface layer formed from the fluorine-containing ether composition according to any one of claims 1 to 7.
  10. 　ポリ（オキシペルフルオロアルキレン）鎖および下式（ＩＸ）で表される基を有する化合物（ＡＨ）と、遷移金属化合物とを含み、前記化合物（ＡＨ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍである含フッ素エーテル組成物を製造する方法であって、
    　ポリ（オキシペルフルオロアルキレン）鎖および下式（ＩＩＩ）で表される基を有する化合物（Ｂ）と、下式（Ｓ）で表される化合物とを、前記化合物（Ｂ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍである量の前記遷移金属化合物の存在下に反応を行って、前記化合物（ＡＨ）を生成させることを特徴とする含フッ素エーテル組成物の製造方法。
    　－ＣＨ＝ＣＨ２　・・・（ＩＩＩ）
    　ＨＳｉＲｎＬ３－ｎ　・・・（Ｓ）
    　－ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ　・・・（ＩＸ）
    　ただし、Ｌは水酸基または加水分解性基であり、
    　Ｒは水素原子または１価の炭化水素基であり、
    　ｎは０～２の整数であり、
    　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
    　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。     A compound (AH) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (IX), and a transition metal compound, wherein the mass ratio of the transition metal compound to the compound (AH) is converted to transition metal A method for producing a fluorine-containing ether composition having a concentration of 300 to 4,000 ppm,
    A compound (B) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (III), and a compound represented by the following formula (S) are converted into the transition metal compound for the compound (B): A method for producing a fluorine-containing ether composition, wherein the compound (AH) is produced by reacting in the presence of the transition metal compound in an amount of 300 to 4,000 ppm in terms of transition metal in terms of mass ratio .
    -CH = CH 2 (III)
    HSiR n L 3-n (S)
    —CH 2 CH 2 —SiR n L 3-n (IX)
    However, L is a hydroxyl group or a hydrolysable group,
    R is a hydrogen atom or a monovalent hydrocarbon group,
    n is an integer from 0 to 2,
    when n is 0 or 1, (3-n) L's may be the same or different;
    When n is 2, n R may be the same or different.
  11. 　ポリ（オキシペルフルオロアルキレン）鎖および下式（ＩＸ）で表される基を有する化合物（ＡＨ）と、遷移金属化合物とを含み、前記化合物（ＡＨ）に対する前記遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍである含フッ素エーテル組成物を製造する方法であって、
    　ポリ（オキシペルフルオロアルキレン）鎖および下式（ＩＩＩ）で表される基を有する化合物（Ｂ）と、下式（Ｓ）で表される化合物とを、前記化合物（Ｂ）に対する前記遷移金属化合物の質量割合が遷移金属換算で１ｐｐｍ以上３００ｐｐｍ未満である量の前記遷移金属化合物の存在下に反応を行って前記化合物（ＡＨ）を生成させ、
    　次いで、前記化合物（ＡＸ）に対する遷移金属化合物の質量割合が遷移金属換算で３００～４，０００ｐｐｍとなるように、反応生成物に遷移金属化合物を添加することを特徴とする含フッ素エーテル組成物の製造方法。
    　－ＣＨ＝ＣＨ２　・・・（ＩＩＩ）
    　ＨＳｉＲｎＬ３－ｎ　・・・（Ｓ）
    　－ＣＨ２ＣＨ２－ＳｉＲｎＬ３－ｎ　・・・（ＩＸ）
    　ただし、Ｌは水酸基または加水分解性基であり、
    　Ｒは水素原子または１価の炭化水素基であり、
    　ｎは０～２の整数であり、
    　ｎが０または１のとき（３－ｎ）個のＬは、同一であっても異なっていてもよく、
    　ｎが２のときｎ個のＲは、同一であっても異なっていてもよい。     A compound (AH) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (IX), and a transition metal compound, wherein the mass ratio of the transition metal compound to the compound (AH) is converted to transition metal A method for producing a fluorine-containing ether composition having a concentration of 300 to 4,000 ppm,
    A compound (B) having a poly (oxyperfluoroalkylene) chain and a group represented by the following formula (III), and a compound represented by the following formula (S) are converted into the transition metal compound for the compound (B): Reaction is performed in the presence of an amount of the transition metal compound having a mass ratio of 1 ppm or more and less than 300 ppm in terms of transition metal to produce the compound (AH),
    Next, the transition metal compound is added to the reaction product so that the mass ratio of the transition metal compound to the compound (AX) is 300 to 4,000 ppm in terms of transition metal. Production method.
    -CH = CH 2 (III)
    HSiR n L 3-n (S)
    —CH 2 CH 2 —SiR n L 3-n (IX)
    However, L is a hydroxyl group or a hydrolysable group,
    R is a hydrogen atom or a monovalent hydrocarbon group,
    n is an integer from 0 to 2,
    when n is 0 or 1, (3-n) L's may be the same or different;
    When n is 2, n R may be the same or different.
  12. 　前記化合物（ＡＸ）が、下式（ＡＸ１）で表される化合物である、請求項１０または１１に記載の含フッ素エーテル組成物の製造方法。
    　［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］ａＺ１Ｘ［－ＳｉＲｎＬ３－ｎ］ｂ　・・・（ＡＸ１）
    　ただし、Ｌ、Ｒおよびｎはそれぞれ前記と同義であり、
    　Ｒｆ１は、ペルフルオロアルキル基であり、
    　Ｑは、単結合、１個以上の水素原子を含むオキシフルオロアルキレン基、または該オキシフルオロアルキレン基の２～５個が結合してなるポリオキシフルオロアルキレン基であり、該基を構成するオキシフルオロアルキレン基は全てが同一であっても異なっていてもよく、
    　Ｒｆｅは、前記ポリ（オキシペルフルオロアルキレン）鎖であり、
    　Ｚ１Ｘは、（ａ＋ｂ）価の連結基であり、－ＳｉＲｎＬ３－ｎとの結合末端に－ＣＨ２ＣＨ２－を有し、
    　ａは、１以上の整数であり、
    　ｂは、１以上の整数であり、
    　ａが２以上のときａ個の［Ｒｆ１－Ｏ－Ｑ－Ｒｆｅ－］は、同一であっても異なっていてもよく、
    　ｂが２以上のときｂ個の［－ＳｉＲｎＬ３－ｎ］は、同一であっても異なっていてもよい。     The method for producing a fluorinated ether composition according to claim 10 or 11, wherein the compound (AX) is a compound represented by the following formula (AX1).
    [R f1 -OQR fe- ] a Z 1X [-SiR n L 3-n ] b (AX1)
    However, L, R, and n are respectively synonymous with the above,
    R f1 is a perfluoroalkyl group;
    Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups. The alkylene groups may all be the same or different,
    R fe is the poly (oxyperfluoroalkylene) chain,
    Z 1X is a (a + b) -valent linking group, and has —CH 2 CH 2 — at the bond terminal to —SiR n L 3-n ,
    a is an integer of 1 or more,
    b is an integer of 1 or more,
    When a is 2 or more, a [R f1 -OQR fe- ] may be the same or different,
    When b is 2 or more, b [-SiR n L 3-n ] may be the same or different.
  13. 　前記遷移金属化合物が白金化合物である、請求項１０～１２のいずれか一項に記載の含フッ素エーテル組成物の製造方法。 The method for producing a fluorinated ether composition according to any one of claims 10 to 12, wherein the transition metal compound is a platinum compound.
PCT/JP2018/010306 2017-03-27 2018-03-15 Fluorinated ether composition and method for producing same WO2018180561A1 (en)

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