WO2018180561A1 - Composition d'éther fluoré et procédé de production associé - Google Patents

Composition d'éther fluoré et procédé de production associé Download PDF

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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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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 CN201880017367.0A priority Critical patent/CN110392711B/zh
Priority to JP2019509261A priority patent/JP6977767B2/ja
Publication of WO2018180561A1 publication Critical patent/WO2018180561A1/fr

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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

L'invention concerne : une composition d'éther fluoré qui peut être formée en une couche de surface présentant une excellente durabilité sans détériorer la transparence d'une base ; et un procédé de production d'une composition d'éther fluoré. L'invention concerne une composition d'éther fluoré contenant un composé (A) ayant une chaîne poly(oxyperfluoroalkylène) et un groupe représenté par la formule (I) et un composé de métal de transition, le rapport de la masse du composé de métal de transition à la masse du composé (A) étant de 300 à 4 000 ppm en termes de teneur du métal de transition. (I) -SiRnL3-n ; dans laquelle L représente un groupe hydroxy ou un groupe hydrolysable, R représente un atome d'hydrogène ou un groupe hydrocarboné monovalent et n représente un nombre entier de 0 à 2.
PCT/JP2018/010306 2017-03-27 2018-03-15 Composition d'éther fluoré et procédé de production associé WO2018180561A1 (fr)

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JP2013510931A (ja) * 2009-11-11 2013-03-28 エシロール アンテルナシオナル （コンパニー ジェネラル ドプティック） 表面処理組成物、その製造方法および表面処理された物品
JP2013227279A (ja) * 2012-03-30 2013-11-07 Daikin Industries Ltd フルオロポリエーテル基含有シリコーン化合物
JP2014505114A (ja) * 2010-11-10 2014-02-27 ダウ・コーニング・コーポレイション 表面処理組成物、表面処理組成物の製造方法、及び表面処理した物品
JP2015199906A (ja) * 2014-03-31 2015-11-12 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
WO2016101185A1 (fr) * 2014-12-24 2016-06-30 E. I. Du Pont De Nemours And Company Perfluoropolyéthersilanes et leur procédé de préparation
JP2016210854A (ja) * 2015-05-01 2016-12-15 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品

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JP2013510931A (ja) * 2009-11-11 2013-03-28 エシロール アンテルナシオナル （コンパニー ジェネラル ドプティック） 表面処理組成物、その製造方法および表面処理された物品
JP2014505114A (ja) * 2010-11-10 2014-02-27 ダウ・コーニング・コーポレイション 表面処理組成物、表面処理組成物の製造方法、及び表面処理した物品
JP2013227279A (ja) * 2012-03-30 2013-11-07 Daikin Industries Ltd フルオロポリエーテル基含有シリコーン化合物
JP2015199906A (ja) * 2014-03-31 2015-11-12 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
WO2016101185A1 (fr) * 2014-12-24 2016-06-30 E. I. Du Pont De Nemours And Company Perfluoropolyéthersilanes et leur procédé de préparation
JP2016210854A (ja) * 2015-05-01 2016-12-15 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品

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