WO2018151055A1 - Composition d'éther fluoré, liquide de revêtement, et article - Google Patents

Composition d'éther fluoré, liquide de revêtement, et article Download PDF

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WO2018151055A1
WO2018151055A1 PCT/JP2018/004714 JP2018004714W WO2018151055A1 WO 2018151055 A1 WO2018151055 A1 WO 2018151055A1 JP 2018004714 W JP2018004714 W JP 2018004714W WO 2018151055 A1 WO2018151055 A1 WO 2018151055A1
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group
compound
fluorine
containing ether
ether compound
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PCT/JP2018/004714
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English (en)
Japanese (ja)
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健二 石関
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Ａｇｃ株式会社
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Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to KR1020197013797A priority Critical patent/KR102531226B1/ko
Priority to CN201880005514.2A priority patent/CN110114410A/zh
Priority to JP2018568501A priority patent/JP6652203B2/ja
Publication of WO2018151055A1 publication Critical patent/WO2018151055A1/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
    • C08G65/04—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 from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
    • 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
    • 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
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a fluorine-containing ether composition, a coating liquid, and an article.
  • Fluorine-containing compounds exhibit high lubricity, water and oil repellency, etc., and are therefore used as surface treatment agents. For example, when a surface layer is formed on the surface of the base material by the surface treatment agent, lubricity, water and oil repellency, etc. are imparted, and it becomes easy to wipe off dirt on the surface of the base material, thereby improving dirt removal.
  • 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 one having a hydrolyzable silyl group has been proposed.
  • a fluorine-containing ether compound has a performance that prevents water and oil repellency from decreasing even when repeatedly rubbed with a finger (rubbing resistance) and a performance that can easily remove fingerprints attached to the surface by wiping (fingerprint stain removability) Is used for a surface treatment agent of a member constituting a surface touched by a finger of a touch panel, for example, which is required to be maintained for a long period of time.
  • Patent Document 1 discloses a composition containing 95% by mass or more of the fluorine-containing ether compound and a mixture containing two kinds of the fluorine-containing ether compound.
  • the surface layer formed by the fluorine-containing ether compound, composition or mixture described in Patent Document 1 has insufficient water droplet sliding properties.
  • the water drop sliding property is a property in which water drops are likely to slide on an inclined surface (the sliding angle is small or / and the sliding speed is fast).
  • An object of this invention is to provide the fluorine-containing ether composition and coating liquid which can form the surface layer excellent in water-drop sliding property, and the article
  • the present invention provides a fluorine-containing ether composition, a coating liquid, and an article having the following configurations [1] to [15].
  • a composition comprising a fluorinated ether compound (A) and a fluorinated ether compound (B),
  • the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are each represented by the following formula (I), a poly (oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one end thereof, and And a group
  • the carbon number of the perfluoroalkyl group of the fluorine-containing ether compound (A) is Less than the carbon number of the perfluoroalkyl group (B) has,
  • the fluorine-containing ether compound (A) content is 30 to 95% by mass with respect to the total of the fluorine-containing ether
  • Ether composition -SiR n L 3-n (I)
  • 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 Rs may be the same or different
  • the groups represented by the formula (I) which each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) have may be the same or different.
  • the perfluoroalkyl group of the fluorine-containing ether compound (A) has 1 to 19 carbon atoms, and the perfluoroalkyl group of the fluorine-containing ether compound (B) has 2 to 20 carbon atoms.
  • a fluorine-containing ether composition [1] A fluorine-containing ether composition.
  • the perfluoroalkyl group of the fluorine-containing ether compound (A) has 1 carbon
  • the perfluoroalkyl group of the fluorine-containing ether compound (B) has 2 or 3, or the fluorine-containing ether
  • the number of the groups represented by the formula (I) that each of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) has is 1 to 3, [1] to [3] Any fluorine-containing ether composition of these.
  • the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are both fluorine-containing ether compounds represented by the following formula (A / B), and the composition contains in combination with the fluorine-containing ether compound (a) and the fluorine-containing ether compound (B) contained, the carbon number of R f in the fluorine-containing ether compound (a), fluorine-containing ether compound in (B) of the R f
  • the fluorine-containing ether composition according to [1] which has less carbon number.
  • R f is a perfluoroalkyl group, and when r is 2 or more, r perfluoroalkyl groups are the same 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, RPF is a poly (oxyperfluoroalkylene) chain; Z is a (r + s) -valent linking group, -SiR n L 3-n is a group represented by the formula (I), and when s is 2 or more, s groups represented by the formula (I) are the same group; r and s are each an integer of 1 or more, and r + s is 8 or less.
  • [8] The fluorine-containing ether composition of [6] or [7], wherein s is 1 to 3.
  • R fa and R fb are perfluoroalkyl groups, and the number of carbon atoms in R fa is less than the number of carbon atoms in R fb , Q a and Q b are 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 oxyfluoroalkylene groups constituting may all be the same or different, R PFa and R PFb are poly ( oxyperfluoro
  • r1 R fa , Q a and R PFa may be the same or different, and r2 is 2 when r2 is 2 or more.
  • R fb , Q b and R PFb may be the same or different
  • s1 and s2 are integers of 1 or more, and when s1 is 2 or more, s1 [-SiR a n1 L a 3-n1 ] may be the same or different, and s2 is 2 or more Sometimes s2 [—SiR b n2 L b 3-n2 ] may be the same or different.
  • the carbon number of R fa in the formula (A1) is 1, the carbon number of R fb in the formula (B1) is 2 or 3, or the carbon number of R fa in the formula (A1)
  • a coating liquid comprising the fluorine-containing ether composition according to any one of [1] to [13] and a liquid medium.
  • the fluorine-containing ether composition and the coating liquid of the present invention it is possible to form a surface layer having excellent water droplet sliding properties.
  • the article of the present invention has a surface layer that is excellent in water slidability.
  • a compound represented by the formula (1) is referred to as a compound (1), and a group represented by the formula (I) is referred to as a group (I).
  • group (I) is referred to as a group (I).
  • 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.
  • the fluorine-containing ether composition of the present invention (hereinafter also referred to as “the present composition”) comprises a fluorine-containing ether compound (A) (hereinafter also referred to as “compound (A)”) and a fluorine-containing ether compound (B). (Hereinafter also referred to as “compound (B)”).
  • the composition does not contain a liquid medium as described later.
  • the present composition may be composed of the compound (A) and the compound (B).
  • other fluorine-containing ether compounds other than the compound (A) and the compound (B), the compound (A), the compound ( Impurities other than B) and other fluorine-containing ether compounds may be contained.
  • Compound (A) and Compound (B) are each a poly (oxyperfluoroalkylene) chain (hereinafter also referred to as “ RPF chain”) and a perfluoroalkyl group (hereinafter referred to as “R f group”) bonded to one end thereof. And a group represented by the following formula (I) (hereinafter also referred to as “group (I)”).
  • 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 number of carbon atoms in the R f group that the compound (A) has is less than the number of carbon atoms in the R f group that the compound (B) has. That is, this composition contains 2 types from which carbon number of Rf group differs as a fluorine-containing ether compound which has RPF chain
  • the RPF chain and group (I) possessed by each of the compound (A) and the compound (B) may be the same or different.
  • the number of carbon atoms in the R f group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint of further improving the lubricity and friction resistance of the surface layer.
  • compound (A) R f carbon atoms 1 to 19 groups having preferably a carbon number of the R f group to the compound (B) has is 2 ⁇ 20, the R f group having compound (A) carbon atoms 1-9, more preferably carbon number of the R f group is 2 to 10 compound (B) has, compound the carbon number of the R f group (a) has 1 to 5, compound ( more preferably carbon number of the R f group is 2 to 6 B) has, compound (number of carbon atoms in the R f group is 1 a) has a carbon number of the R f group to the compound (B) has 2 It is particularly preferable that the number of carbon atoms in the R f group of the compound (A) is 2, and the number of carbon atoms of the R f group in the compound (B) is 3.
  • the R f group may be branched or linear, and is preferably linear.
  • Examples of the R f group include CF 3 —, CF 3 CF 2 —, CF 3 CF 2 CF 2 — and the like, and CF 3 —, CF 3 CF 2 — are particularly preferable.
  • the number of R f groups that the compound (A) has is the same as the number of R PF chains. If the compound (A) has two or more R f group may be all the the R f group has optionally substituted by one or more identical radicals, preferably identical radicals. Similarly, the number of R f groups that compound (B) has is the same as the number of R PF chains. When the compound (B) has two or more R f group may be all the the R f group has optionally substituted by one or more identical radicals, preferably identical radicals.
  • the number of carbon atoms of the most common the R f group with the carbon number of the R f group to compound (A) is, than the number of carbon atoms in the least the R f group with the carbon number of the R f group to the compound (B) has Few.
  • Examples of the combination of the R f group, compound (A) having the R f group is CF 3 -, the compound (B) the R f group having there is CF 3 CF 2 - a combination of the the R f group to compound (A) CF 3 -, the compound (B) the R f group having there is CF 3 CF 2 CF 2 - a combination of the compound (a) the R f group having there is CF 3 CF 2 -, is the R f group having compound (B)
  • a combination of CF 3 CF 2 — is preferable, and a combination of CF 3 — as the R f group of the compound (A) and CF 3 CF 2 — as the R f group of the compound (B) is particularly preferable.
  • the Rf group is typically attached to one end of the RPF chain via a linking group.
  • group (II) is preferred. That is, it is preferable that the R f group is bonded to one end of each RPF chain of each of the compound (A) and the compound (B) via the group (II). However, the left side of the group (II) is bonded to the Rf group.
  • -OQ- (II) Q represents 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 groups. It is. All of the oxyfluoroalkylene groups constituting the group may be the same or different.
  • the number of carbon atoms of the oxyfluoroalkylene group in Q is preferably 2 to 6, 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 an oxyfluoroalkylene group having no branched structure or an oxyfluoroalkylene group having a branched structure. An oxyfluoroalkylene group having no branched structure is preferable from the viewpoint of further excellent wear resistance and lubricity of the surface layer.
  • 2 to 5 oxyfluoroalkylene groups may 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—, — from the viewpoint of ease of production of the compound (A) and the compound (B).
  • a group selected from the group consisting of OCH 2 CF 2 O— and —CF 2 CF 2 OCF 2 CH 2 OCH 2 CF 2 O— (where the left side is bonded to O) is preferred.
  • R PF chain The R PF chain, for example, the R PF chain represented by the following formula (1).
  • R F O m1
  • R F is a perfluoroalkylene group
  • m1 is an integer from 2 to 200
  • R F O m1 may be composed of two or more R F Os having different carbon numbers.
  • the number of carbon atoms in R F is, from the viewpoint of further excellent abrasion resistance and fingerprint removal of the surface layer is preferably 1 to 6, more preferably 1 to 4, from the viewpoint of further excellent lubricity 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 F 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 weights of the compound (A) and the compound (B) are too large, the number of groups (I) present per unit molecular weight is reduced, and the friction resistance is lowered.
  • R F O (R F O) In m1 , when two or more types of R F O having different carbon numbers exist, the bonding order of each R F O is not limited. For example, if the two R F O are present, the two R F O is random, alternating, or may be arranged in blocks.
  • 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
  • the bonding order of m11 CF 2 O and m12 CF 2 CF 2 O Is not limited.
  • m13 and m14 are each an integer of 2 to 200
  • m15 is an integer of 1 to 100.
  • m15 is preferably an integer of 2 to 100.
  • the compound (A) and the compound (B) each may have one RPF chain or two or more RPF chains. From the viewpoint of friction resistance, 1 to 3 is preferable, and 1 to 2 is particularly preferable.
  • the number of RPF chains, and thus the number of Rf groups is 1 or more, the surface layer is excellent in water droplet sliding property, water / oil repellency, durability, fingerprint stain removability, and lubricity. If the number of RPF chains is not more than the upper limit of the above range, the appearance of the surface layer is excellent.
  • Compound (A), compound (B) may have two or more R PF chain, each R PF chain may be the same or different.
  • 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 alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable.
  • L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of easy production of the compound (A) and the compound (B).
  • a halogen atom a chlorine atom is particularly preferable.
  • L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint that the outgassing during coating is small and the storage stability of the compound (A) and the compound (B) is excellent, and the compound (A) and the compound (B) An ethoxy group is particularly preferred when long-term storage stability is required, 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.
  • monovalent hydrocarbon groups include saturated hydrocarbon groups such as alkyl groups and cycloalkyl groups, alkenyl groups such as allyl groups, and the like, and saturated hydrocarbon groups are preferred.
  • the number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 in terms of easy production of the compound (A) and the compound (B).
  • 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.
  • the group (I) possessed by each of the compound (A) and the compound (B) may be one or two or more. One to three is preferable from the viewpoint of further excellent water droplet sliding property of the surface layer, and two or three is particularly preferable from the viewpoint of further excellent friction resistance of the surface layer.
  • all of the groups (I) may or may not be the same group. In terms of ease of production of the compound (A), it is preferred that all are the same group.
  • the number average molecular weight (Mn) of each of the compound (A) and the compound (B) is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, and particularly preferably 3,000 to 10,000. . When the number average molecular weight is within the above range, the friction resistance is excellent.
  • the number average molecular weight (Mn) is measured by the measuring method described in the examples described later.
  • the difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is small.
  • the smaller the molecular weight the easier it is to evaporate first and to deposit on the substrate.
  • the difference in the number average molecular weight (Mn) is smaller, unevenness in the distribution of the compound (A) and the compound (B) is less likely to occur in the formed surface layer.
  • the difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is preferably 2,000 or less, and particularly preferably 1,000 or less.
  • the surface layer is formed by a wet coating method
  • the surface layer is formed even if there is a difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B). Since unevenness of the distribution of the compound (A) and the compound (B) hardly occurs, the difference between them is not particularly limited.
  • the dry coating method and the wet coating method will be described in detail later.
  • the compound (A) and the compound (B) are not particularly limited as long as each has an RPF chain, an Rf group and a group (I).
  • it can be appropriately selected from known fluorine-containing ether compounds such as fluorine-containing ether compounds and commercially available 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.
  • R PF chain has the R f group and a group (I), the R f group is CF 3 -
  • the fluorine-containing ether compound is is manufactured by Daikin Industries, Ltd. of Optool (registered trademark) UD509, manufactured by Shin-Etsu Chemical Co., Examples thereof include KY-178, KY-185, and KY-1900 manufactured by the same company.
  • Examples of fluorine-containing ether compounds having an RPF chain, an R f group and a group (I), and the R f group is CF 3 CF 2 CF 2 — include OPTOOL DSX, AES and Toray Dow manufactured by Daikin Industries, Ltd.
  • this composition contains a fluorine-containing ether compound which is CF 3- as the compound (A) and a fluorine-containing ether compound whose R f group is CF 3 CF 2 CF 2- as the compound (B). It may be.
  • each of the compound (A) and the compound (B) may be a single compound composed of one kind of compound or a mixture composed of two or more kinds of compounds.
  • 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 compound group except that it has a distribution in m11 and m12 includes a fluorine-containing ether compound that is a single compound.
  • a fluorine-containing ether compound represented by the following formula (A / B) is preferable.
  • R f in the following formula (A / B) represents the R f group, and in the combination of the compound (A) and the compound (B) contained in the present composition, the carbon of R f in the compound (A) The number is smaller than the carbon number of R f in the compound (B).
  • R PF represents the R PF chain, and Q and SiR n L 3-n are the same as those described above.
  • R f is a perfluoroalkyl group, and when r is 2 or more, r perfluoroalkyl groups are the same 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, RPF is a poly (oxyperfluoroalkylene) chain; Z is a (r + s) -valent linking group, -SiR n L 3-n is a group represented by the formula (I), and when s is 2 or more, s groups represented by the formula (I) are the same group; r and s are each an integer of 1 or more, and r + s is 8 or less.
  • the r represents the number of RPF chains, and thus the number of Rf groups, and is an integer of 1 or more. As described above, r is preferably 1 to 3, and particularly preferably 1 to 2, from the viewpoint of friction resistance.
  • the above s represents the number of groups (I), and as described above, 1 to 3 is preferable from the viewpoint of further excellent water droplet sliding properties of the surface layer, and 2 or 3 from the viewpoint of further excellent friction resistance of the surface layer. Is particularly preferred.
  • r + s is preferably 2 to 6, and particularly preferably 3 to 5.
  • Z as the (r + s) -valent linking group is preferably a linking group represented by Z a or Z b described later, for example, a carbon atom of a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted hydrocarbon group.
  • a group having a group or atom other than a hydrocarbon group, or an organopolysiloxane group between carbon atoms or / and at the terminal may be mentioned.
  • Preferred Z is the same linking group as preferred Z a and Z b below.
  • the compound (A) is a fluorinated ether compound (A1) represented by the following formula (A1) (hereinafter also referred to as “compound (A1)”)
  • the compound (B) Is a fluorine-containing ether compound (B1) represented by the following formula (B1) (hereinafter also referred to as “compound (B1)”). That is, the composition of this embodiment includes the compound (A1) and the compound (B1), and the content of the compound (A1) is 30 to 95 mass with respect to the total of the compound (A1) and the compound (B1). %.
  • R fa and R fb are R f groups, and R fa has fewer carbon atoms than R fb , Q a and Q b are 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 oxyfluoroalkylene groups constituting may all be the same or different, R PFa and R PFb are R PF chains; Z a is a (r1 + s1) -valent linking group
  • r1 R fa , Q a and R PFa may be the same or different, and r2 is 2 when r2 is 2 or more.
  • R fb , Q b and R PFb may be the same or different
  • s1 and s2 are integers of 1 or more, and when s1 is 2 or more, s1 [-SiR a n1 L a 3-n1 ] may be the same or different, and when s2 is 2 or more
  • the s2 [—SiR b n2 L b 3-n2 ] may be the same or different.
  • the R f group is the same as described above, and the preferred embodiment is also the same.
  • r1 is 2 or more, it is preferable that r1 R fas have the same carbon number, and from the viewpoint of ease of production, they are the same group, that is, the same carbon number and the same chemical structure. Is preferred.
  • the group having the same carbon number and the same chemical structure means that, for example, when r1 is 2, two R fa are CF 3 CF 2 CF 2 — (the two R fa are (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.)
  • r2 is 2 or more, it is preferable that r2 R fb have the same carbon number, and from the viewpoint of ease of production, it is the same group, that is, a group having the same carbon number and the same chemical structure. Is preferred.
  • R fa preferably has 1 to 19 carbon atoms and R fb has 2 to 20 carbon atoms, and R fa has a carbon number of Is more preferably 1 to 9, and R fb has 2 to 10 carbon atoms, R fa has 1 to 5 carbon atoms, R fb has 2 to 6 carbon atoms, and R fa has 2 to 6 carbon atoms. It is particularly preferred that the carbon number is 1, R fb has 2 or 3 carbon atoms, or R fa has 2 carbon atoms and R fb has 3 carbon atoms.
  • Q a and Q b are the same as Q in the group (II), and preferred embodiments are also the same.
  • the R PF chains of R PFa and R PFb are the same as described above, and the preferred embodiments are also the same.
  • L a and L b are the same as L in the group (I), and preferred embodiments are also the same.
  • R a and R b are the same as R in the group (I), and preferred embodiments are also the same.
  • n1 and n2 are the same as n in the group (I), and preferred embodiments are also the same.
  • the preferable values of r1 and r2 are the same as the preferable number of RPF chains that the compound (A) and the compound (B) have.
  • r1 and r2 are preferably 1 to 3 and particularly preferably 1 to 2 from the viewpoint of friction resistance.
  • the preferred values of s1 and s2 are the same as the preferred number of groups (I) that compound (A) and compound (B) have. That is, s1 and s2 are preferably from 1 to 3, and particularly preferably from 2 to 3, from the viewpoint of excellent water droplet sliding property of the surface layer.
  • the Z a for example, (r1 + s1) valent substituted or unsubstituted hydrocarbon group, the carbon of a substituted or unsubstituted hydrocarbon group - between carbon atoms and / or at the end, with a group or atom other than a hydrocarbon group (R1 + s1) -valent group, (r1 + s1) -valent organopolysiloxane group, and the like.
  • Z b may be the same as Z a except that the valence is (r2 + s2).
  • 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.
  • 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.
  • substituents 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 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 fa, Q a, R PFa, R a, L a and n1 have the same meanings as defined above
  • Q 32a is a fluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms
  • R 33a is a hydrogen atom or an alkyl group
  • p1 is 0 or 1
  • R 34a is a single bond, an alkylene group, or a group having an etheric oxygen atom at the end of the alkylene group (provided
  • the fluoroalkylene group is preferably a perfluoroalkylene group or a fluoroalkylene group containing one or more hydrogen atoms. Accordingly, as Q 32a , a perfluoroalkylene group, a fluoroalkylene group containing one or more hydrogen atoms, a group having an etheric oxygen atom between carbon-carbon atoms of a perfluoroalkylene group having 2 or more carbon atoms, or one or more Of these, a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms containing a hydrogen atom is preferred.
  • the Q 32a preferably a perfluoroalkylene group, perfluoroalkylene group preferably has no branched structure. If Q 32a is a perfluoroalkylene group having no branched structure, the friction resistance and lubricity of the surface layer are further improved. When p1 is 0, Q 32a is typically carbon when R PFa is ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ or (CF 2 CF 2 O) m13.
  • R PFa is (CF 2 CF 2 CF 2 O) m14 , it is typically a C 2 perfluoroalkylene group, and R PFa is (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) m15 is typically a straight-chain perfluoroalkylene group having 3 carbon atoms.
  • examples of Q 32a include the following groups.
  • R 34a is preferably 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 — (the left side is bonded to Q 32a ) is preferred.
  • R 34a 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 35a 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 35a one having no etheric oxygen atom is 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 35a 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 fa —O—Q a —R PFa —.
  • a preferable form of W is a combination of the above-mentioned preferable R fa , Q a and R PFa .
  • a preferable range of Q 32a is as described above.
  • Compound (A12) The compound (A12) is represented by the following formula (A12).
  • R fa, Q a, R PFa, R a, L a and n1 have the same meanings as defined above
  • R 42a is a perfluoroalkylene group
  • R 43a is a single bond, an alkylene group, a group having an etheric oxygen atom or —NH— at the end of the alkylene group (excluding the end bonded to N), or a carbon of an alkylene group having 2 or more carbon atoms.
  • a group having an oxygen atom or -NH-, R 44a is an alkylene group or a group having an etheric oxygen atom or —NH— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms;
  • Two [—R 44a —SiR a n1 L a 3-n1 ] may be the same or different.
  • the compound (A12) is a compound in which, in the above formula (A1), r1 is 1, s1 is 2, and Z is —R 42a —R 43a —N [—R 44a —] 2 .
  • R 42a is preferably a perfluoroalkylene group having no branched structure. If R 42a is a perfluoroalkylene group having no branched structure, the friction resistance and lubricity of the surface layer are further improved. R 42a is typically a C 1 perfluoroalkylene group when R PFa is ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ or (CF 2 CF 2 O) m13.
  • R PFa is (CF 2 CF 2 CF 2 O) m14 , it is typically a perfluoroalkylene group having 2 carbon atoms, and R PFa is (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) is when an m15 is typically a perfluoroalkylene group linear 3 carbon atoms.
  • R 43a is —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 44a is —CH 2 CH 2 CH 2 — or —CH 2 CH 2 OCH 2 CH 2 CH 2 — (where the right side is bonded to Si from the viewpoint of ease of production of the compound (A12)). ) Is preferred. Since R 44a has a high polarity and does not have an ester bond having insufficient chemical resistance and light resistance, it has excellent initial water repellency, chemical resistance and light resistance of the surface layer. As R 44a , one having no etheric oxygen atom is particularly preferred from the viewpoint of excellent light resistance of the surface layer.
  • the two R 44a in the compound (A12) may be the same group or not the same group.
  • 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 fa —O—Q a —R PFa —.
  • a preferable form of W is a combination of the above-mentioned preferable R fa , Q a and R PFa .
  • a preferred range for R 42a is as described above.
  • Compound (A13) is represented by the following formula (A13). [R fa -OQ a -R PFa -R 51a -R 52a -O-] e1 Z 3a [-O-R 53a -SiR a n1 L a 3-n1 ] f1 (A13)
  • R fa, Q a, R PFa, R a, L a and n1 have the same meanings as defined above
  • R 51a is a linear perfluoroalkylene group
  • R 52a is an alkylene group
  • Z 3a is a (e1 + f1) -valent hydrocarbon group, or a group having 2 or more carbon atoms and a (e1 + f1) -valent group having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group
  • R 53a is an alkylene group
  • e1 is an integer of 1 or more
  • f1 is an integer greater than or equal
  • R 51a is typically —CF 2 —, for example when R PFa is ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ or (CF 2 CF 2 O) m13 , When R PFa is (CF 2 CF 2 CF 2 O) m14 , it is typically —CF 2 CF 2 —, and R PFa is (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) When it is m15 , it is typically —CF 2 CF 2 CF 2 —. If R 51a is a straight-chain compound (A13), a surface layer having excellent friction resistance and lubricity can be formed.
  • R 52a 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 fa —O—Q a —R PFa —R 51a — group includes the point that the surface layer is further excellent in water and oil repellency, durability, fingerprint stain removability, lubricity, and appearance, and the compound (A13). From the viewpoint of ease of production, the group (R f -1), the group (R f -2), or the group (R f -3) is 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 order of bonding of 2 O and m22 CF 2 CF 2 O is not limited; m25 is an integer of 1 to 100.
  • Z 3a examples include a residue obtained by removing a hydroxyl group from a polyhydric alcohol having (e1 + f1) hydroxyl groups.
  • Specific examples of Z 3a include a group of the following formula.
  • Z 3a 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 easy availability of the raw material, (Z-2) or group (Z-3) is particularly preferred.
  • R 4 is an alkyl group, preferably a methyl group or an ethyl group.
  • R 53a 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.
  • the preferable values of e1 and f1 are the same as the preferable values of r1 and r2, respectively.
  • Examples of the compound (A13) include compounds (1-1) to (1-6) shown below.
  • 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 fa —O—Q a —R PFa —.
  • a preferable form of W is a combination of the above-mentioned preferable R fa , Q a and R PFa .
  • a preferred form of R 51a is as described above.
  • ⁇ Preferred Form of Compound (B1)> As the compound (B1), at least one selected from the group consisting of the following compound (B11), compound (B12) and compound (B13) is used because the surface layer is further excellent in friction resistance and fingerprint stain removability. preferable.
  • Compound (B11) The compound (B11) is represented by the following formula (B11).
  • R fa , Q b , R PFb , R b , L b and n2 are as defined above
  • Q 32b is a fluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms
  • R 33b is a hydrogen atom or an alkyl group
  • p2 is 0 or 1
  • R 34b is a single bond, an alkylene group, or a group having an etheric oxygen atom at the end of the alkylene group (provided
  • Q 32b , R 33b , p 2, R 34b , and R 35b are the same as Q 32a , R 33a , p 1, R 34a , and R 35a in the formula (A11), respectively, and preferred embodiments are also the same.
  • Compound (B12) The compound (B12) is represented by the following formula (B12).
  • R fa , Q b , R PFb , R b , L b and n2 are as defined above
  • R 42b is a perfluoroalkylene group
  • R 43b represents a single bond, an alkylene group, a group having an etheric oxygen atom or —NH— at the end of the alkylene group (excluding the end bonded to N), or a carbon of an alkylene group having 2 or more carbon atoms.
  • a group having an oxygen atom or -NH-, R 44b is an alkylene group or a group having an etheric oxygen atom or —NH— between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms; Two [—R 44b —SiR b n2 L b 3-n2 ] may not be the same group.
  • R 42b , R 43b and R 44b are the same as R 42a , R 43a and R 44a in the formula (A12), respectively, and the preferred embodiments are also the same.
  • Compound (B13) The compound (B13) is represented by the following formula (B13). [R fb -O-Q b -R PFb -R 51b -R 52b -O-] e2 Z 3b [-O-R 53b -SiR b n2 L b 3-n2 ] f2 (B13)
  • R fa , Q b , R PFb , R b , L b and n2 are as defined above
  • R 51b is a linear perfluoroalkylene group
  • R 52b is an alkylene group
  • Z 3b is an (e2 + f2) -valent hydrocarbon group or a group having 2 or more carbon atoms and an (e2 + f2) -valent group having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group
  • R 53b is an alkylene group
  • e2 is an integer of 1 or more
  • f2 is an integer greater
  • R 51b , R 52b , Z 3b , R 53b , e 2 and f 2 are the same as R 51a , R 52a , Z 3a , R 53a , e1 and f1 in the formula (A13), respectively, and the preferred embodiments are also the same. .
  • the present composition may further contain a fluorine-containing ether compound other than the compound (A) and the compound (B).
  • 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)).
  • Examples of the compound (C) include the compound (C1).
  • a 31 and A 32 each independently represent a perfluoroalkyl group having 1 to 20 carbon atoms;
  • Q 51 represents a single bond, a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, one A group having an etheric oxygen atom at the end of a fluoroalkylene group having no branched structure containing the above hydrogen atoms (excluding the end on the side bonded to A 31 —O), containing one or more hydrogen atoms
  • R F3 is a perfluoroalkylene group having no branched structure
  • (R F3 O) m30 may be composed of two or more types of R F3 O having different carbon numbers
  • p3 is 0 when Q 51 is a single bond, and Q 51 is 1 for cases other than single bonds.
  • 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).
  • the present composition may contain impurities other than the compound (A), the compound (B) and other fluorine-containing ether compounds.
  • impurities other than the compound (A), the compound (B) and other fluorine-containing ether compounds include compounds unavoidable for the production of the compound (A), the compound (B) and other fluorine-containing ether compounds.
  • composition of this composition the content of the compound having the smaller number of carbon atoms in the R f group among the compound (A) and the compound (B) is 30 to 95 mass with respect to the total of the compound (A) and the compound (B). %, Preferably 40 to 90% by mass, particularly preferably 40 to 80% by mass. If the content of the Rf group having a smaller number of carbon atoms is within the above range, the surface layer will have excellent water droplet sliding properties.
  • the total amount of the compound (A) and the compound (B) is preferably 10% by mass or more, particularly preferably 20% by mass or more based on the total mass of the present composition.
  • An upper limit is not specifically limited, 100 mass% may be sufficient.
  • the coating liquid of the present invention includes the present composition and a liquid medium.
  • the coating liquid may be liquid, may be a solution, or may be a dispersion.
  • This coating liquid should just contain this composition, and may contain impurities, such as a by-product produced
  • the concentration of the present composition is preferably 0.001 to 50% by mass, more preferably 0.05 to 30, still more preferably 0.05 to 10 and particularly preferably 0.1 to 1% by mass in the present coating liquid. .
  • an organic solvent is preferable.
  • the organic solvent may be a fluorinated organic solvent, a non-fluorinated organic solvent, or may include both solvents.
  • fluorinated organic solvent examples include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
  • fluorinated alkane a compound having 4 to 8 carbon atoms is preferable.
  • Commercially available products include, for example, C 6 F 13 H (Asahi Glass Co., Ltd., Asahi Culin (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.
  • fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
  • 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., Asahi Clin (registered trademark) AE-3000), C 4 F 9 OCH 3 (manufactured by 3M, Novec (registered trademark) 7100), C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200), C 2 F 5 CF (OCH 3 ) C 3 F 7 (manufactured by 3M, Novec (registered trademark) 7300), etc. .
  • Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
  • fluoroalcohol examples include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
  • non-fluorine-based organic solvent a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, a hydrocarbon-based organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, Examples include ether organic solvents and ester organic solvents.
  • the coating liquid preferably contains 50 to 99.999% by mass of a liquid medium, more preferably 70 to 99.5% by mass, further preferably 90 to 99.5% by mass, and more preferably 99 to 99.99% by mass. It is particularly preferable to contain 9% by mass.
  • the present coating liquid may contain other components as long as the effects of the present invention are not impaired.
  • the other components include known additives such as an acid catalyst and a basic catalyst that promote hydrolysis and condensation reaction of the hydrolyzable silyl group.
  • the content of other components in the coating solution is preferably 10% by mass or less, and particularly preferably 1% by mass or less.
  • the solid content concentration of the coating liquid is preferably 0.001 to 50% by mass, more preferably 0.05 to 30, still more preferably 0.05 to 10, and particularly preferably 0.01 to 1% by mass.
  • 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 of the present invention has a surface layer formed from the composition on the surface of the substrate.
  • the silanol group (Si— OH) is formed, and the silanol group reacts between molecules to form a Si—O—Si bond, or the silanol group chemically reacts with a hydroxyl group (substrate—OH) on the surface of the substrate.
  • a bond (substrate-O-Si) is formed. Therefore, the surface layer contains the compound (A) and the compound (B) in a state where a part or all of the groups (I) of the compound (A) and the compound (B) are hydrolyzed.
  • L in the group (I) is a hydroxyl group
  • the above reaction proceeds without undergoing a hydrolysis reaction.
  • 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 in the present invention is not particularly limited as long as it is required to impart lubricity and water / oil repellency.
  • the material for the substrate include metals, resins, glass, sapphire, ceramics, stones, and composite materials 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.
  • the base material for touch panels, the base material for displays, and the base material for eyeglass lenses are suitable, and the base material for touch panels is especially 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.
  • glass or transparent resin is preferable.
  • the article of the present invention can be manufactured, for example, by the following method. -The method of obtaining the article
  • 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 vapor deposition method is particularly preferable from the viewpoint of suppressing decomposition of the compound (A) and the compound (B) and the simplicity of the apparatus.
  • a pellet-like substance obtained by impregnating a porous metal body such as iron or steel with the present composition or the present coating liquid may be used.
  • 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 compound (B) 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 present coating liquid contain the compound (A) and the compound (B), and the content of the compound (A) having a small number of carbon atoms in the R f group is the compound (A) and the compound (B). Since it is 30 to 95% by mass with respect to the total of (B), a surface layer excellent in water droplet sliding property can be formed.
  • Each compound (A) and compound (B), by the R f group to one end of the R PF chain is attached, the other end side based on the R PF chain (I) is present.
  • the R f group of each compound when the surface layer is formed on the substrate, the R f group of each compound is easily oriented on the side opposite to the substrate side. When the Rf group is oriented on the side opposite to the substrate side, the surface energy of the formed surface layer is lowered.
  • the number of carbon atoms of each of the R f group is different, different the R f group carbon numbers are distributed in a specific ratio on the surface of the surface layer, It is considered that a physical or physical fine uneven structure is formed. Thereby, it is considered that the water repellency of the surface of the surface layer is further increased, and the contact angle and the falling angle of the water droplet are reduced, and excellent water droplet sliding property is exhibited.
  • the present coating liquid and the article are not particularly limited.
  • display input devices such as touch panels; surface protective coats made of transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members, antifouling coats for kitchens; water and moisture repellent coats 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.
  • 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 coat, solar cell water-repellent coat, printed circuit board waterproof / water-repellent coat, waterproof / water-repellent coat for electronic equipment casings and electronic parts, transmission line insulation improvement coat, various filter waterproof / 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 sieve 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 present composition, the present coating liquid, and the article are suitably used for applications that require water drop slidability.
  • Such applications include, for example, kitchen antifouling coatings; heat exchanger water and moisture repellent and antifouling coatings and toiletry antifouling coatings; coatings for materials that require liquid repellency while conducting electrical conduction; A waterproof / sliding coat can be used.
  • 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, the group (I) or the Rf group.
  • the angle (inclination angle) between the surface of the article and the horizontal plane was set to 40 °, 50 ⁇ L of water droplets were dropped on the surface (surface layer) of the article, and the time when the water drops moved 50 mm was measured. This moving time is defined as the sliding speed.
  • Example 1 The compound (A-1) and the compound (B-1) were used and mixed at a mass ratio shown in Table 1 to prepare a composition, which was subjected to the following evaluation. However, only compound (A-1) was used in Example 1, and only compound (B-1) was used in Example 2.
  • VTR-350M vacuum deposition apparatus
  • the boat on which the composition was placed was heated at a rate of temperature rise of 10 ° C./min or less, and when the deposition rate by the quartz oscillation type film thickness meter exceeded 1 nm / second, the shutter was opened and the surface of the substrate was formed. The membrane was started.
  • the shutter was closed to finish the film formation on the surface of the substrate.
  • the substrate on which the composition was deposited was heat-treated at 120 ° C. for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.
  • ⁇ Wet coating method> Each compound or composition obtained in Examples 1 to 10 and C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200) as a liquid medium were mixed to obtain a solid content concentration of 0.05. % Coating solution was prepared. 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 120 ° C. for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.
  • compositions of Examples 3 to 9 containing the compound (A-1) and the compound (B-1), and the content of the compound (A-1) is 30 to 95% by mass based on the total of them.
  • the sliding angle was low, the sliding speed was high, and the surface layer was excellent in water droplet sliding ability.
  • the water droplet sliding property of the surface layer in Example 10 in which the content of the compound (A-1) was less than 30% by mass relative to the total of them was the same as Example 1.
  • compositions of Examples 13 to 19 including the compound (A-2) and the compound (B-2), and the content of the compound (A-2) is 30 to 90% by mass based on the total of them.
  • the sliding angle was low, the sliding speed was high, and the surface layer was excellent in water droplet sliding properties.
  • the water droplet sliding property of the surface layer in Example 20 in which the content of the compound (A-2) was less than 30% by mass relative to the total of them was the same as in Example 11.
  • the present composition and the present coating liquid can be used in various applications that require lubricity and water / oil repellency.
  • display input devices such as touch panels; surface protective coats made of transparent glass or transparent plastic parts, antifouling coats for kitchens; water and water repellent and antifouling coats for electronic devices, heat exchangers, batteries, etc.
  • Antifouling coating coating on a member that requires liquid repellency while conducting; water-repellent / waterproof / sliding coat of heat exchanger; surface sieve such as vibrating screen or inside cylinder, etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Paints Or Removers (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Lubricants (AREA)

Abstract

L'invention fournit une composition d'éther fluoré permettant de former une couche superficielle dotée d'excellentes propriétés de glissement des gouttes d'eau, un liquide de revêtement, et un article possédant une telle couche superficielle dotée d'excellentes propriétés de glissement des gouttes d'eau. Plus précisément, l'invention concerne une composition d'éther fluoré qui contient un composé éther fluoré (A) et un composé éther fluoré (B). Le composé (A) et le composé (B) possèdent chacun une chaîne poly(oxyperfluoroalkylène), un groupe perfluoroalkyle lié à une terminaison de cette chaîne, et un groupe représenté par la formule (I). Dans la combinaison dudit composé (A) et dudit composé (B) contenus dans ladite composition, le nombre d'atomes de carbone du groupe perfluoroalkyle appartenant audit composé (A), est inférieur au nombre d'atomes de carbone du groupe perfluoroalkyle appartenant audit composé (B). La teneur en composé (A) est comprise entre 30 et 95% en masse pour le total dudit composé (A) et dudit composé (B). －ＳｉＲｎＬ３－ｎ（Ｉ） L représente un groupe hydroxyle ou un groupe hydrolysable, R représente un atome d'hydrogène ou un groupe hydrocarbure monovalent, et n représente un nombre entier de 0 à 2.
PCT/JP2018/004714 2017-02-14 2018-02-09 Composition d'éther fluoré, liquide de revêtement, et article WO2018151055A1 (fr)

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CN201880005514.2A CN110114410A (zh) 2017-02-14 2018-02-09 含氟醚组合物、涂布液和物品
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JPWO2019088129A1 (ja) * 2017-10-31 2020-04-02 ダイキン工業株式会社 硬化性組成物
JPWO2019088110A1 (ja) * 2017-10-31 2020-07-02 ダイキン工業株式会社 硬化性組成物
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JPWO2019088129A1 (ja) * 2017-10-31 2020-04-02 ダイキン工業株式会社 硬化性組成物
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CN114127026B (zh) * 2019-07-18 2024-01-30 Ａｇｃ株式会社 带表面层的物品
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JP7031689B2 (ja) 2022-03-08
JP2022069480A (ja) 2022-05-11
JPWO2018151055A1 (ja) 2019-12-12
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