WO2018168497A1 - 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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Publication number
WO2018168497A1
WO2018168497A1 PCT/JP2018/007781 JP2018007781W WO2018168497A1 WO 2018168497 A1 WO2018168497 A1 WO 2018168497A1 JP 2018007781 W JP2018007781 W JP 2018007781W WO 2018168497 A1 WO2018168497 A1 WO 2018168497A1
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compound
group
fluorine
containing ether
chain
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PCT/JP2018/007781
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English (en)
Japanese (ja)
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星野　泰輝
小林　大介
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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 KR1020197022850A priority Critical patent/KR102526826B1/ko
Priority to JP2019505865A priority patent/JP6617853B2/ja
Priority to CN201880017366.6A priority patent/CN110402271B/zh
Publication of WO2018168497A1 publication Critical patent/WO2018168497A1/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
    • 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
    • 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
    • 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.
  • Fluorine-containing ether composition in which a fluorine-containing oil, that is, a non-reactive fluorine-containing ether compound having no hydrolyzable silyl group, is blended with a fluorine-containing ether compound having a hydrolyzable silyl group in order to enhance lubricity has been proposed (for example, Patent Document 1).
  • the surface layer formed of the fluorine-containing ether composition as described above tends to deteriorate in performance such as lubricity and water / oil repellency when friction with a finger or the like is repeated. It was found that (durability is low). Therefore, it is difficult to achieve both the lubricity and durability characteristics at a high level.
  • An object of the present invention is to provide a fluorine-containing ether composition and a coating liquid capable of forming a surface layer excellent in lubricity and durability, and an article having a surface layer excellent in lubricity and durability.
  • the present invention provides a fluorine-containing ether composition, a coating liquid, and an article having the following configurations [1] to [15].
  • [1] comprising a fluorinated ether compound (A) and a fluorinated ether compound (B),
  • the fluorine-containing ether compound (A) is a compound having a poly (oxyperfluoroalkylene) chain containing a (CF 2 O) unit and a group represented by the following formula (I):
  • the fluorinated ether compound (B) is a compound having a poly (oxyperfluoroalkylene) chain not containing a (CF 2 O) unit and a group represented by the formula (I) Composition.
  • 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 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), R f in the fluorine-containing ether compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF 2 O) unit, The fluorine-containing ether composition according to [1], wherein R f in the fluorine-containing ether compound (B) is a poly (oxyperfluoroalkylene) chain not containing a (CF 2 O) unit.
  • 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 oxyfluoroalkylene groups constituting may all be the same or different, R f 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), When r is 2 or more, r [R f1 —OQR f —] are the same group, 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 3 to 8.
  • the poly (oxyperfluoroalkylene) chain containing the (CF 2 O) unit is a poly (oxyperfluoroalkylene) chain containing a (CF 2 O) unit and a (CF 2 CF 2 O) unit. [1] or [2] fluorine-containing ether composition. [4]
  • the poly (oxyperfluoroalkylene) chain not containing the (CF 2 O) unit is a (CF 2 CF 2 O) unit, a (CF 2 CF 2 CF 2 O) unit, and a (CF 2 CF 2 CF 2 CF).
  • the poly (oxyperfluoroalkylene) chain not containing the (CF 2 O) unit is a poly (oxyperfluoroalkylene) chain containing a (CF 2 CF 2 OCF 2 CF 2 CF 2 O) unit.
  • the fluorine-containing ether composition according to any one of [4].
  • a fluorine-containing ether composition comprising the fluorine-containing ether compound (A1) represented by the following formula (A1) and the fluorine-containing ether compound (B1) represented by the following formula (B1).
  • R f1a and R f1b is a perfluoroalkyl group
  • 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, All of the
  • na R a and when nb is 2, nb R b may be the same or different, ra and rb are integers of 1 or more.
  • ra is 2 or more, ra [R f1a -OQ a -R fa- ] may be the same or different, and rb is 2 or when the rb pieces [R f1b -O-Q b -R fb -] may be the same or different and sa and sb is an integer of 1 or more, sa is sa number when two or more [-SiR a na L a 3- na] may be different even in the same, sb 2 or more Sometimes, the sb [-SiR b nb L b 3-nb ] may be the same or different.
  • a surface layer excellent in lubricity and durability can be formed.
  • the article of the present invention has a surface layer excellent in lubricity and durability.
  • 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 group that is a hydrolyzable group.
  • the chemical formula of the oxyperfluoroalkylene group is expressed by describing the oxygen atom on the right side of the perfluoroalkylene group.
  • the fluorinated ether composition of the present invention (hereinafter also referred to as the present composition) comprises a fluorinated ether compound (A) (hereinafter also referred to as the compound (A)) and a fluorinated ether compound (B) (hereinafter referred to as the “compound”). 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.
  • the compound (A) has a poly (oxyperfluoroalkylene) chain (hereinafter also referred to as A chain) containing a (CF 2 O) unit, and a group (I).
  • the compound (B) has a poly (oxyperfluoroalkylene) chain (hereinafter also referred to as B chain) that does not contain a (CF 2 O) unit, and a group (I). Compound (B) does not have an A chain.
  • 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 (I) possessed by each of the compound (A) and the compound (B) may be the same or different.
  • each of the compound (A) and the compound (B) can further have a group (II).
  • group (II) which each has may be the same or different.
  • R f1 -OQ- (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.
  • a chain examples of the A chain include a poly (oxyperfluoroalkylene) chain represented by the following formula (a1) and containing (CF 2 O) units and (R f2 O) units. ⁇ (CF 2 O) m1 (R f2 O) m2 ⁇ (a1)
  • R f2 is a perfluoroalkylene group having 2 or more carbon atoms
  • m1 is an integer of 1 or more
  • m2 is an integer of 0 or more
  • (m1 + m2) is an integer of 2 to 200
  • the bonding order of m1 CF 2 O and m2 R f2 O is not limited
  • When m2 is 2 or more (R f2 O) m2 may be composed of two or more types of R f2 O having different carbon numbers.
  • R f2 may be branched or linear, and is preferably linear from the viewpoint of further excellent lubricity of the surface layer.
  • the number of carbon atoms in R f2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 from the viewpoint that the durability and lubricity of the surface layer are further improved, and more preferably 2 to 4.
  • (M1 + m2) is an integer of 2 to 200. Therefore, when m1 is 1, the minimum value of m2 is 1, and there is at least one (R f2 O). When m1 is 2 or more, the minimum value of m2 is 0, and (R f2 O) may or may not exist.
  • (M1 + m2) is preferably an integer of 10 to 150, particularly preferably an integer of 20 to 100. If (m1 + m2) is not less than the lower limit of the above range, the lubricity of the surface layer is excellent. If (m1 + m2) is not more than the upper limit of the above range, the durability of the surface layer is excellent. 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 durability is lowered.
  • the ratio of m1 to m2 (m1 / m2) is preferably 100/0 to 30/70, particularly preferably 90/10 to 40/60. There exists a tendency for the lubricity of a surface layer to be excellent, so that the ratio of m1 is high within the said range.
  • each oxyperfluoroalkylene group (m1 CF 2
  • the bonding order of O and m2 Rf2O ) is not limited.
  • each oxyperfluoroalkylene group may be arranged randomly, alternately, or in blocks.
  • the (CF 2 O) unit and the (R f2 O) unit are preferably arranged at random.
  • (R f2 O) m2 may be composed of two or more types of R f2 O having different carbon numbers.
  • the binding order of m2 amino R f2 O is not limited.
  • a chain examples include the following (a2) to (a6).
  • m01 is an integer of 2 to 200
  • 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 preferred ranges of m01 and (m11 + m12) are the same as (m1 + m2).
  • the ratio of m11 to m12 (m11 / m12) is preferably 99/1 to 30/70, particularly preferably 90/10 to 40/60.
  • (a3) to (a5) are preferable, and (a3) is particularly preferable.
  • B chain examples of the B chain include a poly (oxyperfluoroalkylene) chain including at least one (R f3 O) unit represented by the following formula (b1).
  • R f3 is a perfluoroalkylene group having 2 or more carbon atoms
  • m3 is an integer from 2 to 200
  • (R f3 O) m3 may be composed of two or more types of R f2 O having different carbon numbers
  • R f3 O When m3 is composed of two or more types of R f2 O having different carbon numbers, the bonding order of each R f2 O is not limited.
  • R f3 may be branched or linear, and is preferably linear because the lubricity of the surface layer is further improved.
  • the number of carbon atoms in R f3 is preferably 2 to 6 because the durability and lubricity of the surface layer are further improved.
  • M3 is an integer of 2 to 200, preferably an integer of 10 to 150, particularly preferably an integer of 15 to 100. If m3 is not less than the lower limit of the above range, the lubricity of the surface layer is excellent. When m3 is not more than the upper limit of the above range, the durability of the surface layer is excellent. That is, when the number average molecular weight of the compound (B) is too large, the number of groups (I) present per unit molecular weight is reduced, and durability is lowered.
  • each R f3 O When m3 is composed of two or more types of R f2 O having different carbon numbers, the bonding order of each R f3 O is not limited. For example, each R f3 O may be arranged randomly, alternately, or in blocks.
  • R f3 O As the B chain when m3 is composed of two or more types of R f2 O having different carbon numbers, those represented by the following formula (b2) are preferable. ⁇ (CF 2 CF 2 O) m4 (R f4 O) m5 ⁇ (b2)
  • R f4 is a C 3-6 perfluoroalkylene group
  • m4 is an integer of 1 or more
  • m5 is an integer of 1 or more
  • (M4 + m5) is an integer of 2 to 200
  • the bonding order of m4 CF 2 CF 2 O and m5 R f4 O is not limited.
  • R f4 is preferably CF 2 CF 2 CF 2 CF 2 .
  • the preferred range of (m4 + m5) is the same as m3.
  • the ratio of m4 to m5 (m4 / m5) is preferably 90/10 to 10/90, particularly preferably 70/30 to 30/70.
  • the higher the ratio of m4 within the above range the better the lubricity.
  • ⁇ (CF 2 CF 2 O) m4 (R f4 O) m5 ⁇ , ⁇ (CF 2 CF 2 O) m41 - (R f4 O) m51 ⁇ include m6.
  • m41 is an integer of 1 to 3
  • m51 is an integer of 1 to 3
  • m6 is an integer of 1 or more
  • (m41 + m51) ⁇ m6 is an integer of 2 to 200.
  • the poly (oxyperfluoroalkylene) chain is one or more units in which 1 to 3 units of (CF 2 CF 2 O) and 1 to 3 units of (R f3 O) are connected in series.
  • ⁇ (CF 2 CF 2 O ) m41 - (R f4 O) m51 ⁇ m6 is, ⁇ (CF 2 CF 2 O ) m41 - (R f4 O) m51 ⁇ to a unit of poly (oxyperfluoroalkylene) chains can also be regarded as, it can be considered as (CF 2 CF 2 O) m41 units and (R f4 O) and m51 units are arranged in alternating poly (oxyperfluoroalkylene) chains.
  • the B chain is a poly (oxyperfluoroalkylene) containing at least one selected from a (CF 2 CF 2 O) unit, a (CF 2 CF 2 CF 2 O) unit, and a (CF 2 CF 2 CF 2 O) unit.
  • a chain is preferred.
  • a poly (oxyperfluoroalkylene) chain containing a (CF 2 CF 2 OCF 2 CF 2 CF 2 O) unit is preferable.
  • Specific examples of preferred B chain include the following (b3) to (b5).
  • (B5) is a poly (oxyperfluoroalkylene) chain comprising (CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O) units, and this poly (oxyperfluoroalkylene) chain is represented by (CF 2 CF 2 O ) Units and (CF 2 CF 2 CF 2 CF 2 O) units may be regarded as a poly (oxyperfluoroalkylene) chain formed by alternately bonding units.
  • 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.
  • 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).
  • a chlorine atom is particularly preferable.
  • 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 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).
  • 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 from the viewpoint 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) and the compound (B) are less likely to aggregate in the coating liquid, and the compound (A) and the compound (B) are less likely to aggregate during the drying process after being applied to the surface of the substrate.
  • the appearance of the surface layer is even better.
  • 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— or —CF 2 CHFCF 2 OCH 2 CF 2 O— from the viewpoint of ease of production of the compound (A) and the compound (B).
  • the number of the A chain that the compound (A) has and the number of the B chain that the compound (B) has may be one each or two or more. One to three is preferable from the viewpoint of ease of production and handling. When the compound (A) has two or more A chains, each A chain may be the same or different. When the compound (B) has two or more B chains, each B chain may be the same or different.
  • the group (I) possessed by each of the compound (A) and 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. Therefore, the group (I) possessed by each of the compound (A) and the compound (B) is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 3 to 4. When compound (A) and compound (B) have two or more groups (I), each group (I) may be the same or different. In terms of ease of production of the compound (A) and the compound (B), it is preferred that all are the same group.
  • the group (II) is bonded to one end of the A chain and the B chain. That is, it is preferable that the compound (A) further has a group (II) bonded to one end of the A chain.
  • the compound (B) preferably further has a group (II) bonded to one end of the B chain. Thereby, the lubricity of the surface layer is further improved.
  • 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 3,000 to 15,000, and particularly preferably 4,000 to 12,000. . If the number average molecular weights of the compound (A) and the compound (B) are not less than the lower limit of the above range, the lubricity of the surface layer is further improved. If the number average molecular weights of the compound (A) and the compound (B) are not less than 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) and the compound (B) are not particularly limited as long as each has the A chain or the B chain and the 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.
  • 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 compound group is a single compound except that it has a distribution in m1 and m2. Let it be a fluorine-containing ether compound.
  • At least one of the compound (A) and the compound (B) has 3 or more, more preferably 3 to 5, groups (I). If at least one has three or more groups (I), the durability of the surface layer is more excellent. When only any one has three or more groups (I), the number of the groups (I) which the other has is 1 or 2, and 2 is preferable from the viewpoint of durability.
  • both of the compound (A) and the compound (B) have 2 or more, more preferably 3 or more, and further preferably 3 to 5 groups (I). . If both have two or more groups (I), the durability of the surface layer is more excellent.
  • 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 3,000 or less, and particularly preferably 2,000 or less.
  • the surface layer is formed by the 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.
  • Examples of preferable combinations of the compound (A) and the compound (B) in the present composition include the following combinations.
  • Combination Example 1 A combination of a compound (A) having one A chain and three groups (I) and a compound (B) having one B chain and three groups (I).
  • Combination Example 2 Combination of a compound (A) having two A chains and four groups (I) and a compound (B) having two B chains and four groups (I).
  • Combination Example 3 Combination of a compound (A) having one A chain and five groups (I) and a compound (B) having one B chain and five groups (I).
  • the compound (A) preferably has a group (II) bonded to one end of the A chain.
  • the compound (B) preferably has a group (II) bonded to one end of the B chain.
  • Both the compound (A) and the compound (B) are preferably fluorine-containing ether compounds represented by the following formula (A / B).
  • R f of the compound (A) is a poly (oxyperfluoroalkylene) chain containing a (CF 2 O) unit
  • R f of the compound (B) is (CF 2 O) A poly (oxyperfluoroalkylene) chain containing no units.
  • R f1 is the R f1
  • Q is the Q
  • —SiR n L 3-n is a group represented by the formula (I).
  • Z is a (r + s) -valent linking group.
  • r is an integer of 1 or more, and is a number corresponding to the number of poly (oxyperfluoroalkylene) chains in the compounds (A) and (B).
  • s is an integer of 1 or more, and is a number corresponding to the number of groups (I) in the compound (A) and the compound (B).
  • r + s is preferably 2 to 13, more preferably 3 to 8, and particularly preferably 4 to 7.
  • Z is a linking group (r + s) value, below the Z a, include groups represented by Z b.
  • r [R f1 —OQR f —] are preferably the same group, and when s is 2 or more, s formula (I) Are preferably the same group.
  • the compound (A) is a fluorinated ether compound (A1) represented by the following formula (A1) (hereinafter also referred to as the compound (A1)), and the compound (B) is represented by the formula:
  • Examples include a fluorine-containing ether compound (B1) represented by (B1) (hereinafter also referred to as compound (B1)). That is, the composition of this aspect contains a compound (A1) and a compound (B1).
  • R f1a and R f1b is a perfluoroalkyl group
  • 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
  • All of the oxyfluoroalkylene groups constituting the fluoroalkylene group may be the same or different
  • R fa is the A chain
  • R fb is the B chain
  • Z a is a (ra + sa
  • na R a and when nb is 2, nb R b may be the same or different, ra and rb are integers of 1 or more.
  • ra is 2 or more, ra [R f1a -OQ a -R fa- ] may be the same or different, and rb is 2 or when the rb pieces [R f1b -O-Q b -R fb -] may be the same or different and sa and sb is an integer of 1 or more, sa is sa number when two or more [-SiR a na L a 3- na] may be different even in the same, sb 2 or more Sometimes, the sb [-SiR b nb L b 3-nb ] may be the same or different.
  • R f1a and R f1b is the same as R f1 of each of said in group (II), preferable embodiments thereof are also the same.
  • the ra R f1a preferably have the same carbon number, and from the viewpoint of ease of production, are the same group, that is, the group having 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 ra is 2, two R f1a are CF 3 CF 2 CF 2 — (of two R fa (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.)
  • rb is 2 or more, it is preferable that rb R f1b have the same carbon number, and from the viewpoint of ease of production, the same group, that is, the same carbon number and the same chemical structure. Is preferred.
  • Q a and Q b are the same as Q in the group (II), and preferred embodiments are also the same.
  • the A chain of R fa and the B chain of R fb 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.
  • na and nb are the same as n in the group (I), and preferred embodiments are also the same.
  • Preferred values of ra and rb are the same as the preferred numbers of the A chain of the compound (A) and the B chain of the compound (B), respectively.
  • ra and rb are each preferably an integer of 1 to 3.
  • the preferred values of s1 and s2 are the same as the preferred number of groups (I) that each of the compound (A) and the compound (B) has. That is, each of s1 and s2 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.
  • the Z a for example, (ra + sa) valent substituted or unsubstituted hydrocarbon group, the carbon of a substituted or unsubstituted hydrocarbon group - between carbon atoms and / or the terminal, the group or atom other than a hydrocarbon group And (ra + sa) -valent groups, (ra + sa) -valent organopolysiloxane groups, and the like.
  • the Z b except that the valency (rb + sb) titer include the same Z a.
  • Examples of the unsubstituted hydrocarbon group include a linear or branched saturated hydrocarbon group, an aromatic hydrocarbon cyclic group (for example, (ra + sa) from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring, or ( rb + sb) a group excluding hydrogen atoms), a group comprising a combination of a linear or branched saturated hydrocarbon group and an aromatic hydrocarbon cyclic group (for example, a substituent on the aromatic hydrocarbon cyclic group)
  • 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.
  • 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 f1a, Q a, R fa, R a, L a and na have the same meanings as defined above
  • Q 32a 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). Except for the case where the other end of the fluoroalkylene group bonded to R fa is a perfluoroalkylene group).
  • R 33a is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, pa is 0 or 1; R 34a is a single bond, an alkylene group having 1 to 6 carbon atoms, and an etheric oxygen at the end of the alkylene group (provided that the end is bonded to C [—R 34a —SiR na L 3-na ] 3 ).
  • a group having an etheric oxygen atom between carbon-carbon atoms of The three [—R 34a —SiR na L 3-na ] may be the same or different.
  • 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 32a 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 32a is typically a C 1 perfluoroalkylene group.
  • examples of Q 32a include the following groups.
  • R 34a 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 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 f1a —OQ a —R fa —.
  • a preferable form of W is a combination of the above-described preferable R f1a , Q a and R fa .
  • a preferable range of Q 32a is as described above.
  • Compound (A12) The compound (A12) is represented by the following formula (A12).
  • R f1a, Q a, R fa, R a, L a and na have the same meanings as defined above
  • R 42a is a C 1-6 perfluoroalkylene group
  • R 43a is 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)
  • the compound (A12) is a compound in which ra is 1, sa is 2, and Z a is —R 42a —R 43a —N [—R 44a —] 2 in the above formula (A1).
  • R 42a 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 42a is typically a C 1 perfluoroalkylene group when R fa is ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ .
  • 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 — and —CH 2 CH 2 OCH 2 CH 2 CH 2 — (provided that 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. Two R 44a in the compound (A12) may be the same or different.
  • 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 f1a —OQ a —R fa —.
  • a preferable form of W is a combination of the above-described preferable R f1a , Q a and R fa .
  • a preferred range for R 42a is as described above.
  • Compound (A13) is represented by the following formula (A13). [R f1a -OQ a -R fa -R 51a -R 52a -O-] ea Z 3a [-O-R 53a -SiR a na L 3-na ] fa (A13)
  • R f1a, Q a, R fa, R a, L a and na have the same meanings as defined above
  • R 51a is a C 1-6 perfluoroalkylene group
  • R 52a is an alkylene group having 1 to 6 carbon atoms
  • Z 3a is a (ea + fa) -valent hydrocarbon group, or a group having 2 or more carbon atoms and a (ea + fa) -valent group having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group
  • R 53a is an alkylene group having 1 to 20 carbon atoms
  • Ea is preferably an integer of 1 to 3.
  • fa 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.
  • R 51a is —CF 2 — when, for example, R fa is ⁇ (CF 2 O) m11 (CF 2 CF 2 O) m12 ⁇ .
  • R 51a is preferably linear. If R 51a is a straight-chain compound (A13), a surface layer that is superior in 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).
  • R f1a —O—Q a —R fa —R 51a — is a group having excellent water and oil repellency, durability, fingerprint stain removability, lubricity, and appearance as well as the compound (A13). From the viewpoint of ease of production, 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 3a includes a residue obtained by removing a hydroxyl group from a polyhydric alcohol having (ea + fa) 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) 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 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.
  • Examples of the compound (A13) include compounds (A13-1) to (A13-6) represented by the following formulas.
  • 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 f1a —OQ a —R fa —.
  • a preferable form of W is a combination of the above-described preferable R f1a , Q a and R fa .
  • a preferred form of R 51a is as described above.
  • Compound (B11) The compound (B11) is represented by the following formula (B11).
  • R f1b , Q b , R fb , R b , L b and nb are each as defined above
  • Q 32b 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 33b is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, pb is 0 or 1, R 34b is a single bond, an alkylene group having 1 to 6 carbon atoms, and an etheric oxygen at the terminal of the alkylene group (however, the terminal of the side bonded to C [—R 34b —SiR nb L 3-nb ] 3 ).
  • a group having an atom, a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 6 carbon atoms, or a terminal of an alkylene group having 2 to 6 carbon atoms (provided that C [—R 34b —SiR nb L 3-nb ] 3 and the terminal having a etheric oxygen atom between carbon-carbon atoms.
  • R 35b represents an alkylene group having 1 to 6 carbon atoms, a group having an etheric oxygen atom at the terminal of the alkylene group (excluding the terminal bonded to Si), or an alkylene group having 2 to 6 carbon atoms
  • a group having an etheric oxygen atom between carbon-carbon atoms of The three [—R 34b —SiR nb L 3-nb ] may be the same or different.
  • the group having an etheric oxygen atom between the carbon-carbon atoms of the fluoroalkylene group and the fluoroalkylene group in Q 32b is respectively the carbon-carbon atom of the fluoroalkylene group and the fluoroalkylene group in Q 32a in the formula (A11) The same as the group having an etheric oxygen atom.
  • the number of (CF 2 O) in Q 32b is preferably 0 to 3.
  • Q 32b is typically a C 1 perfluoroalkylene group when p 1 is 0 and R fb is (CF 2 CF 2 O) m 13.
  • R fb is (CF 2 CF 2 CF 2 O) m14, it is typically a C 2 perfluoroalkylene group.
  • R fb is (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) m15, it is typically a linear perfluoroalkylene group having 3 carbon atoms.
  • R 33b , pb, R 34b and R 35b are the same as R 33a , pa, 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 f1b , Q b , R fb , R b , L b and nb are each as defined above
  • R 42a is a C 1-6 perfluoroalkylene group
  • R 43a is 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)
  • the compound (B12) is a compound in which rb is 1, sb is 2, and Z b is —R 42b —R 43b —N [—R 44b —] 2 in the above formula (B1).
  • R 42b , R 43b and R 44b are the same as R 42a , R 43a and R 44a in the formula (A12), respectively.
  • R 42b is typically a C 1 perfluoroalkylene group when R fb is (CF 2 CF 2 O) m 13.
  • R fb is (CF 2 CF 2 CF 2 O) m14, it is typically a C 2 perfluoroalkylene group.
  • R fb is (CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) m15, it is typically a linear perfluoroalkylene group having 3 carbon atoms.
  • Compound (B13) The compound (B13) is represented by the following formula (B13). [R f1b -OQ b -R fb -R 51b -R 52b -O-] eb Z 3b [-O-R 53b -SiR b nb L b 3-nb ] f (B13)
  • R f1b , Q b , R fb , R b , L b and nb are each as defined above
  • R 51b is a C 1-6 perfluoroalkylene group
  • R 52b is an alkylene group having 1 to 6 carbon atoms
  • Z 3b is an (eb + fb) -valent hydrocarbon group or a group having 2 or more carbon atoms and an (eb + fb) -valent group having at least one etheric oxygen atom between the carbon atom and the carbon atom of the hydrocarbon group
  • R 53b is an alkylene group having 1 to 20
  • R 51b , R 52b , Z 3b , R 53b , eb, and fb are the same as R 51a , R 52a , Z 3a , R 53a , ea, and fa in the formula (A13), respectively.
  • the R f1b —O—Q b —R fb —R 51b —R 52b — group includes a compound and a compound that are superior in terms of water / oil repellency, durability, fingerprint stain removability, lubricity, and appearance of the surface layer ( From the viewpoint of ease of production of B13), the group (R f -3) is preferred.
  • R f11 O (CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O) m25 CF 2 CF 2 OCF 2 CF 2 CF 2 ⁇ (R f ⁇ 3)
  • R f11 is a linear perfluoroalkyl group with 1 to 20 carbon atoms
  • m25 is an integer of 1 to 100.
  • This composition may consist of a compound (A) and a compound (B), and may further contain other fluorine-containing ether compounds other than a compound (A) and a 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)).
  • the poly (oxyperfluoroalkylene) chain may be an A chain or a B 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).
  • 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 (A) relative to the total of the compound (A) and the compound (B) (mass ratio of the compound (A) / [compound (A) + compound (B)]) is 10 to 80 % By mass is preferable, and 20 to 50% by mass is particularly preferable.
  • the higher the content of the compound (A) within the above range the more excellent the lubricity of the surface layer.
  • the lower the content of the compound (A) within the above range that is, the higher the content of the compound (B) relative to the total of the compound (A) and the compound (B)), the more excellent the durability of the surface layer.
  • the total amount of the compound (A) and the compound (B) is preferably 50% by mass or more, particularly preferably 80% 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% by mass, and 0.1 to 1% by mass in the present coating liquid. Particularly preferred.
  • 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 present coating liquid is preferably 0.001 to 50% by mass, more preferably 0.05 to 30%, further preferably 0.05 to 10% by mass, 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 touchscreens, the base material for displays, and a spectacles lens are suitable, and the base material for touchscreens 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 and transparent resin are 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), a surface layer excellent in lubricity and durability can be formed. That is, by forming a surface layer on the surface of the substrate using the present composition or the present coating liquid, excellent initial lubricity, water and oil repellency, and the like are imparted, and the surface is repeatedly formed. Even when rubbed, excellent durability is obtained in which the characteristics are not easily lowered. Further, even if the surface is repeatedly rubbed, the water / oil repellency is unlikely to be lowered, so that the performance of removing fingerprint stains on the surface of the substrate (fingerprint stain removability) can be obtained.
  • the compound (A) contains a (CF 2 O) unit in the A chain, it has excellent lubricity. On the other hand, it is inferior in durability compared with the case where no (CF 2 O) unit is included. Since the compound (B) does not contain a (CF 2 O) unit in the B chain, it is excellent in durability. On the other hand, it is inferior in lubricity compared with the case where a (CF 2 O) unit is included. When these are combined, each excellent characteristic is sufficiently maintained, and both excellent lubricity and durability can be achieved. The reason for this is considered that the durability of the highly durable component (compound (B)) is further enhanced by dispersing the force applied to wear with the highly lubricious component (compound (A)).
  • the base material having a surface layer obtained in this manner is suitable as a member constituting the touch panel.
  • the use of the present composition, the present coating liquid and the article is not limited to the touch panel.
  • display input devices other than touch panels surface protective coats made of transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members, antifouling coats for kitchens; water-repellent moisture-proof 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 coating, water-repellent coating for solar cells, waterproof / water-repellent coating for printed wiring boards, waterproof / water-repellent coating for electronic equipment casings and electronic parts, insulation improvement coating for power transmission lines, various filters Water repellent coat, waterproof coat of radio wave absorber and sound absorbing material, bath, kitchen equipment, antifouling coat for toiletries, water repellent / waterproof / slidable coat of heat exchanger, vibration Low surface friction coating Rui and the cylinder interior and the like, mechanical parts, vacuum equipment parts, bearing parts, automobile parts, surface protection coating such as a tool and the like.
  • the 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).
  • the contact angle (water contact angle) of about 2 ⁇ L of distilled water placed on the surface of the surface layer was measured at 20 ° C. using a contact angle measuring device (DM-701, manufactured by Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface of the surface layer, and the average value was calculated. The 2 ⁇ method was used to calculate the contact angle. The greater the water contact angle, the better the water repellency.
  • A-1) Composition (A-1) obtained in Production Example A-1 described later.
  • A-2) Composition (A-2) obtained in Production Example A-2 described later.
  • A-3) Compound (A-3) obtained in Production Example A-3 described later.
  • A-4) Compound (A-4) obtained in Production Example A-4 described later.
  • A-5) Compound (A-5) obtained in Production Example A-5 described later.
  • Table 1 shows the number (hereinafter also referred to as PEPE number), the number of groups (I), and the number average molecular weight (Mn).
  • the repeating unit “(CF 2 O) (CF 2 CF 2 O)” in (A-1) to (A-5) and (C-1) is a (CF 2 O) unit and a (CF 2 CF 2 ) unit.
  • O) represents a poly (oxyperfluoroalkylene) chain randomly arranged.
  • a cooler kept at 20 ° C., a NaF pellet packed bed and a cooler kept at 0 ° C. were installed in series.
  • a liquid return line for returning the liquid aggregated from the cooler maintained at 0 ° C. to the autoclave was installed.
  • 750 g of ClCF 2 CFClCF 2 OCF 2 CF 2 Cl (hereinafter also referred to as CFE-419) was placed in the autoclave and stirred while maintaining at 25 ° C. After nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown in at 25 ° C. and a flow rate of 2.0 L / hour for 1 hour.
  • the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 0.2 ⁇ m to obtain 6.4 g of compound (A-4) in which five allyl groups of compound (18) were hydrosilylated.
  • the conversion rate of hydrosilylation was 100%, and the compound (18) did not remain.
  • the selectivity for hydrosilylation was 100%.
  • the compound (A-4) is a compound in which WR 51a -in the compound (A13-3) is a group represented by the formula (R f -1).
  • compound (A-5) in which four allyl groups of compound (20) were hydrosilylated was used. 6.4 g was obtained.
  • the compound (A-5) is a compound in which WR 51a -in the compound (A13-4) is a group represented by the formula (R f -1).
  • the compound (11) was changed to the compound (23), the amount of the platinum complex solution was changed to 0.029 g, and the amount of HSi (OCH 3 ) 3 was changed to 1.2 g.
  • the conversion rate of hydrosilylation was 100%, and the compound (23) did not remain.
  • the selectivity for hydrosilylation was 80%.
  • Compound (13) is 6.0 g of Compound (26), the amount of platinum complex solution is 0.07 g, the amount of HSi (OCH 3 ) 3 is 0.78 g, the amount of dimethyl sulfoxide is 0.02 g, 6.7 g of compound (B-3) was obtained in the same manner as in Production Example A-3 except that the amount of 1,3-bis (trifluoromethyl) benzene (Tokyo Chemical Industry Co., Ltd.) was changed to 0.49 g. Yield 100%).
  • compound (B-4) in which five allyl groups of compound (28) were hydrosilylated was used. 6.3 g was obtained.
  • the compound (B-4) is a compound in which WR 51a -of the compound (A13-3) is a group represented by the formula (R f -3).
  • Example 1 A composition was prepared by mixing 50 parts by mass of (A-1) and 50 parts by mass of (B-1). Using this composition, the surface treatment of the substrate was performed by the following dry coating method to obtain the article of Example 1. Chemically tempered glass was used as the substrate. The obtained article was evaluated for durability 1 (the number of times the contact angle was maintained at 100 ° or more), lubricity and durability 2 (hardness to decrease the dynamic friction coefficient). The results are shown in Tables 3-5.
  • Dry coating was performed using a vacuum deposition apparatus (Showa Vacuum Co., SGC-22WA) (vacuum deposition method). 35 mg of the composition was filled in a molybdenum boat in a vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was evacuated to 5 ⁇ 10 ⁇ 3 Pa or less. The boat in which the composition was placed was heated to deposit the composition on the surface of the substrate, thereby forming a deposited film on the surface of the substrate. The substrate on which the deposited film was formed was left overnight under conditions of temperature: 25 ° C. and humidity: 40% to obtain an article having a surface layer on the surface of the substrate.
  • Examples 2 to 40 Except having changed the kind and combination of the compound to be used as shown in Table 2, the composition was prepared in the same manner as in Example 1, the surface layer was formed to obtain the article, and the obtained article was evaluated. It was. In the example in which two compounds are combined, the mass ratio of each compound is 50:50. The results are shown in Tables 3-5.
  • compositions of Examples 1 to 5, 7 to 11, 13 to 17, 19 to 23, and 25 to 29 in which the compound (A) and the compound (B) are combined do not have the compound (B) and the group (I).
  • the durability and lubricity were excellent. Further, it was superior in lubricity as compared with Examples 31 to 35 in which the compound (B) was used alone. Moreover, the tendency for durability to improve was seen as the number of group (I) which each of a compound (A) and a compound (B) has increased.
  • Examples 41-50 A composition was prepared in the same manner as in Example 15 except that the mixing ratio (mass ratio) of (A-3) and (B-3) was as shown in Table 6, and the substrate was prepared by the dry coating method. The surface layer was formed to obtain an article, and the obtained article was evaluated. The results are shown in Table 6. Moreover, the surface treatment of the base material was performed by the following wet coating method using each composition to obtain an article. Chemically tempered glass was used as the substrate. The obtained article was evaluated for durability 1 and lubricity. The results are shown in Table 7.
  • Examples 51-60 A composition was prepared in the same manner as in Example 22 except that the mixing ratio (mass ratio) of (A-4) and (B-4) was as shown in Table 8, and the substrate was prepared by the dry coating method. The surface layer was formed to obtain an article, and the obtained article was evaluated. The results are shown in Table 8.
  • both properties of lubricity and durability could be achieved at a higher level than when each compound was used alone.
  • the durability and lubricity were particularly excellent when the mass ratio of the compound (A) / compound (B) was in the range of 20/80 to 50/50.
  • 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.

Abstract

L'invention concerne une composition d'éther fluoré et un liquide de revêtement qui peuvent former une couche de surface ayant un excellent pouvoir lubrifiant et une excellente durabilité, et un article ayant une couche de surface ayant un excellent pouvoir lubrifiant et une excellente durabilité. Cette composition d'éther fluoré contient un composé éther fluoré (A) et un composé éther fluoré (B), le composé éther fluoré (A) ayant une chaîne poly (oxyperfluoroalkylène) contenant une unité (CF2O, et un groupe représenté par la formule (I), et le composé éther fluoré (B) ayant une chaîne poly (oxyperfluoroalkylène) ne contenant pas une unité (CF2O), et ayant un groupe représenté par la formule (I). Formule (I) :-SiRnL3-n, dans laquelle L représente un groupe hydroxy ou un groupe hydrolysable, et R représente un atome d'hydrogène ou un groupe hydrocarboné monovalent.
PCT/JP2018/007781 2017-03-15 2018-03-01 Composition d'éther fluoré, liquide de revêtement et article WO2018168497A1 (fr)

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JP2020200407A (ja) * 2019-06-11 2020-12-17 日本ペイント・サーフケミカルズ株式会社 親水化処理剤および親水皮膜の形成方法
WO2023085373A1 (fr) * 2021-11-12 2023-05-19 Ａｇｃ株式会社 Composition, agent de traitement de surface, liquide de revêtement, article et procédé de production d'un article
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JP6617853B2 (ja) * 2017-03-15 2019-12-11 Ａｇｃ株式会社 含フッ素エーテル組成物、コーティング液および物品
JPWO2021182166A1 (fr) * 2020-03-09 2021-09-16
KR20240044454A (ko) 2021-08-05 2024-04-04 신에쓰 가가꾸 고교 가부시끼가이샤 발수발유 표면층을 갖는 물품
KR20240042469A (ko) 2021-08-05 2024-04-02 신에쓰 가가꾸 고교 가부시끼가이샤 발수발유 표면층을 갖는 물품

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JP6617853B2 (ja) 2019-12-11

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