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  • 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
  • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
  • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
• • 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
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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  • 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
  • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
  • C08G65/3342—Polymers modified by chemical after-treatment with organic compounds containing sulfur having sulfur bound to carbon and hydrogen
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  • 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
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  • 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
  • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/60—Deposition of organic layers from vapour phase
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2202/00—Metallic substrate
  • B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
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  • B05D2202/00—Metallic substrate
  • B05D2202/40—Metallic substrate based on other transition elements
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  • B05D2203/00—Other substrates
  • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
  • B05D2203/35—Glass
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  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2350/00—Pretreatment of the substrate
  • B05D2350/60—Adding a layer before coating
  • B05D2350/63—Adding a layer before coating ceramic layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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  • B05D2506/00—Halogenated polymers
  • B05D2506/10—Fluorinated polymers
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  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
  • B05D3/0493—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases using vacuum

Definitions

• the present invention relates to a fluorine-containing ether compound, a composition, and an article with a water-repellent oil-repellent layer.
• Fluorine-containing poly (oxyperfluoroalkylene) chain and reactive silyl group to impart water and oil repellency, fingerprint stain removal, lubricity (smoothness when touched by fingers), etc. to the surface of the base material. It is known that a water- and oil-repellent layer made of a condensate of a fluorine-containing compound is formed on the surface of a base material by surface treatment using a compound.
• Patent Document 1 discloses that a silicon oxide layer is provided between a base material and a water-repellent oil-repellent layer.
• the present invention presents a fluorine-containing ether compound, a composition, and a water-repellent ether compound capable of forming a water- and oil-repellent layer having excellent abrasion resistance on the metal surface of a base material having a metal surface containing a metal such as gold, silver, and copper.
• the subject is to provide an article with an oil repellent layer.
• [R f - (OX) m -O-] j1 Y 1 -Z 1 [-L 1 -S-R 11] g11
• R f is a perfluoroalkyl group and X is a fluoroalkylene group having one or more fluorine atoms.
• m is an integer greater than or equal to 2
• Y 1 is a single bond or (j1 + 1) valence linking group.
• Z 1 is a (g11 + g12 + 1) valence linking group.
• L 1 is a single bond or divalent linking group.
• R 11 is a hydrogen atom or a monovalent substituent and R 12 is a monovalent substituent and j1 is an integer greater than or equal to 1 and g11 is an integer of 2 or more, g12 is an integer greater than or equal to 0.
• j1 is an integer greater than or equal to 1 and g11 is an integer of 2 or more, g12 is an integer greater than or equal to 0.
• R 21 and R 24 are independently monovalent substituents, respectively.
• R 22 and R 23 are independently hydrogen atoms or monovalent substituents, respectively.
• L 21 and L 22 are independently single-bonded or divalent linking groups, respectively.
• Z 21 is a (g21 + g22 + 1) valence linking group.
• Z 22 is a (g23 + g24 + 1) valence linking group.
• Y 21 and Y 22 are independently single-bonded or divalent linking groups, respectively.
• X is a fluoroalkylene group having one or more fluorine atoms.
• m is an integer greater than or equal to 2 g21 and g24 are independently integers greater than or equal to 0, respectively.
• g22 and g23 are independently integers of 2 or more. However, neither Y 21 nor Y 22 contains two or more ester bonds.
• [5] A composition comprising the fluorine-containing ether compound according to any one of [1] to [4] and a liquid medium.
• [6] A water- and oil-repellent agent comprising the fluorine-containing ether compound according to any one of [1] to [4] or the composition of [5].
• [7] The water- and oil-repellent repellent of [6] for forming a water- and oil-repellent layer on the metal surface of a base material having a metal surface.
• the water- and oil-repellent agent according to [7] wherein the metal surface is a metal surface containing at least one metal selected from the group consisting of gold, silver and copper.
• the surface of the base material is treated by a dry coating method using the fluorine-containing ether compound according to any one of [1] to [4] to form a water- and oil-repellent layer on the surface of the base material.
• a method for manufacturing a base material with a water- and oil-repellent layer [10] The composition is applied to the surface of a base material by a wet coating method using the composition of [5] and dried to form a water-repellent and oil-repellent layer on the surface of the base material.
• a method for manufacturing a base material with a water-repellent layer is a dry coating method using the fluorine-containing ether compound according to any one of [1] to [4] to form a water- and oil-repellent layer on the surface of the base material.
• a fluorine-containing ether compound capable of forming a water-repellent oil-repellent layer having excellent abrasion resistance on the metal surface of a base material having a metal surface, a composition containing the fluorine-containing ether compound, and a water-repellent oil-repellent layer are provided.
• the compound represented by the formula (1-1) is referred to as a compound (1-1).
• Compounds represented by other formulas are also described in the same manner.
• the group represented by the formula (g1-1) is referred to as a group (g1-1).
• the groups represented by other formulas are also described in the same manner.
• the alkylene group may have an A group
• the alkylene group may have an A group between carbon atoms in the alkylene group, or the alkylene group-. It may have an A group at the end, such as A group.
• the "linking group” is treated as a “linking group” not only as an aggregate of atoms but also as an atom itself if it has a function of linking predetermined groups.
• the nitrogen atom itself is treated as a trivalent linking group.
• the meanings of the terms in the present invention are as follows.
• the "number average molecular weight" (Mn) of a compound is calculated by determining the number (average value) of oxyfluoroalkylene groups with respect to the terminal group by 1 H-NMR and 19 F-NMR.
• the fluorine-containing ether compound of the first embodiment of the present invention is a compound represented by the formula (1-1) described later (compound (1-1)) and has a thiol structure or a thioether structure.
• compound (1-1) a compound represented by the formula (1-1) described later
• compound (1-1) has a thiol structure or a thioether structure.
• the present inventors have found that when a water-repellent oil-repellent layer is formed on a substrate containing gold, silver or copper using compound (1-1), the water-repellent oil-repellent layer is excellent in abrasion resistance. The details of this reason have not been clarified, but it is presumed to be due to the following reasons.
• compound (1-1) has a thiol structure, it is considered that the thiol structure portion forms a bond with gold, silver, or copper contained in the substrate.
• compound (1-1) has a thioether structure
• the thioether structure portion interacts with gold, silver, or copper contained in the base material.
• the adhesion between the water-repellent oil-repellent layer and the base material is improved, and it is presumed that a water-repellent oil-repellent layer having excellent abrasion resistance was obtained.
• Compound (1-1) is a fluorine-containing ether compound represented by the formula (1-1). [R f - (OX) m -O-] j1 Y 1 -Z 1 [-L 1 -S-R 11] g11 [R 12] g12 (1-1)
• R f is a perfluoroalkyl group.
• the number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 3, from the viewpoint of more excellent abrasion resistance of the water- and oil-repellent layer.
• the perfluoroalkyl group may be linear, branched or cyclic.
• Perfluoroalkyl groups include CF 3- , CF 3 CF 2- , CF 3 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 CF 2- , CF 3 CF (CF 3 )-and the like can be mentioned.
• (OX) m is a poly (oxyfluoroalkylene) chain.
• X is a fluoroalkylene group having one or more fluorine atoms.
• the number of carbon atoms of the fluoroalkylene group is preferably 1 to 6 and particularly preferably 2 to 4 from the viewpoint of more excellent weather resistance and corrosion resistance of the water- and oil-repellent layer.
• the fluoroalkylene group may be linear, branched or cyclic.
• the fluoroalkylene group preferably has 1 or more fluorine atoms, and the water- and oil-repellent layer is more excellent in corrosion resistance. Therefore, 2 to 10 groups are preferable, and 2 to 4 groups are particularly preferable.
• As the fluoroalkylene group a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group) is preferable.
• (OX) is, -OCHF -, - OCF 2 CHF -, - OCHFCF 2 -, - OCF 2 CH 2 -, - OCH 2 CF 2 -, - OCF 2 CF 2 CHF -, - OCHFCF 2 CF 2- , -OCF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2- , -OCF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2 CF 2- , -OCF 2 CF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2 CF 2- , -OCF 2 CF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2 CF 2 CF 2- , -OCF 2 CF 2 CF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2 CF 2 CF 2- , -OCF 2 CF 2 CF 2 CF 2 CH 2- , -
• -cycloC 4 F 6- means a perfluorocyclobutane diyl group, and specific examples thereof include a perfluorocyclobutane-1,2-diyl group.
• -CycloC 6 F 10- means a perfluorocyclohexanediyl group, and specific examples thereof include a perfluorocyclohexane-1,4-diyl group.
• m is an integer of 2 or more, preferably 2 to 200, more preferably 5 to 150, particularly preferably 5 to 100, and most preferably 10 to 50.
• (OX) m may contain only one type of (OX), or may contain two or more types of (OX).
• the binding order of two or more types of (OX) is not limited, and may be randomly, alternately, or arranged in blocks. Including two or more kinds of (OX) means that two or more kinds of (OX) having different carbon atoms are present in the compound (1-1), and two or more kinds of (OX) having different hydrogen atom numbers are included.
• m25 is a m25 amino (OCF 2 CF 2) and m25 amino (OCF 2 CF 2 CF 2 CF 2) Indicates that they are arranged alternately.
• (OX) m is [(OCH ma F (2-ma) ) m11 ⁇ (OC 2 H mb F (4-mb) ) m12 ⁇ (OC 3 H mc F (6-mc) ) m13 ⁇ (OC) 4 H md F (8-md) ) m14 ⁇ (OC 5 H me F (10-me) ) m15 ⁇ (OC 6 H mf F (12-mf) ) m16 ⁇ (O-cycloC 4 H mg F (6) -Mg) ) m17 ⁇ (O-cycloC 6 H mh F (10-mh) ) m18 ] is preferable.
• -cycloC 4 H mg F (6- mg) represents a fluorocyclobutane diyl group, and a fluorocyclobutane-1,2-diyl group is preferable.
• -CycloC 6 H mh F (10-mh) represents a fluorocyclohexanediyl group, preferably a fluorocyclohexane-1,4-diyl group.
• ma is 0 or 1
• mb is an integer of 0 to 3
• mc is an integer of 0 to 5
• md is an integer of 0 to 7
• me is an integer of 0 to 9
• mf is an integer of 0 to 9.
• m11, m12, m13, m14, m15, m16, m17 and m18 are each independently an integer of 0 or more, preferably 100 or less.
• m11 + m12 + m13 + m14 + m15 + m16 + m17 + m18 are integers of 2 or more, preferably 2 to 200, more preferably 5 to 150, particularly preferably 5 to 100, and most preferably 10 to 50.
• m12 is preferably 2 or more, and particularly preferably 2 to 200.
• C 3 H mc F (6-mc) , C 4 H md F (8-md) , C 5 H me F (10-me) and C 6 H mf F (12-mf) are linear. However, it may have a branched chain shape, and a linear shape is preferable from the viewpoint of more excellent friction resistance of the water-repellent oil-repellent layer.
• m11 (OCH ma F (2-ma) ), m12 (OC 2 H mb F (4-mb) ), m13 (OC 3 H mc F (6-mc) ), m14 (OC 4 H md F (8-md) ), m15 (OC 5 H me F (10-me) ), m16 (OC 6 H mf F (12-mf) ), m17 ( The binding order of O-cycloC 4 H mg F (6- mg) ) and m18 (O-cycloC 6 H mh F (10-mh) ) is not limited. When m11 is 2 or more, a plurality of (OCH ma F (2-ma) ) may be different.
• a plurality of (OC 2 H mb F (4-mb) ) may be different.
• a plurality of (OC 3 H mc F (6-mc) ) may be different.
• a plurality of (OC 4 H md F (8-md) ) may be different.
• m15 is 2 or more, a plurality of (OC 5 H me F (10-me) ) may be different.
• a plurality of (OC 6 H mf F (12-mf) ) may be different.
• a plurality of (O-cycloC 4 H mg F (6- mg) ) may be different.
• a plurality of (O-cycloC 6 H mh F (10-mh) ) may be different.
• (OX) m preferably has the following structure. ⁇ (OCF 2) m21 ⁇ ( OCF 2 CF 2) m22 ⁇ , (OCF 2 CF 2 ) m23 , (OCF 2 CF 2 CF 2 ) m24 , (OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2) m25, ⁇ (OCF 2 CF 2 CF 2 CF 2 ) m26 ⁇ (OCF 2 ) m27 ⁇ , ⁇ (OCF 2 CF 2 CF 2 CF 2 CF 2 ) m26 ⁇ (OCF 2 CF 2 ) m27 ⁇ , ⁇ (OCF 2 CF 2 CF 2 CF 2 CF 2 ) m26 ⁇ (OCF 2 ) m27 ⁇ , ⁇ (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) m26 ⁇ (OCF 2 ) m27 ⁇ , ⁇ (OCF 2 CF 2 CF
• m21 is an integer of 1 or more
• m22 is an integer of 1 or more
• m21 + m22 is an integer of 2 to 500
• m23 and m24 are independently integers of 2 to 500
• m25 is 1 It is an integer of ⁇ 250
• m26 and m27 are each independently an integer of 1 or more
• m26 + m27 is an integer of 2 to 500
• m28 is an integer of 1 to 250.
• (OX) m is more preferably having the following structure from the viewpoint that compound (1-1) can be easily produced.
• the numbers of m22, m25 and m28 are selected so as to be an integer of 1 or more.
• (OX) m is, ⁇ (OCF 2) m21 ⁇ (OCF 2 CF 2) m22 ⁇ is preferably.
• ⁇ (OCF 2) m21 ⁇ ( OCF 2 CF 2) m22 ⁇ as the m22 / m21, from the viewpoint of abrasion resistance of the water- and oil-repellent layer and fingerprint stain removal properties more excellent, preferably 0.1 to 10, 0.2 to 5.0 is more preferable, 0.2 to 2.0 is further preferable, 0.2 to 1.5 is particularly preferable, and 0.2 to 0.85 is most preferable.
• Y 1 is a single bond or (j1 + 1) valent linking group. As will be described later, 1 is preferable as j1, and when j1 is 1, Y 1 represents a divalent linking group.
• Specific examples of the (j1 + 1) -valent linking group include -C (O) NR 6- , -C (O)-, between carbon-carbon atoms in a hydrocarbon group and a hydrocarbon group having 2 or more carbon atoms. Examples thereof include groups having -NR 6- , -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O- or -SO 2 NR 6-.
• R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
• the hydrocarbon group an aliphatic hydrocarbon group (which may be saturated or unsaturated) and an aromatic hydrocarbon group are preferable, an aliphatic hydrocarbon group is more preferable, and an alkylene group is particularly preferable. ..
• the aliphatic hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
• the hydrocarbon group preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
• the join order is not particularly limited, for example, Y 1 is carbon in the hydrocarbon group having 2 or more carbon atoms - having - -C (O) NR 6 between carbon atoms is a group, -C (O) NR 6 - carbon atoms may be bonded to Z 1 side of formula 1-1, -C (O) NR 6 - nitrogen atom of formula 1-1 It may be coupled to the Z 1 side.
• Z 1 is a (g11 + g12 + 1) valence linking group.
• the (g11 + g12 + 1) valent linking group a trivalent to hexavalent linking group is preferable, and a trivalent linking group or a tetravalent linking group is preferable.
• Specific examples of the (g11 + g12 + 1) valent linking group include a carbon atom, a nitrogen atom, a silicon atom, a ring having at least one of a nitrogen atom or a carbon atom (for example, an isocyanurate ring), an organopolysiloxane residue, and a substitution.
• hydrocarbon group having two or more carbon atoms which may have a group (preferably a halogen atom) and a hydrocarbon group having two or more carbon atoms which may have a substituent (preferably a halogen atom).
• the group represented by 3-i3 (* 1 represents the bonding position with L 1 in the formula (1-1)
• * 2 represents the bonding position with R 12 in the formula (1-1).
• i3 is an integer of 1 to 3).
• R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
• the hydrocarbon group an aliphatic hydrocarbon group (which may be saturated or unsaturated) and an aromatic hydrocarbon group are preferable, an aliphatic hydrocarbon group is more preferable, and an alkylene group is particularly preferable. ..
• the aliphatic hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
• the hydrocarbon group preferably has 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms.
• L 1 is a single bond or divalent linking group.
• the divalent linking group include an alkylene group and a phenylene group.
• the alkylene group has 2 or more carbon atoms
• the alkylene group has -C (O) NR 6- , -C (O)-, -NR 6- , -O- or -S- between carbon-carbon atoms. May have.
• R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
• Carbon atom of the phenylene group may be bonded with -S- (i.e., a group L 1 is represented by -C 6 H 4 -S-, sulfur atom is bonded to Z 1.) ..
• the alkylene group may be linear, branched or cyclic, and is preferably linear or branched.
• the alkylene group preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and particularly preferably 3 to 10 carbon atoms.
• R 11 is a hydrogen atom or a monovalent substituent.
• the monovalent substituent in R 11 include an alkyl group, a group in which the hydrogen atom of the alkyl group is represented by ⁇ Si (R) n L 3-n , a group substituted with a carboxy group or a hydroxyl group, or a group substituted with a carboxy group or a hydroxyl group.
• a group in which the carbon atom of the alkyl group is substituted with a carbonyl group can be mentioned.
• the alkyl group may be linear, branched or cyclic.
• the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
• L is a hydrolyzable group or a hydroxyl group.
• L which is a hydrolyzable group, include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO).
• alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable.
• aryloxy group an aryloxy group having 3 to 10 carbon atoms is preferable.
• the halogen atom a chlorine atom is preferable.
• the acyl group an acyl group having 1 to 6 carbon atoms is preferable.
• acyloxy group an acyloxy group having 1 to 6 carbon atoms is preferable.
• L an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferable.
• R is a monovalent hydrocarbon group.
• the monovalent hydrocarbon group a monovalent aliphatic hydrocarbon group (which may be saturated or unsaturated) and a monovalent aromatic hydrocarbon group are preferable, and a monovalent aliphatic hydrocarbon group is preferable.
• Hydrocarbon groups are more preferred, and alkyl groups are particularly preferred.
• the monovalent hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
• 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.
• R 12 represents a monovalent substituent.
• the monovalent substituent include an alkyl group, a hydroxyl group, an acyloxy group, and a halogen atom, and a hydroxyl group is preferable.
• j1 is an integer of 1 or more, and 1 to 6 is preferable, and 1 is particularly preferable, from the viewpoint that the water- and oil-repellent layer has more excellent water- and oil-repellent properties.
• g11 is an integer of 2 or more, and is preferably 3 or more from the viewpoint of more excellent friction resistance of the water- and oil-repellent layer.
• the g11 is preferably 15 or less, more preferably 8 or less, and particularly preferably 6 or less.
• g12 is an integer of 0 or more, preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0 because the water and oil repellent layer is more excellent in abrasion resistance.
• a plurality of compound (1-1) has [-L 1 -S-R 11] it can be different. If having a plurality of - [(OX) m -O- R f], a plurality of compound (1-1) is [R f - (OX) m -O-] may be different.
• Moiety represented by Y 1 -Z 1 in formula (1-1) is preferably a group represented by the following formula (g1-1) ⁇ formula (G1-8).
• a 1 corresponds to Y 1 in formula 1-1.
• * 1 denotes the bonding position to [-L 1 -S-R 11] in the formula (1-1)
• * 2 Formula (1 It means the connection position with [R 12 ] in 1).
• a 1 is a single bond, an alkylene group, or -C (O) NR 6- , -C (O)-, -OC (O) O-, between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms.
• the hydrogen atom of the alkylene group may be substituted with a fluorine atom.
• Q 11 represents a single bond, -O-, alkylene group or a carbon of an alkylene group having 2 or more carbon atoms - -C between carbon atoms (O) NR 6 -, - C (O) -, - NR 6 - Alternatively, it is a group having —O—.
• Z a1 is a group having a h1 + h2 valent ring structure having a carbon atom or a nitrogen atom and having a carbon atom or a nitrogen atom A 1 is directly bonded [-L 1 -S-R 11] is bonded directly ..
• a specific example of Z a1 is an isocyanurate ring.
• Z a2 is a (i5 + 1) -valent organopolysiloxane residue, and the following groups are preferable.
• Ra in the following formula is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or a phenyl group.
• Re1 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.
• d1 is an integer of 0 to 3, preferably 1 or 2.
• d2 is an integer of 0 to 3, preferably 1 or 2.
• d1 + d2 is an integer of 1 to 3.
• d3 is an integer of 0 to 3, preferably 0 or 1.
• d4 is an integer of 0 to 3, preferably 2 or 3.
• d3 + d4 is an integer of 1 to 3.
• d1 + d3 is an integer of 1 to 5, preferably 1 or 2, and preferably 1.
• d2 + d4 is an integer of 2 to 5, preferably 4 or 5.
• e1 + e2 is 3 or 4.
• e1 is 1 or 2.
• e2 is 2 or 3.
• h1 is an integer of 1 or more, preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.
• h2 is an integer of 2 or more, preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.
• i1 + i2 is 3 or 4.
• i1 is an integer of 1 or more, preferably 1 to 2, and more preferably 1.
• i2 is an integer of 2 or more, preferably 2 or 3.
• i3 is an integer of 1 to 3, preferably 2 or 3.
• i4 is an integer of 2 or more, preferably 2 to 10, and particularly preferably 2 to 6.
• i5 is an integer of 2 to 7.
• Moiety represented by Y 1 -Z 1 in formula (1-1) is, as the compound is a group (g1-2) (1-1), for example, a compound of the formula.
• PFPE in the compound represents R f ⁇ (OX) m + 1 .
• the definitions of R f , X, and m are as described above.
• Moiety represented by Y 1 -Z 1 in formula (1-1) is, as the compound is a group (G1-4) (1-1), for example, a compound of the formula.
• Moiety represented by Y 1 -Z 1 in formula (1-1) is, as the compound is a group (G1-5) (1-1), for example, a compound of the formula.
• divalent linking group in La 1 include the divalent linking group in L 1 of the formula (1-1).
• R 111 is a monovalent substituent.
• monovalent substituent in R 111 include the monovalent substituent in R 11 in the formula (1-1).
• the fluorine-containing ether compound of the second embodiment of the present invention is a compound represented by the formula (1-2) described later (compound (1-2)) and has a thiol structure or a thioether structure.
• the present inventors have found that when a water-repellent oil-repellent layer is formed on a substrate containing gold, silver or copper using compound (1-2), the water-repellent oil-repellent layer is excellent in abrasion resistance. The details of this reason have not been clarified, but it is presumed that the reason is the same as when the fluorine-containing ether compound of the first embodiment is used.
• Compound (1-2) is a fluorine-containing ether compound represented by the formula (1-2). [R 21] g21 [R 22 -S-L 21 -] g22 Z 21 -Y 21 - (OX) m -O-Y 22 -Z 22 [-L 22 -S-R 23] g23 [R 24] g24 (1-2)
• R 21 and R 24 are independently monovalent substituents. Specific examples and preferred embodiments of the monovalent substituent in R 21 and R 24 are the same as those in the monovalent substituent in R 12 in the formula (1-1).
• R 22 and R 23 are independently hydrogen atoms or monovalent substituents. Specific examples and preferred embodiments of the monovalent substituent in R 22 and R 23 are the same as those in the monovalent substituent in R 11 in the formula (1-1).
• L 21 and L 22 are independently single-bonded or divalent linking groups, respectively. Specific examples and preferred embodiments of the divalent linking group in L 21 and L 22 are the same as those in the divalent linking group in L 1 in the formula (1-1).
• Z 21 is a (g21 + g22 + 1) valence linking group. Specific examples and preferred embodiments of the (g21 + g22 + 1) -valent linking group are the same as those of the (g11 + g12 + 1) -valent linking group in Z 1 in the formula (1-1).
• Z 22 is a linking group of (g23 + g24 + 1) valence. Specific examples and preferred embodiments of the (g23 + g24 + 1) -valent linking group are the same as those of the (g11 + g12 + 1) -valent linking group in Z 1 in the formula (1-1).
• Y 21 and Y 22 are independently single-bonded or divalent linking groups, respectively. Specific examples and preferred aspects of the divalent linking group are the same as the linking group (j1 + 1) titers in Y 1 in the formula (1-1). However, when Y 21 and Y 22 are divalent linking groups, the divalent linking group does not contain two or more ester bonds.
• X is a fluoroalkylene group having one or more fluorine atoms, and specific examples and preferred embodiments thereof are the same as those of X in the formula 1-1.
• m is an integer of 2 or more, and specific examples and preferred embodiments thereof are the same as m in the formula (1-1).
• (OX) m is a poly (oxyfluoroalkylene) chain, and specific examples and preferred embodiments thereof are the same as those of (OX) m in the formula (1-1).
• g21 and g24 are independently integers of 0 or more, preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0 because the water and oil repellent layer is more excellent in abrasion resistance.
• g22 and g23 are independently integers of 2 or more, and 3 or more are preferable from the viewpoint of more excellent friction resistance of the water-repellent oil-repellent layer. Independently, g22 and g23 are preferably 15 or less, more preferably 8 or less, and particularly preferably 6 or less.
• a compound (1-2) has may be different.
• the plurality of [-L 22- SR 23 ] contained in compound (1-2) may be different.
• a plurality of R 21 may be different.
• a plurality of R 24 may be different.
• the part represented by Z 21- Y 21 and the part represented by Y 22- Z 22 in the formula (1-2) are independently represented by the following formulas (g2-1) to (g2-8). It is preferably a base.
• a 11 corresponds to Y 21 or Y 22 in formula (1-2).
• * 1 is [R 22 -S-L 21 - ] in equation (1-2) bonding position to or [-L 22 -S-R 23] Means * 2 , and * 2 means the connection position with R 21 or R 24 in the formula (1-2).
• a 11 are the same as those of A 1 in the formulas (g1-1) to (g1-8). However, A 11 does not contain two or more ester bonds.
• the definitions and preferred embodiments of Q 21 , Z a11 , Z a12 and R e11 are the same as those of Q 11 , Z a1 , Z a2 and R e1 in the formulas (g1-1) to (g1-8), respectively.
• d11 is 0 or 1.
• d12 is an integer of 0 to 3.
• d11 + d12 is an integer of 1 to 3.
• d13 is 0 or 1.
• d14 is an integer of 0 to 3.
• d13 + d14 is an integer of 1 to 3.
• d11 + d13 is 1.
• d12 + d14 is an integer of 2 to 5, preferably 4 or 5.
• e11 + e12 is 3 or 4.
• e11 is 1.
• e12 is 2 or 3.
• h11 is 1.
• h12 is an integer of 2 or more, preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.
• i11 + i12 is 3 or 4.
• i11 is 1 or more.
• i12 is an integer of 2 or more, preferably 2 or 3.
• i13 is an integer of 1 to 3, preferably 2 or 3.
• i14 is an integer of 2 or more, preferably an integer of 2 to 10,
• PFPE in the compound of the following formula represents -X- (OX) m -OX-.
• the definitions of X and m are as described above.
• Examples of the compound (1-2) in which the portion represented by Z 21 to Y 21 and the portion represented by Y 22 to Z 22 are a group (g2-2) include the compound of the following formula.
• Examples of the compound (1-2) in which the portion represented by Z 21 to Y 21 and the portion represented by Y 22 to Z 22 are a group (g2-4) include the compound of the following formula.
• Examples of the compound (1-2) in which the portion represented by Z 21 to Y 21 and the portion represented by Y 22 to Z 22 are a group (g2-5) include the compound of the following formula.
• Method for producing compound (1-2) As an example of the method for producing the compound (1-2), there is a method for producing the compound (1b-1) by a thiol-ene reaction between the compound (2a-1) and the above-mentioned compound (1b-1).
• L 22 is the compound (2a-1).
• a method for producing the compound (1-2) by a thiol-ene reaction between the above-mentioned compound (2a-1) and the above-mentioned compound (1b-2) can be mentioned.
• composition of the present invention contains at least one of the above-mentioned compounds (1-1) and compound (1-2) and a liquid medium.
• the composition of the present invention is preferably used as a composition for forming a water-repellent oil-repellent layer having excellent abrasion resistance on a substrate by a wet coating method.
• compound (1-1) and compound (1-2) are also collectively referred to as "compound (1)”.
• containing compound (1) means containing at least one of compound (1-1) and compound (1-2).
• a fluorine-containing ether compound other than the compound (1) is hereinafter referred to as "another fluorine-containing ether compound”.
• the compound (1) and other fluorine-containing ether compounds are collectively referred to as "fluorine-containing ether compound”.
• the composition of the present invention may contain a fluorine-containing ether compound other than the compound (1).
• fluorine-containing ether compounds include a compound in which g11 of the above formula (1-1) is 1, and a compound in which g22 is 1 and g23 is 1 in the above formula (1-2).
• 21 includes a compound having two or more ester bonds
• Y 22 contains a compound having at least one of two or more ester bonds. Two or more kinds of other fluorine-containing ether compounds may be used in combination.
• the content of the compound (1-1) is preferably 10% by mass or more based on the total mass of the fluorine-containing ether compound. 10 to 80% by mass is preferable, and 10 to 50% by mass is particularly preferable.
• the content of the fluorine-containing ether compound other than the compound (1-1) is 40 to 60 with respect to the total mass of the fluorine-containing ether compound. The mass% is preferable, and 45 to 55% by mass is particularly preferable.
• the content of the compound (1-2) is preferably 50% by mass or more based on the total mass of the fluorine-containing ether compound. 80% by mass or more is particularly preferable.
• the content of the fluorine-containing ether compound other than the compound (1-2) is 40 to 60 mass with respect to the total mass of the fluorine-containing ether compound. % Is preferable, and 45 to 55% by mass is particularly preferable.
• the composition of the present invention comprises a liquid medium.
• the liquid medium include water and an organic solvent.
• an organic solvent is preferable, and an organic solvent having a boiling point of 35 to 250 ° C. is more preferable from the viewpoint of excellent coatability.
• the boiling point means a standard boiling point.
• Specific examples of the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent, and a fluorine-based organic solvent is preferable in terms of excellent solubility. Two or more kinds of organic solvents may be used in combination.
• 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, and for example, C 6 F 13 H (AC-2000: product name, manufactured by AGC Inc.), C 6 F 13 C 2 H 5 (AC-6000: product). Name, manufactured by AGC), C 2 F 5 CHFCHFCF 3 (Bertrel: product name, manufactured by DuPont).
• fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
• fluoroalkyl ether a compound having 4 to 12 carbon atoms is preferable, and for example, CF 3 CH 2 OCF 2 CF 2 H (AE-3000: product name, manufactured by AGC), C 4 F 9 OCH 3 (Novec-7100).
• fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
• fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.
• non-fluorine-based organic solvent a compound consisting of only hydrogen atoms and carbon atoms and a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms are preferable, and specifically, a hydrocarbon-based organic solvent and a ketone-based organic solvent are used.
• a hydrocarbon-based organic solvent and a ketone-based organic solvent are used.
• Ether-based organic solvent, ester-based organic solvent, alcohol-based organic solvent can be mentioned.
• Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.
• Specific examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
• ether-based organic solvent examples include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.
• ester-based organic solvent examples include ethyl acetate and butyl acetate.
• alcohol-based organic solvent examples include isopropyl alcohol, ethanol, and n-butanol.
• the content of the liquid medium in the composition of the present invention is preferably 70 to 99.99% by mass, particularly preferably 80 to 99.9% by mass, based on the total mass of the composition.
• the composition of the present invention may contain components other than the above as long as the effects of the present invention are not impaired.
• other components include by-products produced in the production process of compound (1) and other fluorine-containing ether compounds, unreacted raw materials, and other unavoidable compounds in production.
• the content of the other components is preferably 10% by mass or less, more preferably 5% by mass or less, based on the content of the compound (1) in the composition of the present invention. Mass% or less is particularly preferable.
• the compound (1) of the present invention and the composition of the present invention are useful as a water- and oil-repellent agent for forming a water- and oil-repellent layer on the surface of a base material.
• it is useful as a water- and oil-repellent agent for forming a water- and oil-repellent layer on the metal surface of a base material having a metal surface or the resin surface of a base material having a resin surface.
• the surface of the base material can be treated by a dry coating method using the water-repellent oil-repellent agent to form a water-repellent oil-repellent layer on the surface of the base material.
• the present invention also comprises a group with a water-repellent oil-repellent layer, which comprises treating the surface of a base material by a dry coating method using the water-repellent oil-repellent agent to form a water-repellent oil-repellent layer on the surface of the base material. It is a method of manufacturing a material.
• the composition is applied to the surface of a base material by a wet coating method using the composition of the present invention, dried, and a water-repellent oil-repellent layer is applied to the surface of the base material.
• a water-repellent oil-repellent layer is applied to the surface of the base material.
• the present invention is also characterized in that the composition is applied to the surface of a base material by a wet coating method using the composition of the present invention and dried to form a water-repellent and oil-repellent layer on the surface of the base material. This is a method for producing a base material with a water-repellent and oil-repellent layer.
• the formation of the water-repellent oil-repellent layer on the surface of the base material may be performed on the base material constituting the article, and the base as a member before forming the article. It may be done for the material.
• the article with the water-repellent oil-repellent layer described later is produced from the article and the water-repellent oil-repellent agent by the above-mentioned manufacturing method.
• the water- and oil-repellent agent containing the compound (1) used in the dry coating method may have other components that can be deposited on the surface of the substrate together with the compound (1) in the dry coating method.
• the fluorine-containing ether other than the compound (1) mentioned as being may be contained together with the compound (1) in the composition of the present invention. Examples include compounds.
• the water-repellent oil-repellent agent contains a fluorine-containing ether compound other than the compound (1)
• the relative ratio of the compound (1) in the water-repellent oil-repellent agent to the other fluorine-containing ether compound is the composition of the present invention. It is preferable that the ratio is the same as in.
• the water-repellent and oil-repellent agent further contains a component other than the fluorine-containing ether compound other than the compound (1).
• the dry coating method include a vacuum vapor deposition method, a CVD method, and a sputtering method.
• the vacuum vapor deposition method is preferable from the viewpoint of suppressing the decomposition of the compound (1) and the simplicity of the apparatus.
• wet coating method in the wet coating method using the composition of the present invention include a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a dip coating method, a die coating method, an inkjet method, and a flow coating method.
• Roll coat method cast method, Langmuir Brodget method, gravure coat method.
• a base material on which the surface on which the water- and oil-repellent layer is formed is a metal surface or a resin surface is preferable, and a base material having a metal surface is particularly preferable.
• the base material on which the water- and oil-repellent layer is formed is a metal surface, which may be a base material made of a metal material, and a metal layer is provided on the surface of a main body made of a non-metal material such as resin, glass, or ceramics. It may be a composite base material having.
• a base material made of a metal material it may be a composite metal base material having a metal layer made of a metal different from the main body on the surface of the metal main body.
• a metal layer on the surface of the base material a metal layer formed by forming a thin metal layer on the surface of the main body of the base material by plating, vapor deposition or the like, laminating a metal film on the surface of the main body of the base material, or the like is preferable.
• the metal layer may have a multi-layer structure, but the surface on which the water-repellent oil-repellent layer is formed means the outermost layer in contact with the water-repellent oil-repellent layer.
• the metal surface of the surface of the base material may be the entire surface of the surface of the base material or a part of the surface of the base material.
• the entire surface of one side of the sheet may be a metal surface, or a part of one side may be a metal surface.
• a water-repellent and oil-repellent layer is usually formed on the metal surface where the metal layer is present.
• the metal material constituting the metal surface is a metal material containing at least one metal selected from the group consisting of gold, silver, and copper. Is preferable. Specific examples thereof include simple substances of these metals, two or more alloys of these metals, alloys of at least one of these metals with metals other than these metals, and the like. Since the water- and oil-repellent layer has more excellent friction resistance, the metal material on the metal surface is preferably a metal material containing gold because the water- and oil-repellent layer has more excellent friction resistance. It is more preferable that the metal is a simple substance or a gold alloy from the viewpoint of high value.
• the non-metal material includes resin, glass, sapphire, ceramic, stone, and a composite material thereof. ..
• the glass may be chemically strengthened.
• the base material on which the surface on which the water- and oil-repellent layer is formed is a resin surface
• a resin surface may be a base material made of a resin material, and a resin layer is provided on the surface of a main body made of a non-resin material such as glass, ceramics, or metal. It may be a composite base material having.
• the base material may have a resin layer made of a resin different from the main body on the surface of the main body made of the resin material.
• a surface that comes into contact with human skin such as an article that may be held by a human finger (for example, a stylus) or an article that may be used by touching the human finger during operation (for example, a touch panel).
• a substrate having a stylus is particularly suitable.
• a water- and oil-repellent layer is formed on the surface of the base material, which is at least in contact with human skin.
• the surface of the base material on which the water-repellent and oil-repellent layer is formed is preferably a metal surface as described above.
• a touch panel base material and a display base material are preferable, and a touch panel base material is particularly preferable.
• the base material for the touch panel preferably has translucency.
• the material of the base material for the touch panel is preferably glass or a transparent resin. Further, as the base material, there is also a base material whose main body is made of glass or a resin film, which constitutes an exterior part (excluding the display part) of a device such as a mobile phone (for example, a smartphone), a mobile information terminal, a game machine, or a remote controller. preferable.
• the thickness of the water-repellent and oil-repellent layer formed on the surface of the base material is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm.
• the thickness of the water-repellent oil-repellent layer is at least the lower limit, the effect of the water-repellent oil-repellent layer can be sufficiently obtained.
• the thickness of the water-repellent and oil-repellent layer is not more than the above upper limit, the utilization efficiency is high.
• the thickness obtained by the X-ray diffractometer for thin film analysis is defined as the thickness of the water-repellent oil-repellent layer.
• the thickness of the water- and oil-repellent layer is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G manufactured by RIGAKU), and the vibration cycle of the interference pattern. Can be calculated from.
• the water- and oil-repellent layer may be formed directly on the surface of the base material, or may be formed on the base material via another film formed on the surface of the base material.
• the article with a water- and oil-repellent layer of the present invention comprises a base material having a metal surface, and a water- and oil-repellent layer formed of the compound (1) or the composition of the present invention on the metal surface of the base material.
• An article with a water-repellent oil-repellent layer is a member obtained by forming a water-repellent oil-repellent layer on a metal surface of the article surface (that is, a metal surface of a base material constituting the article) as described above, or by forming an article before forming the article. It can be obtained by constructing an article using a base material with a water-repellent and oil-repellent layer.
• the article include a touch panel, a display, a mobile phone (for example, a smartphone), a personal digital assistant, a game machine, a remote controller, a stylus, and the like as described above.
• Examples 1, 2 and 4 to 7 are examples, and example 3 is a comparative example. However, the present invention is not limited to these examples.
• the blending amount of each component in the table described later indicates a mass standard.
• Example 1 0.16 g of compound (1-1A) was placed as a vapor deposition source on a molybdenum boat in a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.). The following base material 1 was placed in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted until the pressure became 5 ⁇ 10 -3 Pa or less. The board is heated to about 1000 ° C., the compound (1-1A) is vacuum-deposited on the surface of the base material 1, and a film is formed when the thickness of the compound (1-1A) reaches about 15 nm. finished.
• Base material 1 A base material (diameter 25 mm, thickness 5 mm) in which the surface of glass is coated in the order of chromium (film thickness 50 to 60 nm) and gold (film thickness 200 nm), and gold is arranged on the outermost surface.
• Example 2 An evaluation sample of Example 2 (article with a water- and oil-repellent layer) was obtained in the same manner as in Example 1 except that compound (1-1B) was used instead of compound (1-1A). The evaluation results of the evaluation samples are shown in Table 1.
• Example 3 30 g of silicon oxide was placed as a vapor deposition source on a copper hearth in a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.), and 0.16 g of compound (X1) was placed as a vapor deposition source on a molybdenum boat.
• the base material 1 was placed in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted until the pressure became 5 ⁇ 10 -3 Pa or less.
• the hearth was heated to about 2000 ° C., and silicon oxide was vacuum-deposited on the surface of the base material to produce a base material with a silicon oxide layer having a silicon oxide layer having a thickness of about 20 nm.
• the board was heated to about 1000 ° C., and the compound (X1) in the composition was vacuum-deposited on the surface of the silicon oxide layer, so that the thickness of the film on the silicon oxide layer became about 15 nm. At that point, the film formation was completed.
• the article on which the compound (X1) was deposited was heat-treated at 140 ° C. for 30 minutes to obtain an evaluation sample (article with a water-repellent oil-repellent layer) in which a substrate, a silicon oxide layer and a water-repellent oil-repellent layer were laminated in this order.
• the evaluation results of the evaluation samples are shown in Table 1.
• Example 4 to 7 Evaluation samples of Examples 4 to 7 (articles with a water-repellent oil-repellent layer) were obtained in the same manner as in Example 1 except that the compound of Table 1 was used instead of the compound (1-1A). The evaluation results of the evaluation samples are shown in Table 1.
• the article with a water-repellent oil-repellent layer of the present invention can be used for various applications in which water-repellent and oil-repellent properties are required.
• display input devices such as touch panels, transparent glass or transparent plastic members, lenses for glasses, antifouling members for kitchens, electronic devices, heat exchangers, water-repellent and moisture-proof members such as batteries, and antifouling members.
• It can be used as an antifouling member for toiletries, a member that requires liquid repellency while conducting, a member for water repellency / waterproofing / sliding of a heat exchanger, a member for vibration sieving, a member for low surface friction such as inside a cylinder, and the like.
• More specific examples of use include display front protective plates, antireflection plates, polarizing plates, antiglare plates, or those with antireflection film treatment applied to their surfaces, mobile phones (for example, smartphones), and personal digital assistants.
• Game machines devices such as remote controls, touch panel sheets, touch panel displays, and other devices that have display input devices that operate on the screen with human fingers or palms (for example, glass or film used for display units, etc., and Glass or film used for exterior parts other than the display part).

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• 2020
  • 2020-12-07 CN CN202080086157.4A patent/CN114787237A/zh active Pending
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• 2022
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