Classifications

• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
  • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
• • 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
  • 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
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
• • 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
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1637—Macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1637—Macromolecular compounds
  • C09D5/165—Macromolecular compounds containing hydrolysable groups
• • 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
• • 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
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
  • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to a composition, a substrate with a surface layer, and a method for producing a substrate with a surface layer.
• Patent Document 1 In order to impart water and oil repellency, fingerprint removability, lubricity (smoothness when touched with a finger) and the like to the surface of a substrate, it is known that a surface layer made of a condensate of a fluorine-containing ether compound is formed on the surface of the substrate by surface treatment using a fluorine-containing ether compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group (Patent Document 1).
• the performance required for a surface layer formed using a fluorinated ether compound has been increasing.
• the surface layer is required to have a performance (e.g., water repellency) that is not likely to decrease even when repeatedly worn, that is, a surface layer having excellent abrasion resistance.
• the present inventors have evaluated a surface layer formed using a fluorine-containing ether compound as described in Patent Document 1 and have found that there is room for improvement in the abrasion resistance of the surface layer.
• the present invention aims to provide a composition capable of forming a surface layer with excellent abrasion resistance, a substrate with a surface layer, and a method for producing a substrate with a surface layer.
• a composition comprising a compound represented by formula (B1) and a second component comprising at least one fluorinated ether compound selected from the group consisting of compounds represented by formula (B2): [R f1 -(OR f11 ) y1 -O-R 1 ] j -L 1 -(R 11 -T 11 ) x1 ...
• R f1 is a fluoroalkyl group having 1 to 20 carbon atoms, and when there are a plurality of R f1s , the plurality of R f1s may be the same or different from each other, R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are multiple R f11 , the multiple R f11 may be the same or different from each other, R 1 is an alkylene group or a fluoroalkylene group, and when there are a plurality of R 1 , the plurality of R 1 may be the same or different; L1 is a single bond or a j+x1-valent group which may have N, O, S, or Si and may have a branch point
• R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are multiple R f12 , the multiple R f12 may be the same or different from each other,
• R2 and R3 each independently represent an alkylene group or a fluoroalkylene group;
• L2 is a single bond or a 1+x2-valent group which may have N, O, S, or Si and may have a branch point, and the atoms bonded to R2 and R21 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having
• R a22 represents a non-hydrolyzable group, and when there are a plurality of R a22 , the plurality of R a22 may be the same or different.
• z21 is an integer of 1 to 3
• x2 and x3 each independently represent an integer of 1 or more
• y2 is an integer of 1 or more, and when y2 is 1, R2 is a fluoroalkylene group;
• Q1 is a r1-valent group having a branch point
• R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f13's may be the same or different.
• Each R 4 is independently an alkylene group or a fluoroalkylene group, and a plurality of R 4s may be the same or different from each other;
• L 4 is a single bond or a 1+x4-valent group which may have N, O, S, or Si and may have a branch point, and the atoms bonded to R 4 and R 41 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group, and a plurality of L 4s may be the same or different from each other
• R 41 is an alkylene group in which the atom adjacent to L 4 may be an ethereal oxygen atom or which may have an ethereal oxygen atom between carbon atoms, and a plurality of R 41 may be the same or different from each other
• T 41 is -SiR a41 z41 R a42 3-z41 , and a plurality of T 41 may be the same
• R a42 is a non-hydrolyzable group, and when there are a plurality of R a42 , the plurality of R a42 may be the same or different.
• z41 is an integer from 1 to 3
• x4 is an integer of 1 or more, and when there are multiple x4s, the multiple x4s may be the same or different from each other
• y3 is an integer of 1 or more, and when there are multiple y3's, the multiple y3's may be the same or different from each other, r1 is 3 or 4;
• R f14 is a fluoroalkyl group having 1 to 20 carbon atoms
• R f15 is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are multiple R f15s , the multiple R f15s may be the same or different from each other
• R5 is an alkylene group which may have a substituent
• R b1 is a hydrogen atom, a
• At least one of R 11 has a carbon chain having 4 or more carbon atoms connected thereto, and the carbon chain is connected to T 11 ;
• at least one of R 21 has a carbon chain having 4 or more carbon atoms linked thereto, and the carbon chain is linked to T 21
• at least one of R 31 has a carbon chain having 4 or more carbon atoms linked thereto, and the carbon chain is linked to T 31 ;
• the fluoroalkylene group represented by R5 has 1 to 20 carbon atoms
• the composition according to [4], wherein, in formula (B2), the total number of carbon atoms in the fluoroalkylene group represented by R 6 and the total number of carbon atoms in the fluoroalkylene group represented by R 7 is 2 to 40.
• a substrate with a surface layer comprising: a substrate; and a surface layer formed on the substrate from the composition according to any one of [1] to [5].
• a method for producing a substrate with a surface layer comprising forming a surface layer on a substrate by a dry coating method or a wet coating method using the composition according to any one of [1] to [5].
• the present invention provides a composition capable of forming a surface layer with excellent abrasion resistance, a substrate with a surface layer, and a method for producing a substrate with a surface layer.
• a compound represented by formula (B1) is referred to as compound (B1).
• Compounds represented by other formulae are also referred to in the same manner.
• a repeating unit represented by formula (f1) is referred to as unit (f1). Repeating units represented by other formulae are also referred to in the same manner.
• a group represented by formula (g1) is referred to as group (g1). Groups represented by other formulae are also referred to in the same manner.
• the fluoroalkyl group is a general term that includes perfluoroalkyl groups and partial fluoroalkyl groups.
• the perfluoroalkyl group means a group in which all hydrogen atoms of an alkyl group are replaced with fluorine atoms.
• the partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are replaced with fluorine atoms and which has one or more hydrogen atoms.
• the fluoroalkyl group is an alkyl group having one or more fluorine atoms.
• the term "reactive silyl group” is a general term for a hydrolyzable silyl group and a silanol group (Si-OH), and the term “hydrolyzable silyl group” refers to a group that can form a silanol group by hydrolysis.
• organic group refers to a hydrocarbon group which may have a substituent and which may have a heteroatom or other bond in the carbon chain.
• hydrocarbon group refers to a group consisting of carbon atoms and hydrogen atoms, and includes aliphatic hydrocarbon groups (for example, divalent aliphatic hydrocarbon groups such as linear alkylene groups, branched alkylene groups, and cycloalkylene groups), aromatic hydrocarbon groups (for example, divalent aromatic hydrocarbon groups such as phenylene groups), and combinations thereof.
• surface layer refers to a layer formed on the surface of a substrate.
• the "molecular weight" of a partial structure such as a fluoroether chain or a fluoropolyether chain and a fluorine-containing ether compound is a number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units based on the terminal group by 1 H-NMR and 19 F-NMR.
• the use of "to" indicating a range of numerical values means that the numerical values before and after it are included as the lower limit and upper limit.
• composition of the present invention comprises a first component comprising at least one fluorinated ether compound selected from the group consisting of a compound represented by formula (A1) described below, a compound represented by formula (A2) described below, and a compound represented by formula (A3) described below; and a second component comprising at least one fluorine-containing ether compound selected from the group consisting of a compound represented by formula (B1) described below and a compound represented by formula (B2) described below.
• the present inventors have found that when a surface layer is formed on a substrate using the composition of the present invention, the water repellency and abrasion resistance of the surface layer are improved. Although the detailed reason for this is not clear, it is presumed that the inclusion of a specific first component and a specific second component greatly contributes to the manifestation of the effect.
• the first component contained in the composition of the present invention is at least one fluorinated ether compound selected from the group consisting of compounds represented by formula (A1), compounds represented by formula (A2), and compounds represented by formula (A3).
• j is an integer of 1 or more, and when j is 1, y1 is an integer of 2 or more, or R1 is a fluoroalkylene group; z11 is an integer from 1 to 3, x1 is an integer of 2 or more, y1 is an integer of 1 or more, and when there are multiple y1's, the multiple y1's may be the same or different.
• R f12 is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are multiple R f12 , the multiple R f12 may be the same or different from each other, R2 and R3 each independently represent an alkylene group or a fluoroalkylene group;
• L2 is a single bond or a 1+x2-valent group which may have N, O, S, or Si and may have a branch point, and the atoms bonded to R2 and R21 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group;
• L3 is a single bond or a 1+x3-valent group which may have N, O, S, or Si and may have a branch point, and the atoms bonded to R3 and R31 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxy
• R a22 represents a non-hydrolyzable group, and when there are a plurality of R a22 , the plurality of R a22 may be the same or different.
• z21 is an integer from 1 to 3
• x2 and x3 each independently represent an integer of 2 or more
• y2 is an integer of 1 or more, and when y2 is 1, R 2 is a fluoroalkylene group.
• Q1 is a r1-valent group having a branch point
• R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f13's may be the same or different.
• Each R 4 is independently an alkylene group or a fluoroalkylene group, and a plurality of R 4s may be the same or different from each other;
• L4 is a single bond or a 1+x4-valent group which may have N, O, S, or Si and may have a branch point, and the atoms bonded to R4 and R41 are each independently N, O, S, Si, a carbon atom constituting a branch point, or a carbon atom having a hydroxyl group or an oxo group, and a plurality of L4s may be the same or different from each other;
• R 41 is an alkylene group in which the atom adjacent to L 4 may be an ethereal oxygen atom or which may have an ethereal oxygen atom between carbon atoms, and a plurality of R 41 may be the same or different from each other, T 41 is -SiR a41 z41 R a42 3-z41 , and a plurality of T 41 may be the same
• R a42 is a non-hydrolyzable group, and when there are a plurality of R a42 , the plurality of R a42 may be the same or different.
• z41 is an integer from 1 to 3
• x4 is an integer of 2 or more
• a plurality of x4's may be the same or different
• y3 is an integer of 1 or more
• a plurality of y3's may be the same or different
• r1 is 3 or 4.
• the structure of each compound will be explained below, and symbols having similar structures will be indicated as such and can be read as appropriate for reference.
• the first component has a reactive silyl group at its end, which is strongly chemically bonded to the substrate, and therefore the surface layer formed using the first component has excellent durability, such as friction resistance.
• the fluoropolyether chain is a group having two or more oxyfluoroalkylene units.
• the fluoropolyether chain may have hydrogen atoms.
• the ratio of fluorine atoms in the fluoropolyether chain represented by the following formula (I) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, that is, a perfluoropolyether chain. If the ratio of fluorine atoms is 60% or more, the amount of fluorine in the fluoropolyether chain increases, and lubricity and fingerprint removability are further improved.
• Formula (I): Percentage of fluorine atoms (%) (number of fluorine atoms)/ ⁇ (number of fluorine atoms)+(number of hydrogen atoms) ⁇ 100
• the molecular weight of each fluoropolyether chain is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, and even more preferably 3,000 to 10,000, in order to achieve both fingerprint removability and lubricity of the surface layer. If the molecular weight of the fluoropolyether chain is 2,000 or more, the flexibility of the fluoropolyether chain is improved and the amount of fluorine in the molecule is increased, resulting in improved lubricity and fingerprint removability. On the other hand, if the molecular weight of the fluoropolyether chain is 20,000 or less, the surface layer will have better abrasion resistance.
• the compound (A1) has a structure represented by the following formula (A1). [R f1 -(OR f11 ) y1 -O-R 1 ] j -L 1 -(R 11 -T 11 ) x1 ... (A1)
• each symbol in formula (A1) is as defined above.
• R f1 is a fluoroalkyl group having 1 to 20 carbon atoms.
• the fluoroalkyl group may be linear or may have a branched and/or cyclic structure. From the viewpoint of abrasion resistance, a linear fluoroalkyl group is preferred, and from the viewpoint of ease of synthesis, the number of carbon atoms of the fluoroalkyl group is preferably 1 to 6, and more preferably 1 to 3.
• R f11 is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are multiple R f11 , the multiple R f11 may be the same or different from each other.
• y1 represents a fluoroether chain or a fluoropolyether chain (when y1 is 1, it represents a fluoroether chain, and as described above, when y1 is 2 or more, it represents a fluoropolyether chain).
• y1 may be an integer of 1 or more, and is preferably 1 to 200.
• (OR f11 ) y1 preferably has a structure represented by the following formula (G11). -[(OG f1 ) m1 (OG f2 ) m2 (OG f3 ) m3 (OG f4 ) m4 (OG f5 ) m5 (OG f6 ) m6 ]-...(G11) however, G f1 is a fluoroalkylene group having 1 carbon atom; G f2 is a fluoroalkylene group having 2 carbon atoms, G f3 is a fluoroalkylene group having 3 carbon atoms, G f4 is a fluoroalkylene group having 4 carbon atoms, G f5 is a fluoroalkylene group having 5 carbon atoms; G f6 is a fluoroalkylene group having 6 carbon atoms; m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more
• the bonding order of (OG f1 ) to (OG f6 ) in formula (G11) is arbitrary.
• m1 to m6 in formula (G11) respectively represent the number of (OG f1 ) to (OG f6 ), and do not represent the arrangement.
• (OG f5 ) m5 represents that the number of (OG f5 ) is m5, and does not represent the block arrangement structure of (OG f5 ) m5 .
• the order of (OG f1 ) to (OG f6 ) does not represent the bonding order of each unit.
• the fluoroalkylene group having 3 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or a fluoroalkylene group having a branched or cyclic structure.
• G f1 include --CF 2 -- and --CHF--.
• G f2 include -CF 2 CF 2 -, -CHFCF 2 -, -CHFCHF-, -CH 2 CF 2 -, -CH 2 CHF-, and the like.
• G f3 include -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CH 2 CF 2 -, -CHFCF 2 CF 2 -, -CHFCHFCF 2 -, -CHFCHFCHF-, -CHFCH 2 CF 2 -, -CH 2 CF 2 CF 2 -, -CH 2 CHFCF 2 -, -CH 2 CH 2 CF 2 -, -CH 2 CF 2 CHF-, -CH 2 CHFCHF-, -CH 2 CH 2 CHF- , -CF (CF 3 )-CF 2 -, -CF(CHF 2 )-CF 2 -, -CF(CH 2 F)-CF 2 -, -CF( CH3 ) -CF2- , -CF(CF3)-CHF-, -CF( CHF2 )-CHF-, -CF( CH2F )-CHF- , -CF(CF(
• G f4 include -CF 2 CF 2 CF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 -, -CH 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CHFCHFCF 2 CF 2 - , -CH 2 CHFCF 2 CF 2 -, -CF 2 CH 2 CF 2 CF 2 -, -CHFCH 2 CF 2 CF 2 -, -CH 2 CH 2 CF 2 CF 2 -, -CHFCF 2 CHFCF 2 -, -CH 2 CHFCF 2 -, -CF 2 CHFCFCF 2 -, -CF 2 CHFCFCF 2 - , -, -CHFCHFCHFCF2- , -CH2CHFCHFCF2- , -CF2CH2CHFCF2-, -CHFCH2CHFCF2- , -CH2CH2CHFCF2- , -CF2CH2CH2CF
• G f5 examples include -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 -, -CH 2 CHFCF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 CF 2 -, -CHFCHFCF 2 CF 2 CF 2 -, -CF 2 CH 2 CF 2 CF 2 -, -CHFCH 2 CF 2 CF 2 CF 2 -, -CH 2 CH 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CHFCF 2 CF 2 -, -CHFCF 2 CHFCF 2 Examples include -CF 2 -, -CH 2 CF 2 CHFCF 2 CF 2 -, -CH 2 CF 2 CF 2 CF 2 CH 2 -, -cycloC 5 F 8 -, and the like.
• Gf6 examples include -CF2CF2CF2CF2CF2CF2CF2- , -CF2CF2CHFCHFCF2CF2CF2- , -CHFCF2CF2CF2CF2CF2CF2CF2- , -CHFCHFCHFCHFCHFCHF- , -CHFCF2CF2CF2CF2CF2CF2CH2- , -CH2CF2CF2CF2CF2CH2- , -cycloC6F10- , and the like .
• -cycloC 4 F 6 - means a perfluorocyclobutanediyl group, a specific example of which is a perfluorocyclobutane-1,2-diyl group
• -cycloC 5 F 8 - means a perfluorocyclopentanediyl group, a specific example of which is a perfluorocyclopentane-1,3-diyl group
• -cycloC 6 F 10 - means a perfluorocyclohexanediyl group, a specific example of which is a perfluorocyclohexane-1,4-diyl group.
• (OR f11 ) y1 preferably has a structure represented by any one of the following formulae (G2) to (G4), in that it provides superior water and oil repellency, friction durability, and fingerprint stain removability.
• G4 ) m3 formula (G4) the symbols in formulas (G2) to (G4) are the same as those in formula (G11) above.
• the bonding order of (OG f1 ) and (OG f2 ), and (OG f2 ) and (OG f4 ) are each arbitrary.
• (OG f1 ) and (OG f2 ) may be arranged alternately, (OG f1 ) and (OG f2 ) may be arranged in blocks, or may be arranged randomly.
• m1 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
• m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
• m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
• m4 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
• m3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
• the ratio of fluorine atoms in the fluoroether chain or fluoropolyether chain (OR f11 ) y1 is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, from the viewpoint of excellent water/oil repellency and fingerprint removability.
• the upper limit is, for example, 100%.
• the molecular weight of the fluoroether chain or fluoropolyether chain (OR f11 ) y1 portion is preferably from 2,000 to 20,000, more preferably from 2,500 to 15,000, and even more preferably from 3,000 to 10,000, from the viewpoint of friction durability.
• R 1 is an alkylene group or a fluoroalkylene group.
• the alkylene group and the fluoroalkylene group in R 1 may be linear, or may have a branched and/or ring structure. From the viewpoint of ease of synthesis, etc., a linear or branched alkylene group or a fluoroalkylene group is preferred, and a linear or branched alkylene group or a fluoroalkylene group having a methylene group or a fluoromethylene group is more preferred.
• the number of carbon atoms in R 1 is preferably 1 to 30, more preferably 1 to 30, and even more preferably 1 to 10.
• j represents the number of [R f1 -(OR f11 ) y1 -O-R 1 ] in one molecule and may be an integer of 1 or more, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.
• R 11 is an alkylene group in which the atom bonded to L 1 may be an ethereal oxygen atom or which may have an ethereal oxygen atom between the carbon atoms.
• the alkylene group in R 11 may be linear or may have a branched and/or cyclic structure.
• a linear or branched alkylene group is preferred, and a linear alkylene group is more preferred, since the compound (A1) is likely to be densely arranged when forming a surface layer.
• the alkylene group for R 11 preferably has a carbon chain in which two or more carbon atoms are linked, in order to provide a surface layer with excellent water and oil repellency, excellent fingerprint removability, and excellent durability such as abrasion resistance.
• the alkylene group in R 11 preferably has a carbon chain with 3 or more carbon atoms, more preferably has a carbon chain with 4 or more carbon atoms, particularly preferably has a carbon chain with 9 or more carbon atoms, and most particularly preferably has a carbon chain with 11 or more carbon atoms.
• the upper limit of the number of carbon atoms is not particularly limited, but from the viewpoint of obtaining superior water and oil repellency and fingerprint removability, the number of carbon atoms is preferably 20 or less, and more preferably 19 or less.
• R 11 is preferably a linear alkylene group having 3 to 20 carbon atoms, more preferably a linear alkylene group having 4 to 20 carbon atoms, still more preferably a linear alkylene group having 9 to 20 carbon atoms, and particularly preferably a linear alkylene group having 11 to 20 carbon atoms.
• having a carbon chain with X or more carbon atoms linked together means that R 11 contains an alkylene group with X or more carbon atoms.
• the carbon atoms of the branched and cyclic structures are also included.
• -CH 2 CH 2 CH(-CH 2 CH 3 )-CH 2 CH 2 CH 2 CH 2 - has a carbon chain with 9 carbon atoms linked together, including the branched carbon atoms.
• At least one of R 11 preferably has a carbon chain with 4 or more carbon atoms linked thereto, and the carbon chain is linked to T 11 , and when there are multiple R 11 , it is more preferable that all of the multiple R 11 have a carbon chain with 4 or more carbon atoms linked thereto, and the carbon chain is linked to T 11.
• the preferred embodiment of the number of carbon atoms linked to the carbon chain is as described above.
• R 11 can be represented by formula (g2). *-(O) a1 -(R g2 O) a2 -R g2 -** ... (g2) however, R g2 is an alkylene group having 1 or more carbon atoms, and a plurality of R g2 may be the same or different.
• a1 is 0 or 1;
• a2 is an integer of 0 or more, * is a bond bonded to L1 , ** is a bond bonded to T11 .
• a1 When a1 is 0, the atom having the bond * is a carbon atom, and when a1 is 1, the atom having the bond * is an oxygen atom.
• a1 may be either 0 or 1, and may be appropriately selected from the viewpoint of synthesis, etc.
• a2 is the number of repetitions of R g2 O, and is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1, from the standpoint of durability as a surface layer, etc.
• the alkylene group represented by R g2 is the same as the alkylene group in R 11 above, and preferred embodiments are also the same.
• R 11 is more preferably a group represented by formula (g3) from the viewpoint of providing a surface layer with excellent water and oil repellency, excellent fingerprint removability, and excellent durability such as abrasion resistance.
• *-(O) a1 -R g3 -** ... (g3) R g3 is an alkylene group; a1, * and ** are the same as in formula (g2).
• the alkylene group represented by R g3 is the same as the alkylene group in R 11 above, and preferred embodiments are also the same.
• T 11 is a group represented by -SiR a11 z11 R a12 3-z11 .
• R a11 , R a12 and z11 are each independently the same as R a11 , R a12 and z11 constituting T 11 in the above formula (A1), and preferred embodiments are also the same.
• x1 represents the number of R 11 -T 11 in one molecule and may be an integer of 1 or more, or may be an integer of 2 or more, preferably an integer of 2 to 32, more preferably an integer of 2 to 18, and even more preferably an integer of 2 to 12.
• the atoms bonded to R 1 and R 11 may be the same atom or different atoms.
• L 1 When L 1 is a trivalent or higher group, L 1 has at least one branch point (hereinafter also referred to as “branch point P 1 ”) selected from the group consisting of C, N, Si, a ring structure, and a (j+x1)-valent organopolysiloxane residue.
• branch point P 1 branch point selected from the group consisting of C, N, Si, a ring structure, and a (j+x1)-valent organopolysiloxane residue.
• the branch point P1 is represented, for example, by *-N(-**) 2 or (*-) 2N -**, where * is a bond on the R1 side and ** is a bond on the R11 side.
• the branch point P1 is represented, for example, by *-C(-**) 3 , (*-) 2C (-**) 2 , (*-) 3C -**, * -CR29 (-**) 2 , or (*-) 2CR29 -**.
• R29 is a monovalent group, for example, a hydrogen atom, a hydroxyl group, a hydrocarbon group, or an alkoxy group.
• the hydrocarbon group include aliphatic hydrocarbon groups such as a linear alkyl group, a branched alkyl group, and a cycloalkyl group, aromatic hydrocarbon groups such as a phenyl group, or a group consisting of a combination of these.
• the branch point P1 can be represented, for example, by *-Si(-**) 3 , (*-) 2Si (-**) 2 , (*-) 3Si -**, * -SiR29 (-**) 2 , or (*-) 2SiR29 -**.
• * is a bond on the R1 side
• ** is a bond on the R11 side
• R29 is a monovalent group, such as a hydrogen atom, a hydroxyl group, a hydrocarbon group, or an alkoxy group.
• hydrocarbon group examples include aliphatic hydrocarbon groups such as a linear alkyl group, a branched alkyl group, or a cycloalkyl group, aromatic hydrocarbon groups such as a phenyl group, or a group consisting of a combination of these.
• the ring structure constituting the branch point P1 from the viewpoints of ease of production of the compound (A1) and further superior abrasion resistance, light resistance and chemical resistance of the surface layer, one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle and a condensed ring consisting of two or more of these rings is preferred, and the ring structure shown in the following formula is more preferred.
• R 25 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
• the number of carbon atoms in the alkyl group and alkoxy group of R 25 is preferably 1 to 10, and more preferably 1. Multiple R 25s may be the same or different.
• L 1 which is divalent or higher is at least one bond selected from the group consisting of -C(O)N(R 26 )-, -N(R 26 )C(O)-, -C(O)O-, -OC(O)-, -C(O)-, -C(OH)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N(R 26 )-, -SO 2 N(R 26 )-, -N(R 26 )SO 2 -, -Si(R 26 ) 2 -, -OSi(R 26 ) 2 -, -Si(CH 3 ) 2 -Ph-Si(CH 3 ) 2 - and a divalent organopolysiloxane residue (hereinafter referred to as ").
• R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group.
• the number of carbon atoms in the alkyl group of R 26 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
• R 27 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
• the number of carbon atoms in the alkyl group and alkoxy group of R 27 is preferably 1 to 10, and more preferably 1. Multiple R 27s may be the same or different.
• bond B1 from the viewpoint of ease of production of compound (A1), at least one bond selected from the group consisting of -C(O)NR -, -N( R )C(O)-, -C(O)- and -NR - is preferred, and from the viewpoint of further improving the light resistance and chemical resistance of the surface layer, -C(O) NR -, -N( R )C(O)- or -C(O)- is more preferred.
• Specific examples of the divalent L 1 include one or more bonds B 1 (for example, *-B 1 -**, *-B 1 -R 28 -B 1 -**).
• R 28 is a single bond or a divalent organic group
• * is a bond on the R 1 side
• ** is a bond on the R 11 side.
• trivalent or higher L 1 include one or more branch points P 1 (for example, ⁇ (*-) jP 1 (-**) x1 ⁇ , ⁇ (*-) jP 1 -R 28 -P 1 (-**) x1 ⁇ , etc.), and combinations of one or more branch points P 1 and one or more bonds B 1 (for example, ⁇ *-B 1 -R 28 -P 1 (-**) x1 ⁇ , ⁇ * -B 1-R 28 -P 1 (-R 28 - B 1 -**) x1 ⁇ , where R 28 is a single bond or a divalent organic group, * is a bond on the R 1 side, and ** is a bond on the R 11 side.
• branch points P 1 for example, ⁇ (*-) jP 1 (-**) x1 ⁇ , ⁇ (*-) jP 1 -R 28 -P 1 (-**) x1 ⁇ , etc.
• bonds B 1 for example, ⁇ *
• the divalent organic group in R 28 includes hydrocarbon groups such as divalent aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups, etc.) and divalent aromatic hydrocarbon groups (phenylene groups, etc.), and the hydrocarbon groups may have a bond B 1 between a carbon-carbon atom.
• the divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.
• a 1 , A 2 or A 3 is connected to R 1 in formula (A1), and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 is connected to R 11 .
• a 1 is a single bond, -B 3 -, -B 3 -R 30 -, or -B 3 -R 30 -B 2 -, where R 30 is an alkylene group or a group having -C(O)NR e6 -, -C(O)-, -NR e6 - or -O- between carbon atoms of an alkylene group having 2 or more carbon atoms, B 2 is -C(O)NR e6 -, -C(O)-, -NR e6 - or -O-, and B 3 is -C(O)NR e6 -, -C(O)-, or -NR e6 -;
• a 2 is a single bond or -B 3
• the orientation of B2 and B3 does not matter.
• the plurality of A1 may be the same or different. The same applies to A2 , A3 , Q22 , Q23 , Q24 , Q25 , R e1 , R e2 , and R e3 .
• d1+d3, d5, d7, d8, and d10 are j
• d2+d4 are d6, 3-d7, d9, d11, and 1+d12 are x1.
• the number of carbon atoms in the alkylene group of R 30 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4, from the viewpoints of ease of production of compound (A1) and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer.
• the lower limit of the number of carbon atoms in the alkylene group is 2. Examples of the ring structure in Z1 include the ring structures described above, and preferred embodiments are also the same.
• the number of carbon atoms in the alkyl group of R e1 , R e2 or R e3 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of compound (A1).
• the number of carbon atoms in the alkyl group portion of the acyloxy group for R e2 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of compound (A1).
• d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoints of ease of production of compound (A1) and of further improving the abrasion resistance and fingerprint removability of the surface layer.
• L1 include groups represented by any one of formulae (L11) to (L17).
• a 1 , A 2 or A 3 is connected to R 1 of formula (A1), and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 is connected to R 11.
• G is the following group (G21), and two or more Gs in L 1 may be the same or different.
• the symbols other than G are the same as the symbols in formulae (L11) to (L17). -Si( R51 ) 3-k ( -Q3- ) k ... (G21)
• R 51 is an alkyl group.
• Q 3 is a single bond or -R 31 -B 3 -, where R 31 is an alkylene group or an alkylene group having 2 or more carbon atoms and having -C(O)NR 32 -, -C(O)-, -NR 32 - or -O- between carbon atoms, or -(OSi(R 22 ) 2 ) p11 -O-, and two or more Q 3s may be the same or different.
• k is 2 or 3.
• R 32 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.
• R 22 is an alkyl group, a phenyl group or an alkoxy group, and two R 22s may be the same or different.
• p11 is an integer of 0 to 5, and when p11 is 2 or more, the 2 or more (OSi(R 22 ) 2 ) may be the same or different.
• the number of carbon atoms in the alkylene group of R 31 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4.
• the lower limit of the number of carbon atoms in the alkylene group is 2.
• the number of carbon atoms in the alkyl group of R 51 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of compound (A1).
• the number of carbon atoms in the alkyl group of R 22 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of compound (A1).
• the number of carbon atoms in the alkoxy group of R 22 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of excellent storage stability of compound (A1).
• p11 is preferably 0 or 1.
• the molecular weight of the group represented by L 1 -(R 11 -T 11 ) x1 is preferably 300 or more, more preferably 450 or more, and even more preferably 600 or more, in view of further improving the friction durability of the surface layer.
• the molecular weight is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less, from the viewpoint of superior antifouling properties.
• the ratio of the molecular weight of the fluoropolyether chain represented by [R f1 -(OR f11 ) y1 -O-R 1 ] j to the molecular weight of the group represented by L 1 -(R 11 -T 11 ) x1 is preferably 10% or more, more preferably 12% or more, and even more preferably 13% or more, from the viewpoint of further improving the friction durability of the surface layer.
• the upper limit of the above ratio is preferably 40% or less, and more preferably 25% or less, in terms of better antifouling properties.
• Examples of compound (A1) include the following:
• each R f2 is independently the same as [R f1 -(OR f11 ) y1 -O-R 1 ] or [R f1 -(OR f11 ) y1 -O-], T is the same as T 11 , and Me is a methyl group.
• the compound (A2) has a structure represented by the following formula (A2). ( T31 - R31 ) x3 - L3 - R3- ( ORf12 ) y2 - OR2 - L2- ( R21 - T21 ) x2 ...(A2)
• each symbol in formula (A2) is as defined above.
• R f12 and (OR f12 ) y2 are the same as R f11 and (OR f11 ) y1 above, and preferred embodiments are also the same.
• R2 and R3 are each independently the same as R1 above, and preferred embodiments are also the same.
• R21 and R31 are the same as R11 , and the preferred embodiments are also the same.
• “bonded to L1” is to be read as “bonded to L2 " in the case of R21 , and as “bonded to L3 “ in the case of R31 .
• “bonded to T11” is to be read as “bonded to T21 “ in the case of R21 , and as “bonded to T31 “ in the case of R31 .
• R 21 and R 31 at least one of R 21 has a carbon chain with 4 or more carbon atoms connected thereto, and the carbon chain is preferably connected to T 21
• all of the multiple R 21 have a carbon chain with 4 or more carbon atoms connected thereto, and the carbon chain is connected to T 21.
• all of the multiple R 31 have a carbon chain with 4 or more carbon atoms connected thereto, and the carbon chain is connected to T 31.
• the preferred embodiment of the number of carbon atoms connected to the carbon chain is as described above.
• T 21 and T 31 are each independently -SiR a21 z21 R a22 3-z21 , and R a21 , R a22 and z21 are each independently the same as R a11 , R a12 and z11 constituting T 11 , and preferred embodiments are also the same.
• x2 and x3 are each independently the same as x1, and the preferred embodiments are also the same.
• L2 and L3 each independently have the same meaning as in the above L1 when j is 1.
• the compound (A2) is represented by the following formula (A2').
• each symbol in formula (A2') is the same as in formula (A2).
• the trivalent or higher L2 or L3 has at least one branch point (hereinafter referred to as "branch point P2 ") selected from the group consisting of C, N, Si, a ring structure, and a (1+x2)- or (1+x3)-valent organopolysiloxane residue.
• branch point P2 branch point selected from the group consisting of C, N, Si, a ring structure, and a (1+x2)- or (1+x3)-valent organopolysiloxane residue.
• the branch point P2 is represented, for example, as *-N(-**) 2 , where * is a bond on the R2 or R3 side, and ** is a bond on the R21 or R31 side.
• the branch point P2 is represented, for example, by *-C(-**) 3 or * -CR29 (-**) 2 , where * is a bond on the R2 or R3 side, ** is a bond on the R21 or R31 side, and R29 is a monovalent group.
• R29 include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.
• the branch point P2 is represented by, for example, *-Si(-**) 3 or *-SiR 29 (-**) 2 .
• * represents a bond on the R2 or R3 side
• ** represents a bond on the R21 or R31 side
• R29 represents a monovalent group. Examples of R29 include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.
• the ring structure and organopolysiloxane residue constituting branch point P2 are the same as those for branch point P1 , and preferred embodiments are also the same. Furthermore, divalent or more L2 or L3 may each independently have the above bond B1 .
• the embodiment of the bond B1 is as described above, and the preferred embodiment is also the same.
• Specific examples of the divalent L 2 or L 3 include one or more bonds B 1 (for example, *-B 1 -**, *-B 1 -R 28 -B 1 -**).
• R 28 is a single bond or a divalent organic group
• * is a bond on the R 2 or R 3 side
• ** is a bond on the R 21 or R 31 side.
• L 2 or L 3 examples include one or more branch points P 2 (for example, ⁇ *-P 2 (-**) x ⁇ , ⁇ *-P 2 -R 28 -P 2 -** x ⁇ , etc.), and combinations of one or more branch points P 2 and one or more bonds B 1 (for example, ⁇ *-B 1 -R 28 -P 2 (-**) x ⁇ , ⁇ *-B 2 -R 28 -P 2 (-R 28 -B 1 -**) x ⁇ , etc.).
• x is x2 in the case of L 2
• x3 in the case of L 3.
• R 28 is a single bond or a divalent organic group, * is a bond on the R 2 or R 3 side, and ** is a bond on the R 21 or R 31 side.
• the embodiments of R 28 are as described above, and the preferred embodiments are also the same.
• a 1 , A 2 or A 3 is connected to R 2 or R 3
• Q 22 , Q 23 , Q 24 , Q 25 or Q 26 is connected to R 21 or R 31 .
• A1 , A2 , A3 , Q11 , Q22 , Q23 , Q24 , Q25, Q26 , R e1 , R e2 , R e3 and R e6 are the same as those explained in L1 above, and preferred embodiments are also the same.
• Z1 is a group having a (1+d9)-valent ring structure having a carbon atom or nitrogen atom to which A3 is directly bonded and a carbon atom or nitrogen atom to which Q24 is directly bonded;
• d2 is an integer from 0 to 3
• d4 is an integer from 0 to 3
• d2+d4 is an integer from 2 to 5;
• d6 is an integer between 2 and 3
• d9 is an integer of 2 or more, d11 is an integer from 2 to 3; and
• d12 is an integer from 1 to 3.
• d2+d4, d6, d9, d11, and 1+d12 are x2 or x3.
• d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoints of ease of production of compound (A2) and of further improving the friction durability and fingerprint removability of the surface layer.
• L2 or L3 include groups represented by any one of formulae (L31) to (L37).
• a 1 , A 2 or A 3 is connected to R 2 or R 3
• Q 22 , Q 23 , Q 24 , Q 25 or Q 26 is connected to R 21 or R 31.
• G is the above group (G21), and preferred embodiments are also the same.
• the symbols other than G are the same as the symbols in formulae (L21) to (L27), and preferred embodiments are also the same.
• the molecular weight of at least one of the group represented by L 2 -(R 21 -T 21 ) x2 and the group represented by (T 31 -R 31 ) x3 -L 3 is preferably 300 or more, more preferably 450 or more, and even more preferably 600 or more, from the viewpoint of further improving the friction durability of the surface layer.
• the molecular weight is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less, from the viewpoint of superior antifouling properties.
• the ratio of the molecular weight of the group represented by R 3 -(OR f12 ) y2 -O-R 2 to the total molecular weight of the group represented by L 2 -(R 21 -T 21 ) x2 and the group represented by (T 31 -R 31 ) x3 -L 3 is preferably 10% or more, more preferably 12% or more, and even more preferably 13% or more, from the viewpoint of further improving the friction durability of the surface layer.
• the upper limit of the above ratio is preferably 40% or less, and more preferably 25% or less, in terms of better antifouling properties.
• Examples of compound (A2) include the following:
• each R f3 independently represents the same as [R 3 --(OR f12 ) y2 --O--R 2 ] or [(OR f12 ) y2 --O], and T represents the same as T 21 or T 31 .
• Compound (A3) has a structure represented by the following formula (A3).
• Q 1 [-(OR f13 ) y3 -O-R 4 -L 4 -(R 41 -T 41 ) x4 ] r1 ...(A3)
• each symbol in formula (A3) is as defined above.
• R f13 and (OR f13 ) y3 are the same as R f11 and (OR f11 ) y1 above, and preferred embodiments are also the same.
• R4 is the same as R1 above, and the preferred embodiments are also the same.
• R 41 is the same as R 11 , and the preferred embodiments are also the same. However, “bonded to L 1 " should be read as “bonded to L 4 ". Furthermore, “bonded to T 11 " should be read as “bonded to T 41 ". As a specific example of a preferred embodiment of R 41 , it is preferable that at least one of R 41 has a carbon chain with 4 or more carbon atoms linked thereto, and the carbon chain is linked to T 41 , and when there are multiple R 41 , it is more preferable that all of the multiple R 41 have a carbon chain with 4 or more carbon atoms linked thereto, and the carbon chain is linked to T 41. The preferred embodiment of the number of carbon atoms linked to the carbon chain is as described above.
• T 41 is --SiR a41 z41 R a42 3-z41 , and R a41 , R a42 and z41 are each independently the same as R a11 , R a12 and z11 constituting T 11 , and preferred embodiments are also the same.
• Q 1 is a r1-valent group having a branch point, and r1 is 3 or 4.
• branch point P3 examples include N, C, Si, and a ring structure.
• the number of branch points P3 may be one or more.
• the branch point P3 is expressed as, for example, N(-*) 3 , NR29 (-*) 2 .
• examples of the branch point P3 include C(-*) 4 , CR29 (-*) 2 , and C( R29 ) 2 (-*) 2 .
• examples of the branch point P3 include Si(-*) 4 , SiR29 (-*) 3 , and Si( R29 ) 2 (-*) 2 .
• * represents a bond on the OR f13 side
• R 29 represents a monovalent group. Examples of R 29 include a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, and a fluoropolyether chain not having R 41 -T 41 .
• Examples of the ring structure constituting the branch point P3 include the same ring structure as the ring structure constituting the branch point P1 , and the ring structure may have, in addition to the above-mentioned substituents, at least one group selected from the group consisting of a fluorine atom, a fluoroalkyl group, and a fluoropolyether chain not having R 41 -T 41 as a substituent.
• a 11 , A 12 or A 13 is connected to (OR f13 ).
• a 11 represents a single bond, -R 40 -, or -B 13 -R 40 -, in which R 40 represents an alkylene group, a fluoroalkylene group, or a group having -C(O)NR e16 -, -C(O)-, -CO(O)-, -NR e16 -, or -O- between carbon-carbon atoms of an alkylene group or fluoroalkylene group having 2 or more carbon atoms, and B 13 represents -C(O)NR e16 -, -C(O)-, -NR e16 -, or -O-,
• a 12 is a single bond or —R 40 —;
• a 13 is A 11 when the atom in Z 1 to which A 13 is bonded is a carbon atom, and is A 12 when the atom in Z 1 to which
• the number of carbon atoms in the alkylene group or fluoroalkylene group of R 40 is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of compound (A3) and of further improving the friction durability, light resistance, and chemical resistance of the surface layer.
• the lower limit of the number of carbon atoms is 2. Examples of the ring structure in Z1 include the ring structure constituting the branch point P3 described above, and preferred embodiments are also the same.
• the alkyl group or fluoroalkylene group for R e11 , R e12 or R e13 preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms, from the viewpoint of ease of production of compound (A3).
• the molecular weight of at least one of the groups represented by L 4 -(R 41 -T 41 ) x4 is preferably 300 or more, more preferably 450 or more, and even more preferably 600 or more, from the viewpoint of further improving the friction durability of the surface layer.
• the molecular weight is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less, from the viewpoint of superior antifouling properties. It is also preferable that the molecular weight of each of the groups represented by L 4 -(R 41 -T 41 ) x4 is within the above range.
• the ratio of the sum of the molecular weights of r1 groups represented by (OR f13 ) y3 -O-R 4 and the sum of the molecular weights of the group represented by Q 1 to the sum of the molecular weights of r1 groups represented by L 4 -(R 41 -T 41 ) x4 is preferably 10% or more, more preferably 12% or more, and even more preferably 13% or more, from the viewpoint of further improving the friction durability of the surface layer.
• the upper limit of the above ratio is preferably 40% or less, and more preferably 25% or less, in terms of better antifouling properties.
• Examples of compound (A3) include the following:
• each ⁇ --O--R f4 -- ⁇ is independently the same as [--(OR f13 ) y3 --O--R 4 --] r1 or [--(OR f13 ) y3 --O--] r1
• T is the same as T41 .
• the present composition may contain one type of the first component alone, or may contain two or more types.
• the content of the first component is preferably from 1 to 99% by mass, more preferably from 5 to 95% by mass, and even more preferably from 10 to 90% by mass, based on the total mass of the composition.
• the concentration of the first component relative to the total molar amount of the first component and the second component contained in the composition is preferably 5 to 95 mol %, and more preferably 10 to 90 mol %.
• the second component contained in the composition of the present invention is at least one fluorine-containing ether compound selected from the group consisting of compound (B1) and compound (B2).
• the second component may contain both compound (B1) and compound (B2), or only one of them.
• R f14 is a fluoroalkyl group having 1 to 20 carbon atoms
• R f15 is a fluoroalkylene group having 1 to 6 carbon atoms, and when there are multiple R f15s , the multiple R f15s may be the same or different from each other
• R5 is an alkylene group which may have a substituent
• R b1 is a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom
• y4 is an integer of 1 or more.
• R f17 and R f19 each independently represent a fluoroalkyl group having 1 to 20 carbon atoms;
• R f16 and R f18 each independently represent a fluoroalkylene group having 1 to 6 carbon atoms, and when there is a plurality of R f16s , the plurality of R f16s may be the same as or different from one another, and when there is a plurality of R f18s , the plurality of R f18s may be the same as or different from one another,
• R 6 and R 7 each independently represent an alkylene group which may have a substituent;
• L b1 represents a single bond or a divalent linking group (excluding (OR f18 ) y7 and (R f16 O) y8 , where y7 and y8 are each independently an integer of 1 or more);
• Each of y5 and y6 independently represents an integer of 1 or more.
• the compound (B1) is a compound represented by formula (B1). R f14 -(OR f15 ) y4 -O-R 5 -R b1 ... (B1)
• each symbol in formula (B1) is as defined above.
• R f14 is a fluoroalkyl group having 1 to 20 carbon atoms.
• the number of carbon atoms in the fluoroalkyl group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3, in terms of providing a surface layer with better water repellency.
• the fluoroalkyl group may be linear, branched or cyclic.
• the fluoroalkyl group is preferably a fluoroalkyl group in which all hydrogen atoms have been substituted with fluorine atoms (perfluoroalkyl group).
• R f15 is a fluoroalkylene group having 1 to 6 carbon atoms.
• the preferred embodiments of R f15 are the same as those of R f11 in the above formula (A1).
• the preferred embodiments of (OR f15 ) are the same as those of (OR f11 ) in the above formula (A1).
• the number of repetitions y4 of (OR f15 ) is an integer of equal to or greater than 1.
• Preferred embodiments of y4 are the same as the number of repetitions y1 of (OR f11 ) described above.
• R5 is an alkylene group which may have a substituent.
• the number of carbon atoms in the alkylene group which may have a substituent is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10, and particularly preferably 1 to 6.
• the number of carbon atoms of the substituent is not included in the number of carbon atoms in the alkylene group which may have a substituent.
• the alkylene group which may have a substituent may be any of linear, branched and cyclic.
• alkylene group can have includes, for example, halogen atom, hydroxyl group, and amino group.
• the halogen atom includes, for example, fluorine atom, chlorine atom, bromine atom, and iodine atom, and fluorine atom is preferred.
• alkylene group has fluorine atom, that is, fluoroalkylene group, it can be a group (perfluoroalkylene group) in which all hydrogen atoms in fluoroalkylene group are replaced with fluorine atom.
• R5 is preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (i.e., a fluoroalkylene group excluding perfluoroalkylene groups), and further preferably -Rfb1 - Rb11- .
• Rfb1 is a perfluoroalkylene group having 1 to 6 carbon atoms
• Rb11 is an unsubstituted alkylene group having 1 to 6 carbon atoms
• Rb11 is bonded to Rb1 .
• the total number of carbon atoms of Rfb1 and Rb11 is the same as the number of carbon atoms of R5 described above.
• R b1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.
• R b1 is preferably a hydrogen atom or an iodine atom, and more preferably a hydrogen atom.
• Two or more types of compound (B1) may be used in combination.
• compound (B1) Specific examples of compound (B1) are shown below.
• PFPE in the following compounds is the same as R f14 -(OR f15 ) y4 - in formula (B1), and the preferred embodiments are also the same.
• R fb1 is a perfluoroalkylene group having 1 to 6 carbon atoms, and represents a partial structure of R 5 in formula (B1).
• X in the following compounds is the same as R b1 in formula (B1), and the preferred embodiments are also the same.
• R is the same as the substituent that the alkylene group which may have a substituent represented by R 5 in formula (B1) may have, and the preferred embodiments are also the same.
• the method for producing compound (B1) is not particularly limited, but may be described in WO 2013/121984.
• the compound (B2) is a compound represented by formula (B2).
• each symbol in formula (B2) is as defined above.
• R f17 and R f19 each independently represent a fluoroalkyl group having 1 to 20 carbon atoms.
• Preferred embodiments of R f17 and R f19 are the same as those of R f14 in formula (B1) above.
• R f16 and R f18 are each independently a fluoroalkylene group having 1 to 6 carbon atoms. Preferred embodiments of R f16 and R f18 are the same as those of R f15 in formula (B1) above.
• the repeat number y5 of (R f16 O) is an integer of equal to or greater than 1.
• Preferred embodiments of y5 are the same as the repeat number y4 of (OR f15 ) described above.
• the number of repetitions y6 of (OR f18 ) is an integer equal to or greater than 1.
• Preferred embodiments of y6 are the same as the number of repetitions y4 of (OR f15 ) described above.
• R f16 and R f18 in formula (B2) are preferably the same groups as R f11 in formula (A1), R f12 in formula (A2), and R f13 in formula (A3) of the first component.
• R6 and R7 are alkylene groups which may have a substituent. Preferred embodiments of R6 and R7 are the same as R5 in the above formula (B1).
• the total number of carbon atoms in the alkylene group which may have a substituent represented by R6 and the alkylene group which may have a substituent represented by R7 is preferably 2 to 40, more preferably 2 to 20, and even more preferably 2 to 16.
• R 6 and R 7 may be the same group or different groups, but are preferably the same group.
• R 6 is preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (i.e., a fluoroalkylene group excluding a perfluoroalkylene group), and further preferably -R fb2 -R b12 -.
• R fb2 is a perfluoroalkylene group having 1 to 6 carbon atoms
• R b12 is an unsubstituted alkylene group having 1 to 6 carbon atoms
• R b12 is bonded to L b1 (when L b1 is a single bond, R 6 ).
• R 7 is preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (i.e., a fluoroalkylene group excluding a perfluoroalkylene group), and further preferably -R b13 -R fb3 -.
• R fb3 is a perfluoroalkylene group having 1 to 6 carbon atoms
• R b13 is an unsubstituted alkylene group having 1 to 6 carbon atoms
• R b13 is bonded to L b1 (when L b1 is a single bond, R 7 ).
• the total number of carbon atoms of R fb3 and R b13 is the same as the number of carbon atoms of R 7 described above.
• L b1 represents a single bond or a divalent linking group (excluding (OR f18 ) y7 and (R f16 O) y8 , where y7 and y8 are each independently an integer of 1 or greater).
• the divalent linking group include an alkylene group, an etheric oxygen atom, an amide bond, and a group formed by combining these.
• an alkylene group, a group formed by combining an alkylene group and an etheric oxygen atom, and a group formed by combining an alkylene group and an amide bond are preferred from the viewpoints of ease of production of the compound (B2) and thermal stability and chemical stability.
• the divalent linking group in L b1 does not include (OR f18 ) y7 and (R f16 O) y8 .
• (OR f18 ) and (R f16 O) are as defined above, and y7 and y8 each independently represent an integer of 1 or more.
• L b1 is preferably a single bond in that the effects of the present invention are more excellent.
• Two or more types of compound (B2) may be used in combination.
• R fb2 is a perfluoroalkylene group having 1 to 6 carbon atoms, and represents the partial structure of R 6 in formula (B2).
• R fb3 is a perfluoroalkylene group having 1 to 6 carbon atoms, and represents the partial structure of R 7 in formula (B2).
• R in the following compounds is the same as the substituent that may be possessed by the alkylene group that may have a substituent represented by R 6 and R 7 in formula (B2), and the preferred embodiments are also the same.
• the method for producing compound (B2) is not particularly limited, but an example is a method in which compounds (B1) are subjected to a known coupling reaction.
• the composition of the present invention may be a composition used in a dry coating method, or a composition used in a wet coating method.
• the composition of the present invention preferably contains a liquid medium.
• the liquid medium include water and organic solvents.
• the liquid medium preferably contains an organic solvent, and from the viewpoint of excellent coatability, more preferably contains an organic solvent having a boiling point of 35 to 250° C.
• the boiling point means the normal boiling point.
• Specific examples of the organic solvent include fluorine-based organic solvents and non-fluorine-based organic solvents, and fluorine-based organic solvents are preferred in terms of excellent solubility.
• the organic solvents may be used alone or in combination of two or more kinds.
• fluorine-based organic solvent examples include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and hydrofluoroolefins.
• the fluorinated alkane is preferably a compound having a carbon number of 4 to 8.
• Examples of commercially available products include C 6 F 13 H (manufactured by AGC, Asahiklin (registered trademark) AC-2000), C 6 F 13 C 2 H 5 (manufactured by AGC, Asahiklin (registered trademark) AC-6000), and C 2 F 5 CHFCHFCF 3 (manufactured by Chemours, Vertrel (registered trademark) XF).
• Examples of the fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.
• the fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms.
• CF 3 CH 2 OCF 2 CF 2 H manufactured by AGC, Asahiklin (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
• fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
• fluoroalcohols examples include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.
• hydrofluoroolefins include 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd), a reaction product of methanol and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene, and a reaction product of methanol and 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene.
• Commercially available products include Amorea® AS-300 manufactured by AGC and Opteon® (SF01, SF05, SF10, SF30, SF33, SF70, SF79, and SF80) manufactured by Chemours.
• the non-fluorine-based organic solvent is preferably a compound consisting only of hydrogen atoms and carbon atoms, or a compound consisting only of hydrogen atoms, carbon atoms, and oxygen atoms.
• Specific examples of the non-fluorine-based organic solvent include hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, alcohol organic solvents, amide organic solvents, and sulfoxide organic solvents.
• the organic hydrocarbon solvent is a compound consisting only of hydrogen atoms and carbon atoms, and any of aromatic hydrocarbons, aliphatic hydrocarbons, and unsaturated hydrocarbons can be used.
• Aromatic hydrocarbons include, for example, benzene, toluene, and xylene.
• Aliphatic hydrocarbons include, for example, n-hexane, n-heptane, n-octane, and n-decane.
• Unsaturated hydrocarbons include, for example, cyclopentene, hexene, heptene, and butene.
• Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, 2-heptanone, diisobutyl ketone, and diacetone alcohol.
• ether-based organic solvents include diethyl ether, diisopropyl ether, methyl t-butyl ether, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, cyclopentyl methyl ether, 4-methyltetrahydrofuran, 2-methyltetrahydrofuran, and glycol-based solvents.
• glycol-based solvents include mono- or di-alkylene glycol mono- or di-alkyl ethers, and mono- or di-alkylene glycol mono- or di-alkyl ether acetates.
• the alkylene group is preferably an ethylene group or a propylene group.
• the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. More specific examples of glycol-based solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether.
• ester-based organic solvent examples include ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, methyl formate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate, as well as ester compounds of the above glycol-based solvents with carboxylic acids such as acetic acid.
• Specific examples of the alcohol-based organic solvent include methanol, ethanol, propanol, isopropanol, and butanol. Note that the following glycol-based solvents are not included in the alcohol-based solvents.
• An example of an amide-based organic solvent is N,N-dimethylformamide.
• An example of a sulfoxide organic solvent is dimethyl sulfoxide.
• composition of the present invention may contain components other than those described above, provided that the effects of the present invention are not impaired.
• other components include compounds that are unavoidable in the production process, such as by-products produced in the production process of the first component or the second component, and unreacted raw materials.
• the content of the first component is preferably 20 to 99 mass%, more preferably 30 to 90 mass%, even more preferably 40 to 80 mass%, and particularly preferably 50 to 80 mass%, based on the total solid content mass of the composition of the present invention, from the viewpoint of more excellent effects of the present invention.
• the content of the second component is preferably 1 to 80 mass%, more preferably 10 to 70 mass%, further preferably 20 to 60 mass%, particularly preferably 20 to 50 mass%, based on the total solid content mass of the composition of the present invention, from the viewpoint of more excellent effects of the present invention.
• the content of the second component means the total content of the compound (B1) and the compound (B2), and when only one of them is contained, it means the content of that compound.
• the mass of the solid content of a composition refers to the mass of the composition excluding the liquid medium when the composition contains a liquid medium.
• the mass ratio of the content of the second component to the content of the first component is preferably 0.01 to 4.00, more preferably 0.01 to 1.50, even more preferably 0.01 to 1.00, and particularly preferably 0.01 to 0.50. If the mass ratio is within the above range, the wear resistance of the surface layer is more excellent.
• the content of the liquid medium is preferably 70 to 99.99 mass % relative to the total mass of the composition of the present invention, and particularly preferably 80 to 99.9 mass %.
• the content of other components in the composition of the present invention is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass, relative to the content of the specific fluorinated ether compound.
• the substrate with a surface layer of the present invention has a substrate and a surface layer formed from the above composition. Since the substrate with a surface layer of the present invention has a surface layer formed from the above composition, it has excellent abrasion resistance and also excellent water and oil repellency.
• the substrate is not particularly limited as long as it is a substrate that may be used by contacting with other articles (e.g., a stylus) or human fingers, a substrate that may be held by human fingers during operation, and/or a substrate that may be placed on other articles (e.g., a mounting table), and is required to be imparted with water and oil repellency.
• Specific examples of substrate materials include metals, resins, glass, sapphire, ceramics, stone, and composite materials thereof. Glass may be chemically strengthened.
• the substrate is preferably a substrate for a touch panel or a display substrate, more preferably a substrate for a touch panel.
• the substrate for a touch panel is preferably light-transmitting.
• Light-transmitting means that the normal incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more.
• the material of the substrate for a touch panel is preferably glass or a transparent resin.
• glass or resin films used for building materials, decorative building materials, interiors, transport equipment (e.g., automobiles), signs and notices, drinking vessels and tableware, aquariums, ornamental equipment (e.g., frames, boxes), laboratory equipment, furniture, art, sports and games, and glass sheets or resin films used for exterior parts (excluding display parts) of devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles and remote controls are also preferred.
• the substrate may be a substrate on one or both surfaces of which has been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment.
• a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment.
• the surface layer may be formed directly on the surface of the substrate, or may be formed on the substrate via another film formed on the surface of the substrate.
• Specific examples of the other film include a base film formed on the surface of the substrate by subjecting the substrate to a base treatment using the compounds described in paragraphs 0089 to 0095 of International Publication No. 2011/016458, SiO 2 , or the like.
• the surface layer is a layer formed from the above composition.
• the surface layer contains a condensate obtained by hydrolysis and dehydration condensation of a part or all of the reactive silyl groups of the specific fluorine-containing ether compound, which is the first component, and also contains the above-mentioned second component or a component derived therefrom.
• the thickness of the surface layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. When the thickness of the surface layer is equal to or greater than the lower limit, the effect of the surface layer can be sufficiently obtained. When the thickness of the surface layer is equal to or less than the upper limit, the utilization efficiency is high.
• the thickness of the surface layer can be calculated from the vibration period of an interference pattern obtained by X-ray reflectometry (XRR) using an X-ray diffractometer for thin film analysis.
• the method for producing the substrate with a surface layer of the present invention is a method for forming a surface layer on a substrate by a dry coating method or a wet coating method using the above-mentioned composition.
• the substrate with a surface layer of the present invention can be produced, for example, by the following method.
• a method of treating the surface of a substrate by a dry coating method using the above composition not containing a liquid medium (hereinafter also referred to as a "dry coating composition") to obtain a substrate with a surface layer in which a surface layer is formed on the surface of the substrate.
• a method in which the above-mentioned composition containing a liquid medium hereinafter also referred to as "wet coating composition” is applied to the surface of a substrate by a wet coating method, and then dried to obtain a substrate with a surface layer in which a surface layer is formed on the surface of the substrate.
• dry coating methods include vacuum deposition, CVD, and sputtering.
• vacuum deposition is preferred from the viewpoints of suppressing decomposition of the specific fluorine-containing ether compound and of the simplicity of the equipment.
• a pellet-like material in which a dry coating composition is supported on a metal porous body such as iron or steel, or a pellet-like material obtained by impregnating a wet coating composition and drying it may be used.
• wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.
• the drying temperature after wet coating of the composition is preferably 20 to 200°C, and particularly preferably 80 to 160°C.
• Examples 1-1 to 1-12 and Examples 2-1 to 2-12 are working examples, and Examples 1-13 and 2-13 are comparative examples. However, the present invention is not limited to these examples.
• the amounts of each component in the tables below are based on mass.
• a mixture containing compound Y6 was obtained by performing flash column chromatography using silica gel. It was confirmed by NMR measurement that compound X7 was obtained with a selectivity of 79%. In the formula, the average value of the number of repeating units n is 13.
• Example 1-1 A composition (1-1) was obtained by mixing 99 parts by mass of the compound A1-1 as the first component and 1 part by mass of the compound B1-1 as the second component.
• a molybdenum boat in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.) was filled with composition (1-1) (0.14 g) as a deposition source, and the vacuum deposition apparatus was evacuated to 1 ⁇ 10 -3 Pa or less.
• the boat in which composition (1-1) was placed was heated at a temperature increase rate of 10 ° C.
• the substrate on which composition (1-1) was deposited was heat-treated at 200 ° C. for 30 minutes and washed with dichloropentafluoropropane (AK-225 manufactured by AGC Co., Ltd.) to obtain a substrate with a surface layer having a surface layer on the surface of the substrate.
• Example 1-2 to Example 1-13 Except for changing the types and contents of the first and second components as shown in Tables 1 and 2, the same procedure as in Example 1-1 was carried out to obtain substrates with a surface layer in each example.
• ⁇ Initial water contact angle> The 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.). Measurements were performed at three different points on the surface of the surface layer, and the average value was calculated to obtain the initial water contact angle. The 2 ⁇ method was used to calculate the contact angle. Based on the obtained initial water contact angle value, the water repellency was evaluated according to the following evaluation criteria. A: Contact angle is 115 degrees or more. B: Contact angle is 105 degrees or more and less than 115 degrees. C: Contact angle is less than 105 degrees.
• ⁇ Wear resistance> For the surface layer, a reciprocating traverse tester (manufactured by KNT Co., Ltd.) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) to reciprocate steel wool Bonstar (number: #0000) at a pressure of 98.07 kPa and a speed of 320 cm/min. After 10,000 reciprocating steel wool abrasions, the water contact angle of the surface layer was measured, and the abrasion resistance was evaluated according to the following evaluation criteria. The smaller the change in the water contact angle before and after the abrasion test, the smaller the deterioration in performance due to abrasion, and the more excellent the abrasion resistance.
• the change in the water contact angle is less than 2 degrees.
• B The change in the water contact angle is 2 degrees or more and less than 4 degrees.
• C The change in the water contact angle is 4 degrees or more and less than 6 degrees.
• D The change in the water contact angle is 6 degrees or more.
• a surface layer having an excellent initial water contact angle and excellent abrasion resistance can be formed by using a composition containing a first component consisting of at least one selected from the group consisting of the compounds represented by compound (A1), compound (A2), and compound (A3), and a second component consisting of at least one selected from the group consisting of compound (B1) and compound (B2). It was confirmed that when the mass ratio of the content of the second component to the content of the first component was 0.01 to 0.50, the abrasion resistance was superior (Examples 1-1 to 1-12, Examples 2-1 to 2-12).
• At least one of R 11 has a carbon chain having 4 or more carbon atoms connected thereto, and the carbon chain is connected to T 11 ;
• at least one of R 21 has a carbon chain having 4 or more carbon atoms linked thereto, and the carbon chain is linked to T 21 , and at least one of R 31 has a carbon chain having 4 or more carbon atoms linked thereto, and the carbon chain is linked to T 31 ;
• formula (A3) when at least one of R 41 has a carbon chain with four or more carbon atoms linked thereto, and the carbon chain is linked to T 41 , it has been confirmed that the abrasion resistance is superior (Examples 1-4 and 2-4).

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Polyethers (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=90669620

Family Applications (1)

Country Status (5)

Citations (3)

Family Cites Families (1)

• 2023
  • 2023-10-11 CN CN202380072025.XA patent/CN120019117A/zh active Pending
  • 2023-10-11 JP JP2024551725A patent/JPWO2024080313A1/ja active Pending
  • 2023-10-11 WO PCT/JP2023/036909 patent/WO2024080313A1/ja not_active Ceased
  • 2023-10-11 KR KR1020257009381A patent/KR20250084119A/ko active Pending
• 2025
  • 2025-04-09 US US19/174,068 patent/US20250236763A1/en active Pending

Patent Citations (3)

Also Published As

Similar Documents

Legal Events