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WO2025182641A1 - Composition polymère contenant un groupe fluoropolyéther, agent de revêtement, article et procédé de modification de surface d'article - Google Patents

Composition polymère contenant un groupe fluoropolyéther, agent de revêtement, article et procédé de modification de surface d'article

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Publication number
WO2025182641A1
WO2025182641A1 PCT/JP2025/005176 JP2025005176W WO2025182641A1 WO 2025182641 A1 WO2025182641 A1 WO 2025182641A1 JP 2025005176 W JP2025005176 W JP 2025005176W WO 2025182641 A1 WO2025182641 A1 WO 2025182641A1
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Prior art keywords
group
formula
containing polymer
fluoropolyether
integer
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PCT/JP2025/005176
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English (en)
Japanese (ja)
Inventor
貴司 内田
美希 茂木
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Publication of WO2025182641A1 publication Critical patent/WO2025182641A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a composition containing a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule). More specifically, the present invention relates to a fluoropolyether group-containing polymer composition capable of forming a cured coating that has excellent water and oil repellency and abrasion resistance (particularly abrasion resistance to steel wool and nonwoven fabrics), a coating agent containing the composition, an article having a layer made of the cured product of the coating agent, and a method for modifying the surface of an article, which includes the steps of applying and curing the coating agent to form a layer.
  • a fluoropolyether group-containing polymer a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule. More specifically, the present invention relates to a fluoropolyether group-containing polymer composition capable of forming a cured coating that has excellent water
  • fluoropolyether group-containing compounds have extremely low surface free energy, resulting in properties such as water and oil repellency, chemical resistance, lubricity, mold release properties, and stain resistance. Utilizing these properties, they are widely used industrially as water, oil, and stain repellent agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, mold release agents, cosmetics, and protective films. However, these properties also mean that they are non-sticky and non-adherent to other substrates, and while they can be applied to the surface of a substrate, it has been difficult to ensure that the coating adheres to it.
  • silane coupling agents are well known for bonding organic compounds to the surface of substrates such as glass and cloth, and are widely used as coating agents for various substrate surfaces.
  • Silane coupling agents contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in each molecule.
  • the hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating.
  • This coating is durable and strong because the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.
  • compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, thereby forming coatings that adhere easily to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, and stain resistance (Patent Documents 1 to 6: JP-T-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, JP-A-2015-199906).
  • a cured coating (thin anti-fouling coating layer) on the surface of a glass substrate or the like that has been surface-treated with a composition containing a fluoropolyether group-containing polymer in which a hydrolyzable silyl group has been introduced into the fluoropolyether group-containing compound has excellent abrasion resistance against steel wool and high slipperiness.
  • the anti-fouling coating layer on the surface of a touch panel display has also been given importance for its usability when using the touch panel (good slipperiness and smooth feel).
  • a good usability is related to a low coefficient of friction (Patent Document 6: JP 2015-199906 A).
  • the present invention has been developed in light of the above circumstances, and aims to provide a fluoropolyether group-containing polymer composition capable of forming a cured coating that exhibits excellent water and oil repellency and abrasion resistance against various scrubbing materials (particularly abrasion resistance against steel wool and nonwoven fabrics); a coating agent containing the composition; an article having a layer made of the cured product of the coating agent; and a surface modification method for an article that includes the steps of applying and curing the coating agent to form a layer.
  • a coating agent containing the fluoropolyether group-containing polymer composition using the fluoropolyether group-containing polymers and/or partial (hydrolyzed) condensates thereof in combination can form a cured coating that is excellent in water and oil repellency and abrasion resistance to steel wool and nonwoven fabric, and thus completed the present invention.
  • the present invention provides the following fluoropolyether group-containing polymer composition, coating agent and article, and method for modifying the surface of an article.
  • A is a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 — or CF 2 H— and which may contain an oxygen atom;
  • Rf is —C d F 2 d —O—(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u —C d F 2 d -(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 200, the sum of p, q, r, s, t, and u is an integer of 1 to 250, and each of these
  • Y is independently a single bond, or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond
  • R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms
  • X is independently a hydroxyl group or a hydrolyzable group
  • a is independently 2 or 3 for each unit bonded to the silicon atom
  • W is a hydrogen atom or -OV
  • V is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (1a):
  • T is a single bond or a divalent group
  • L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms
  • k is an integer from 0 to 20
  • E is a monovalent hydrocarbon
  • D is represented by the following formula (2a):
  • M is a divalent to hexavalent hydrocarbon group which may have a silicon atom and/or a siloxane bond
  • m is an integer of 1 to 5
  • n is an integer of 1 to 3 for each unit bonded to a silicon atom.
  • Rf is represented by the following formula: (In the formula, p', q', r', s', t', and u' each represent an integer of 1 to 200, the sum of p', q', r', s', t', and u' is 10 to 250, and each of these units is linear.
  • each of the repeating units shown in parentheses with p', q', r', s', t', and u' may be bonded randomly.
  • d' is independently an integer of 0 to 5 for each unit, and each of these units is linear.
  • X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.
  • Abrasive material Bemcot (M-3II, manufactured by Ozu Sangyo Co., Ltd.) Load: 1 kgf Round trip distance: 40 mm Reciprocating speed: 60 reciprocations per minute Test environment conditions: 25°C, relative humidity 50% The water contact angle of the abraded portion is measured every 5,000 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle remains at 100 degrees or more is defined as the abrasion durability cycle of the nonwoven fabric.
  • a surface modification method for an article comprising a step of applying a coating agent containing the fluoropolyether group-containing polymer composition according to any one of [1] to [7] to the entire surface or a part of the surface of the article by a dry method or a wet method, and curing the coating agent to form a layer.
  • the fluoropolyether group-containing polymer composition of the present invention can provide a cured coating that has excellent water and oil repellency and high abrasion resistance against various scrubbing materials (particularly steel wool and nonwoven fabrics).
  • articles e.g., portable electronic device terminals, etc.
  • having a layer made of a cured product of a coating agent containing the composition of the present invention have water and oil repellency and high abrasion resistance (particularly abrasion resistance against steel wool and nonwoven fabrics).
  • partial (hydrolyzed) condensate refers to a partial condensate or a partial hydrolyzed condensate.
  • the fluoropolyether group-containing polymer composition of the present invention comprises fluoropolyether group-containing polymers and/or partial (hydrolyzed) condensates thereof of two specific components (components (I) and (II)) in specific proportions.
  • component (I) is a polymer and/or partial (hydrolyzed) condensate thereof that has a fluorooxyalkyl group at one end and two or more reactive functional groups (hydroxyl-containing silyl groups or hydrolyzable silyl groups) at the other end.
  • Component (II) is a polymer and/or partial (hydrolyzed) condensate thereof that has a fluorooxyalkylene group in its molecule and has reactive functional groups (hydroxyl-containing silyl groups or hydrolyzable silyl groups) bonded to both ends of the fluorooxyalkylene group via linking groups that do not have polar groups.
  • component (I) is a fluoropolyether group-containing polymer represented by the following formula (1) and/or a partial (hydrolyzed) condensate thereof.
  • A is a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 — or CF 2 H— and which may contain an oxygen atom;
  • Rf is —C d F 2 d —O—(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u —C d F 2 d -(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 200, the sum of p, q, r, s, t, and u is an integer of 1 to 250, and each of these units may be linear or branched.
  • Y is independently a single bond, or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond
  • R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms
  • X is independently a hydroxyl group or a hydrolyzable group
  • a is independently 2 or 3 for each unit bonded to the silicon atom
  • W is a hydrogen atom or -OV
  • V is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (1a):
  • T is a single bond or a divalent group
  • L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms
  • k is an integer from 0 to 20
  • E is a monovalent hydrocarbon
  • A is a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom
  • the monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably one in which the polymer terminal is CF3- or CF2H- .
  • Examples of such monovalent fluorine-containing hydrocarbon groups in which the terminal of A is CF 3 — or CF 2 H— and which may contain an oxygen atom include the following groups.
  • A is preferably a fluorine atom.
  • Rf is represented by the following formula: where d is independently an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0 or 1 for each unit.
  • p, q, r, s, t, and u are each independently an integer of 0 to 200, preferably an integer of 0 to 150, more preferably an integer of 0 to 100, and even more preferably an integer of 0 to 60, and the sum of p, q, r, s, t, and u is an integer of 1 to 250, preferably an integer of 3 to 200, more preferably an integer of 7 to 140, and even more preferably an integer of 10 to 70.
  • Each of these units may be linear or branched.
  • the repeating units shown in parentheses with p, q, r, s, t, and u may be randomly bonded.
  • the divalent fluoropolyether group Rf can be specifically represented by the following structure.
  • p', q', r', s', t', and u' each represent an integer of 1 to 200, and the sum of p', q', r', s', t', and u' is 10 to 250.
  • Each of these units may be linear or branched, but is preferably linear.
  • each of the repeating units shown in parentheses followed by p', q', r', s', t', and u' may be bonded randomly.
  • d' is independently an integer of 0 to 5 for each unit. Each of these units may be linear or branched, but is preferably linear.
  • Rf the following can be preferably used.
  • p" and q" are each an integer of 1 to 199, and the sum of p" and q" is an integer of 10 to 200, and the repeating units ( CF2CF2O ) and ( CF2O ) in the formula are arranged randomly.
  • Y is a single bond or a divalent hydrocarbon group which may have one or more bonds selected from fluorine atoms, silicon atoms, and siloxane bonds.
  • the divalent hydrocarbon group which may have one or more bonds selected from fluorine atoms, silicon atoms, and siloxane bonds is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms and containing a fluorine atom, alkylene groups containing an arylene group having 6 to 8 carbon atoms (alkylene-arylene groups), divalent groups in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopol
  • Y other than a single bond include the following: In the following structure, it is preferable that the left bond is bonded to a carbon atom and the right bond is bonded to a silicon atom.
  • R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with methyl and ethyl groups being preferred.
  • X is independently a hydroxyl group or a hydrolyzable group.
  • hydrolyzable groups for X include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups having 2 to 10 carbon atoms, such as acetoxy and propionoxy; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups, such as chlorine, bromine, and iodo. Among these, methoxy, ethoxy, isopropenoxy, and chlorine are preferred for X.
  • a is independently 2 or 3 for each unit bonded to a silicon atom, and is preferably 3 from the standpoints of reactivity and adhesion to the substrate.
  • W is a hydrogen atom or —OV
  • V is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (1a):
  • examples of monovalent hydrocarbon groups having 1 to 10 carbon atoms for V include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenylethyl. Of these, alkyl groups having 1 to 3 carbon atoms and phenyl groups are preferred.
  • T represents a single bond or a divalent group, and is preferably a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a silalkylene bond (e.g., a silethylene bond or a silpropylene bond), a silarylene bond (e.g., a silphenylene bond), and a diorganosilylene group (e.g., a dialkylsilylene group such as a dimethylsilylene group, or a dialkoxysilylene group such as a dimethoxysilylene group), or a divalent siloxane bond, silalkylene group, or diorganosilylene group; specific examples of T other than a single bond include those shown below. In the following structure, it is preferable that the right bond is bonded to L or E.
  • L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, such as an alkylene group, including a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group), and each (LO) unit may have a single carbon atom or a mixture of carbon atoms.
  • k is an integer from 0 to 20, preferably an integer from 0 to 10, and more preferably an integer from 0 to 6.
  • k is preferably 1 or greater, and particularly preferably 2 or greater.
  • E is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group; a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a phenyl group; or a monovalent hydroxyl-containing silyl group-containing or hydrolyzable silyl group-containing group represented by the following formula (1b): (In the formula, Y, R, X, and a are the same as above.)
  • Y, R, X, and a are the same as those described above, and examples thereof include the same as those exemplified for Y, R, X, and a in the above formula (1).
  • Examples of the monovalent group represented by the above formula (1a) include the groups shown below.
  • fluoropolyether group-containing polymer represented by the above formula (1) examples include the following. (In the formula, A and Rf are the same as above.)
  • Component (I) may be a single fluoropolyether group-containing polymer represented by the above formula (1), or a combination of two or more. It may also contain a partial (hydrolyzed) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer represented by the above formula (1), or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer in advance using a known method.
  • the number average molecular weight of the fluoropolyether group-containing polymer represented by the above formula (1) and/or its partial (hydrolyzed) condensate is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, and particularly preferably 3,000 to 6,000. If the number average molecular weight is less than 1,000, the surface coverage of the resulting coating agent will be poor and good water and oil repellency may not be obtained, whereas if it exceeds 10,000, the surface adhesion of the resulting coating agent will be poor and good abrasion resistance may not be obtained.
  • the number average molecular weight can be calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on 19F -NMR analysis, or can be determined as the number average molecular weight (or number average degree of polymerization) converted into polymethyl methacrylate resin by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as the developing solvent, but is preferably calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on 19F -NMR analysis (the same applies below).
  • GPC gel permeation chromatography
  • component (II) is a fluoropolyether group-containing polymer represented by the following formula (2) and/or a partial (hydrolyzed) condensate thereof.
  • Rf is the same as above, and D independently represents a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at a terminal and having no polar group.
  • the fluoropolyether group-containing polymer represented by the above formula (2) has a structure in which a fluorooxyalkylene group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group that does not have a polar group.
  • a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group at each end, for a total of two or more per molecule.
  • hydrolyzable silyl groups or hydroxyl group-containing silyl groups there are no polar groups within the molecule, specifically carbonyl groups, -NH- groups, amide groups, hydroxyl groups, etc., resulting in a simpler bonding pattern.
  • Rf is the same as above, and examples thereof include those similar to those exemplified for Rf in the above formula (1).
  • D independently represents a monovalent group having a hydroxyl-containing silyl group or a hydrolyzable silyl group at a terminal and no polar group, and is preferably a monovalent group consisting of a hydroxyl-containing silyl group or a hydrolyzable silyl group at a terminal and a linking group that links the silyl group with an O group (an ether-bonded oxygen atom) and has no polar group (such as a carbonyl group, an —NH— group, an amide group, or a hydroxyl group), and as such D, a group represented by the following formula (2a) is preferred: (In the formula, R and X are the same as above, M is a divalent to hexavalent hydrocarbon group which may have a silicon atom and/or a siloxane bond, m is an integer of 1 to 5, and n is an integer of 1 to 3 for each unit bonded to a silicon atom.)
  • the fluoropolyether group-containing polymer represented by the above formula (2) is preferably represented by the following formula (3).
  • M is independently a divalent to hexavalent hydrocarbon group, which may have a silicon atom and/or a siloxane bond
  • m is independently an integer of 1 to 5
  • n is independently an integer of 1 to 3 for each unit bonded to a silicon atom.
  • Rf, R, and X are the same as those described above, and examples thereof include the same Rf, R, and X as those exemplified in the above formula (1).
  • M is independently a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, which may contain a silicon atom and/or a siloxane bond, and by not containing polar groups in the molecule, a coating film with excellent water and oil repellency can be obtained.
  • M include alkylene groups having 3 to 10 carbon atoms, such as propylene, butylene, and hexamethylene; alkylene groups having 2 to 10 carbon atoms, including arylene groups having 6 to 8 carbon atoms, such as phenylene (for example, alkylene/arylene groups having 8 to 16 carbon atoms); divalent groups in which alkylene groups having 2 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure; and alkylene groups having 2 to 10 carbon atoms bonded to a bond of a linear, branched, or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms.
  • alkylene groups having 3 to 10 carbon atoms such as propylene, butylene, and hexamethylene
  • alkylene groups having 2 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms, such
  • Examples include divalent to hexavalent groups to which an alkylene group is bonded, preferably an alkylene group having 3 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms that includes a phenylene group, a divalent group in which alkylene groups having 2 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms, and more preferably an alkylene group having 3 to 6 carbon atoms.
  • Examples of the linear, branched or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 10, preferably 2 to 5, silicon atoms include the following: (wherein R1 is the same as above; x is an integer of 1 to 9, preferably an integer of 1 to 4; y1 is an integer of 2 to 6, preferably an integer of 2 to 4; y2 is an integer of 0 to 8, preferably 0 or 1; y1+y2 is an integer of 3 to 10, preferably an integer of 3 to 5; and z is 2 or 3.)
  • M examples include groups represented by the following formulas. (In the formula, x is the same as above. v is an integer of 3 to 10, preferably an integer of 3 to 6. v0 is an integer of 2 to 10, preferably an integer of 3 to 6. v1 is an integer of 2 to 6, preferably an integer of 2 to 4. v2 is independently an integer of 2 to 10, preferably an integer of 3 to 6.)
  • M include the following groups.
  • n is independently an integer of 1 to 5. If it is less than 1, adhesion to the substrate decreases, and if it is 6 or more, the terminal alkoxy value becomes too high and adversely affects performance. Therefore, m is preferably an integer of 1 to 3, and particularly preferably 1.
  • n is an integer of 1 to 3, which is independent for each unit bonded to a silicon atom, and is preferably 3 from the viewpoints of reactivity and adhesion to a substrate.
  • Examples of the fluoropolyether group-containing polymer represented by the above formula (2) include the following. (In the formula, p" and q" are each an integer of 1 to 199, and the sum of p" and q" is 10 to 200.)
  • Component (II) may be a single fluoropolyether group-containing polymer represented by formula (2) above, or two or more may be used in combination. It may also contain a partial (hydrolyzed) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer represented by formula (2) above, or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer in advance using a known method.
  • the number-average molecular weight of the fluoropolyether group-containing polymer represented by formula (2) above and/or its partial (hydrolyzed) condensate is preferably 1,000 to 10,000, more preferably 3,000 to 8,000, and particularly preferably 4,000 to 8,000. If the number-average molecular weight is less than 1,000, the surface coverage of the resulting coating agent will be poor and good water and oil repellency may not be achieved. If it exceeds 10,000, the surface adhesion of the resulting coating agent will be poor and good abrasion resistance may not be achieved.
  • the content of component (I) in the total of components (I) and (II) is 16% by mass or more but less than 55% by mass, preferably 16 to 50% by mass, and more preferably 16 to 40% by mass.
  • the content of component (II) in the total of components (I) and (II) is greater than 45% by mass but less than 84% by mass, preferably 50 to 84% by mass, and more preferably 60 to 84% by mass.
  • a component (I) content of less than 16% by mass (a component (II) content greater than 84% by mass)
  • high steel wool abrasion resistance due to the polymer mobility of component (I) cannot be obtained.
  • With a component (I) content of 55% by mass or more (a component (II) content of 45% by mass or less) high nonwoven fabric abrasion resistance due to the substrate adhesion of component (II) cannot be obtained.
  • the number average molecular weight of component (II) is preferably 0.6 to 1.6 times, and more preferably 0.7 to 1.4 times, the number average molecular weight of component (I).
  • the fluoropolyether group-containing polymer composition of the present invention can contain optional components such as hydrocarbon oils, silicone oils, fluoropolyether oils, silane coupling agents, surfactants, etc., as long as the purpose of the present invention is not impaired.
  • the present invention provides a coating agent containing the above-mentioned fluoropolyether group-containing polymer composition.
  • the coating agent of the present invention may contain a hydrolysis condensation catalyst, such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.).
  • acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable.
  • the amount of the hydrolysis and condensation catalyst added is a catalytic amount, which is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer composition.
  • the coating agent of the present invention may contain a suitable solvent.
  • suitable solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
  • fluorine-modified solvents are preferable in terms of solubility and wettability, and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are particularly preferred.
  • Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate).
  • the optimal concentration of the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) to be dissolved in the solvent varies depending on the processing method, and any amount that is easy to weigh may be used.
  • the concentration is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate).
  • the concentration is preferably 1 to 100 parts by mass, and more preferably 3 to 30 parts by mass, per 100 parts by mass of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate).
  • the coating agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition.
  • the heating method used during vapor deposition can be either resistance heating or electron beam heating, and is not particularly limited.
  • the curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), a temperature of 25 to 200°C, particularly 25 to 80°C, is preferred for 30 minutes to 36 hours, particularly 1 to 24 hours. When applied by vapor deposition, a temperature range of 20 to 200°C, particularly 25 to 80°C, is preferred for 30 minutes to 36 hours, particularly 30 minutes to 24 hours.
  • curing may be performed under humid conditions.
  • spray coating for example, diluting the agent in a fluorine-based solvent to which moisture has been added beforehand, hydrolyzing the agent (i.e., generating Si-OH groups), and then spray coating the agent will result in rapid curing after application.
  • the thickness of the cured coating is selected appropriately depending on the type of substrate, but is typically 0.1 to 100 nm, and particularly 1 to 20 nm.
  • the thickness can be measured, for example, by spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, or X-ray fluorescence measurement.
  • the substrate to be treated with the coating agent of the present invention is not particularly limited and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz.
  • the coating agent of the present invention can impart water and oil repellency and abrasion resistance (resistance to steel wool abrasion) to the substrate, and can also form a cured coating that maintains high abrasion resistance even after surface cleaning. In particular, it can be used as a coating agent for SiO2 -treated glass or film.
  • Articles that can be treated with the coating agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, and other optical articles.
  • the coating agent of the present invention can also be used to treat the housings of mobile phones, smartphones, PCs, and other devices.
  • the coating agent of the present invention prevents the adhesion of fingerprints and sebum to the above-mentioned articles and also provides scratch resistance (abrasion resistance), making it particularly useful as a water- and oil-repellent layer for the housings of mobile phones, smartphones, PCs, and other devices.
  • the coating agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins, an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., and headlamp covers, a water- and oil-repellent coating for exterior wall building materials, an oil-stain-resistant coating for kitchen building materials, an anti-fouling coating for telephone booths and to prevent posters and graffiti, a coating for imparting fingerprint resistance to artworks, etc., and an anti-fingerprint coating for compact discs, DVDs, etc. It is also useful as an anti-fouling coating for building materials, particularly flooring and wall materials.
  • the fluoropolyether group-containing polymer composition of the present invention can also be suitably used as a mold release agent for molds, a paint additive, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, or a water and oil repellent for tapes, films, etc.
  • the surface of an article can be modified by applying a coating agent containing the fluoropolyether group-containing polymer composition of the present invention to the entire surface or a portion of the surface of the article by a dry method (vapor deposition treatment) or a wet method (brushing, dipping, spraying, etc.), and then curing the coating agent to form a layer.
  • a coating agent containing the fluoropolyether group-containing polymer composition of the present invention to the entire surface or a portion of the surface of the article by a dry method (vapor deposition treatment) or a wet method (brushing, dipping, spraying, etc.), and then curing the coating agent to form a layer.
  • An article having a layer made of the cured product of the coating agent of the present invention has excellent abrasion resistance against various abrasive materials.
  • the abrasion durability when rubbed with steel wool is preferably 7,500 or more times, and more preferably 10,000 or more times, under the test conditions described below. If the abrasion durability when rubbed with steel wool is less than 7,500 times, the water repellency of the cured coating film is likely to decrease and scratches are likely to occur.
  • an abrasion durability when rubbed with steel wool of the above value or more can be achieved by setting the content of component (I) to 16% by mass or more but less than 55% by mass of the total of components (I) and (II).
  • Step wool abrasion durability test conditions Evaluation of steel wool abrasion resistance using a reciprocating abrasion tester.
  • Abrasive material Steel wool #0000 (Bonstar) Load: 1 kgf Round trip distance: 40 mm Reciprocating speed: 60 reciprocations per minute Test environment conditions: 25°C, relative humidity 50% The water contact angle of the abraded portion was measured every 2,500 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle was maintained at 100 degrees or more was taken as the steel wool abrasion durability cycle.
  • the abrasion durability when rubbed with a nonwoven fabric is preferably 20,000 times or more, and more preferably 30,000 times or more, under the test conditions described below. If the abrasion durability when rubbed with a nonwoven fabric is less than 20,000 times, the water repellency of the cured coating film is likely to decrease and scratches are likely to occur.
  • an abrasion durability when rubbed with a nonwoven fabric of the above value or more can be achieved by setting the content of component (I) to 16% by mass or more and less than 55% by mass of the total of components (I) and (II).
  • Nonwoven fabric abrasion durability test conditions Evaluation of abrasion durability of nonwoven fabric using a reciprocating abrasion tester.
  • Abrasive material Bemcot (M-3II, manufactured by Ozu Sangyo Co., Ltd.) Load: 1 kgf Round trip distance: 40 mm Reciprocating speed: 60 reciprocations per minute
  • Test environment conditions 25°C, relative humidity 50% The water contact angle of the abraded portion is measured every 5,000 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle remains at 100 degrees or more is defined as the abrasion durability cycle of the nonwoven fabric.
  • the number-average molecular weight of the fluoropolyether group-containing polymer is a value calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on 19F-NMR analysis, and the number of repeating fluorooxyalkylene units in the fluorooxyalkylene group-containing polymer residue is a number-average value calculated from 19F -NMR.
  • the repeating units shown in parentheses with p1 and q1 are randomly bonded.
  • the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometer. The test environmental conditions were 25°C and 50% relative humidity.
  • a chemically strengthened glass substrate with SiO 2 (10 nm thick) was placed in a resistance heating vacuum deposition apparatus (VTR-350M, manufactured by ULVAC Kiko Co., Ltd.), and 6 ⁇ L of the following surface treatment agent was dropped onto the resistance heating section, followed by depressurization.
  • VTR-350M resistance heating vacuum deposition apparatus
  • 6 ⁇ L of the following surface treatment agent was dropped onto the resistance heating section, followed by depressurization.
  • the power input to the resistance heating was adjusted so that the maximum evaporation rate measured by a quartz crystal film thickness meter installed approximately 20 cm away from the resistance heating section was 1.0 nm/sec. Resistance heating was continued for 100 seconds after the evaporation rate measured by the quartz crystal film thickness meter had decreased to 0.1 nm/sec.
  • the apparatus was allowed to cool for 5 minutes, after which it was opened to the atmosphere, yielding a substrate coated with a fluoropolyether group-containing polymer.
  • the glass substrate coated with the above fluoropolyether group-containing polymer was left to stand for 30 minutes in an environment of 80°C and 80% relative humidity to cure, yielding a glass substrate having a cured coating of the fluoropolyether group-containing polymer with a thickness of 13 to 15 nm.
  • the thickness of the water- and oil-repellent surface layer was calculated by quantifying the intensity of fluorescent X-rays derived from elemental fluorine using a fluorescent X-ray measuring device (manufactured by Rigaku Corporation, trade name: fluorescent X-ray measuring device Primini) and using a calibration curve.
  • a fluorescent X-ray measuring device manufactured by Rigaku Corporation, trade name: fluorescent X-ray measuring device Primini
  • Component (I) A fluoropolyether group-containing polymer having a structure represented by the following formula (A) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (B) (number average molecular weight: 5,900) A fluoropolyether group-containing polymer having a structure represented by the following formula (C) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (D) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (E) (number average molecular weight: 5,900)
  • Component (II) A fluoropolyether group-containing polymer having a structure represented by the following formula (F) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (G) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (H) (number average molecular weight: 5,900) A fluoropolyether group-containing polymer having a structure represented by the following formula (I) (number average molecular weight: 5,900)
  • Steel wool abrasion durability of 10,000 strokes or more was evaluated as ⁇ (excellent), 7,500 to less than 10,000 strokes as ⁇ (good), 5,000 to less than 7,500 strokes as ⁇ (passable), and less than 5,000 strokes as ⁇ (unacceptable).
  • the evaluation results are shown in Tables 4, 5, and 6.
  • a nonwoven fabric abrasion durability of 30,000 strokes or more was evaluated as ⁇ (excellent), 20,000 to less than 30,000 strokes as ⁇ (good), 10,000 to less than 20,000 strokes as ⁇ (passable), and less than 10,000 strokes as ⁇ (unacceptable).
  • the evaluation results are shown in Tables 4, 5, and 6.
  • the cured coatings of the examples in which the fluoropolyether group-containing polymer of component (I) and the fluoropolyether group-containing polymer of component (II) were used in specific ratios had good water repellency and excellent steel wool abrasion resistance and nonwoven fabric abrasion resistance.

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Abstract

La présente invention concerne une composition polymère contenant un groupe fluoropolyéther comprenant, selon un rapport spécifique, (I) un polymère ayant un groupe fluorooxyalkyle au niveau d'une extrémité et ayant, au niveau de l'autre extrémité, au moins deux groupes fonctionnels réactifs (groupes silyle contenant un groupe hydroxyle ou groupes silyle hydrolysables), et/ou un condensat partiel (hydrolysé) du polymère, et (II) un polymère ayant un groupe fluorooxyalkylène dans la molécule et ayant des groupes fonctionnels réactifs (groupes silyle contenant un groupe hydroxyle ou groupes silyle hydrolysables) liés aux deux extrémités du groupe fluorooxyalkylène par l'intermédiaire d'un groupe de liaison ne comportant pas de groupe polaire, et/ou un condensat partiel (hydrolysé) du polymère. Un agent de revêtement contenant la composition polymère contenant un groupe fluoropolyéther peut former un film de revêtement durci qui présente un excellent caractère hydrofuge et oléofuge et une durabilité à l'abrasion contre un non tissé et une laine d'acier.
PCT/JP2025/005176 2024-02-29 2025-02-17 Composition polymère contenant un groupe fluoropolyéther, agent de revêtement, article et procédé de modification de surface d'article Pending WO2025182641A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007197425A (ja) * 2005-12-26 2007-08-09 Shin Etsu Chem Co Ltd フッ素含有オルガノポリシロキサン及びこれを含む表面処理剤並びに該表面処理剤で表面処理された物品
JP2011116947A (ja) * 2009-10-27 2011-06-16 Shin-Etsu Chemical Co Ltd フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品
JP2012072272A (ja) * 2010-09-28 2012-04-12 Shin-Etsu Chemical Co Ltd フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品
JP2015199906A (ja) * 2014-03-31 2015-11-12 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
JP2022059417A (ja) * 2020-10-01 2022-04-13 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー組成物、コーティング剤及び物品
WO2023199768A1 (fr) * 2022-04-15 2023-10-19 信越化学工業株式会社 Polymère contenant un groupe fluoropolyéther, agent de traitement de surface et article

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007197425A (ja) * 2005-12-26 2007-08-09 Shin Etsu Chem Co Ltd フッ素含有オルガノポリシロキサン及びこれを含む表面処理剤並びに該表面処理剤で表面処理された物品
JP2011116947A (ja) * 2009-10-27 2011-06-16 Shin-Etsu Chemical Co Ltd フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品
JP2012072272A (ja) * 2010-09-28 2012-04-12 Shin-Etsu Chemical Co Ltd フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品
JP2015199906A (ja) * 2014-03-31 2015-11-12 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
JP2022059417A (ja) * 2020-10-01 2022-04-13 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー組成物、コーティング剤及び物品
WO2023199768A1 (fr) * 2022-04-15 2023-10-19 信越化学工業株式会社 Polymère contenant un groupe fluoropolyéther, agent de traitement de surface et article

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