WO2017094371A1 - Composition de matériau de revêtement - Google Patents

Composition de matériau de revêtement Download PDF

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Publication number
WO2017094371A1
WO2017094371A1 PCT/JP2016/080666 JP2016080666W WO2017094371A1 WO 2017094371 A1 WO2017094371 A1 WO 2017094371A1 JP 2016080666 W JP2016080666 W JP 2016080666W WO 2017094371 A1 WO2017094371 A1 WO 2017094371A1
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Prior art keywords
group
polymer
mol
hydrolyzable
composition according
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PCT/JP2016/080666
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English (en)
Japanese (ja)
Inventor
高至 松田
祐治 山根
隆介 酒匂
則之 小池
Original Assignee
信越化学工業株式会社
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Application filed by 信越化学工業株式会社 filed Critical 信越化学工業株式会社
Priority to CN201680070484.4A priority Critical patent/CN108368379B/zh
Priority to JP2017553692A priority patent/JP6497449B2/ja
Priority to KR1020187015854A priority patent/KR102511340B1/ko
Publication of WO2017094371A1 publication Critical patent/WO2017094371A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a coating composition that is effective as a surface modifier used to form a layer imparting functions such as antifouling and low friction (slidability) on the surface of various substrates, and the coating
  • the present invention relates to an article in which a cured film of the composition is formed on the surface by treatment with an agent composition, and a surface treatment method for an article using the coating agent composition.
  • a perfluorooxyalkylene group-containing compound has a very small surface free energy, and thus has water and oil repellency, chemical resistance, lubricity, release properties, antifouling properties and the like. Utilizing its properties, it is widely used industrially for water and oil repellent and antifouling agents such as paper and fiber, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, and protective films. ing.
  • the property means that it is non-adhesive and non-adhesive to other substrates at the same time, and even if it can be applied to the surface of the substrate, it was difficult to make the film adhere to it. .
  • a silane coupling agent is well known as a material for bonding a substrate surface such as glass or cloth to an organic compound.
  • the silane coupling agent is composed of a monovalent hydrocarbon group containing an organic functional group such as an amino group, an epoxy group or a (meth) acryloxy group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group in one molecule. Etc.).
  • Hydrolyzable silyl groups such as alkoxysilyl groups undergo a self-condensation reaction with moisture (humidity) in the air to form siloxane and form a film.
  • a hydrolyzable silyl group such as an alkoxysilyl group is chemically and physically bonded to the surface of glass or metal to form a strong coating having durability.
  • Silane coupling agents are widely used as coating agents for various substrate surfaces using this property, and compounds that apply silane coupling agents to impart the characteristics of perfluorooxyalkylene groups to the substrate surface are known. Proposed.
  • Patent Document 1 high water and oil repellency is realized by applying a fluoroaminosilane compound represented by the following formula to glass.
  • the compound has a short perfluorooxyalkylene chain and cannot provide sufficient lubricity, releasability and antifouling properties.
  • R 6 and R 7 are alkyl groups having 1 to 4 carbon atoms
  • R 5 is CH 2 CH 2 CH 2 or CH 2 CH 2 NHCH 2 CH 2 CH 2
  • h is an integer of 0 to 8
  • i is 2 or 3.
  • Patent Document 2 describes a perfluoropolyether-modified aminosilane containing a branched long-chain perfluorooxyalkylene group represented by the following formula.
  • the perfluoropolyether-modified aminosilane has high water and oil repellency, but has a branched structure in the main chain, so that the dirt wiping property and lubricity are not sufficient.
  • X represents a hydrolyzable group
  • R 8 represents a monovalent hydrocarbon group
  • R 10 represents a hydrogen atom or a monovalent hydrocarbon group
  • R 9 represents an alkylene group which may intervene an NH group.
  • J represents (An integer of 14 to 49, k is 2 or 3.)
  • Patent Document 3 describes a perfluoropolyether-modified silane containing a linear perfluorooxyalkylene group represented by the following formula.
  • the lens or antireflection film treated with the perfluoropolyether-modified silane is excellent in slipperiness, releasability, and wear resistance, but has insufficient lubricity because both ends are fixed to the substrate.
  • Rf is a divalent linear perfluoropolyether group
  • R is an alkyl group or phenyl group having 1 to 4 carbon atoms
  • X is a hydrolyzable group
  • l 0 to 2
  • m is 1 to 5
  • A is 2 or 3.
  • Patent Document 4 describes a perfluoropolyether-modified silane represented by the following formula as a treatment agent having improved lubricity. However, since this compound does not have a fluorine-containing group at the terminal, it is inferior in water / oil repellency, low dynamic friction, and releasability.
  • Rf is a group containing a divalent perfluoroether residue
  • Q is a divalent organic group
  • Z 1 and Z 2 are organopolysiloxane residues
  • A is a monovalent having a terminal reactive silyl group.
  • ⁇ represents an integer of 1 to 8, and ⁇ is a number greater than 0 and less than 2.
  • Patent Document 5 describes a linear chain having — (CF 2 ) d — (OC 2 F 4 ) e (OCF 2 ) f —O (CF 2 ) d — having a main chain structure and a hydrolyzable silyl group at one end.
  • Patent Document 6 describes that the alkali resistance and acid resistance are improved by having a cyclic siloxane residue at the linking site, but on the other hand, the steel wool wear durability has not reached satisfactory performance.
  • Patent Document 7 describes that by introducing an isopropenoxy group into the hydrolyzable silyl group, it can be cured in a short time even by wet coating such as spray coating. As for durability, it has not reached a performance that can satisfy the level required in recent years.
  • coating manufacturers have desired to provide surface treatment materials that can be cured in a short time after being applied to a substrate and exhibit the above-described surface characteristics (that is, excellent scratch resistance and low dynamic friction properties).
  • Methods for applying the surface treatment agent to the substrate include dry coating methods such as vacuum deposition and wet coating methods such as dip coating and spray coating.
  • the above-mentioned patent document 5 is excellent by applying the surface treatment agent having a trimethoxysilyl group at the end of the polymer to the substrate surface by vacuum vapor deposition, and then curing for 2 hours in an atmosphere of 40 ° C. and 80% humidity. Further, it is described that a cured film having scratch resistance and low dynamic friction can be provided.
  • the surface treatment agent is applied to the surface of the substrate by a wet coating method, a problem has arisen in that a cured film having excellent surface properties cannot be obtained by subsequent short-time curing. This is because when coating is performed by vacuum deposition, the SiO 2 layer on the substrate surface is deposited, so that it is possible to provide a cured film having excellent surface characteristics by short-time curing. This is probably because the SiO 2 layer is not deposited during coating.
  • the present invention can provide a cured film having excellent surface characteristics, particularly excellent wear durability and low dynamic friction even when the curing time after application is short as in the wet coating method.
  • An object of the present invention is to provide a coating agent composition, various articles on which a cured film of the composition is formed, and a surface treatment method for the article using the agent composition.
  • the present invention provides the following coating agent composition and various articles having a surface treated with the coating agent composition (surface modifier) (that is, having a cured film of the coating agent composition on the surface). And a surface treatment method for an article using the coating agent composition.
  • the Rf group is a group represented by — (CF 2 ) d — (OY) e —O (CF 2 ) d —, wherein d is each independently 0 or an integer of 1 to 5; Is one or more groups selected from the group consisting of OCF 2 CF 2 CF 2 CF 2 , OCF 2 CF 2 CF 2 , OCF (CF 3 ) CF 2 , OCF 2 CF 2 and OCF 2 , The order may be random or block, and e is an integer of 5 to 200.
  • A is a monovalent fluorine-containing group having a terminal —CF 3 group, and Q is a carbon number of 2 to 6 which may contain an ether bond.
  • Q is a hydrolyzable group, and c is an integer of 3 to 8.
  • the both ends with respect to the total mole of the said one terminal hydrolyzable polymer and the said both terminal hydrolysable polymer are included including the linear fluorooxyalkylene group containing polymer (henceforth a both terminal hydrolysable polymer) represented by these.
  • a coating agent composition wherein the content of the hydrolyzable polymer is more than 0 mol% and less than 20 mol%.
  • the following formula (3) A-Rf-A (3) (In the formula, Rf and A are the same as described above.)
  • a piece containing a fluorooxyalkylene group-containing polymer represented by the formula hereinafter referred to as a non-functional polymer
  • [3] [2] The coating agent composition according to [2], wherein the content of the non-functional polymer with respect to the total moles of the one-end hydrolyzable polymer, the both-end hydrolyzable polymer and the non-functional polymer is more than 0 mol% and less than 30 mol%. object.
  • the coating agent composition according to any one of [1] to [3], which further contains a fluorinated solvent which further contains a fluorinated solvent.
  • the divalent hydrocarbon group Q is a group represented by the following formula: —CH 2 OCH 2 CH 2 CH 2 — (However, the left end is connected to the Rf group, and the right end is connected to Si.)
  • the hydrolyzable group X is at least one group selected from a methoxy group, an ethoxy group, an isopropenoxy group, and an acetoxy group, and any one of [1] to [5]
  • An optical article having a cured film of the coating agent composition according to any one of [1] to [6] on its surface.
  • a touch panel having a cured film of the coating agent composition according to any one of [1] to [6] on a surface thereof.
  • An antireflection film having a cured film of the coating agent composition according to any one of [1] to [6] on its surface.
  • [11] [1] to [6] SiO 2 treated glass having a cured film of the coating agent composition according to any one of [1] to [6] on its surface.
  • a method for surface treatment of an article comprising a step of treating the surface of the article by a dry coating method or a wet coating method using the coating agent composition according to any one of [1] to [6].
  • the coating agent composition (surface modifier) of the present invention can impart excellent water and oil repellency, low dynamic friction and scratch resistance to the substrate surface in a short time by dry coating method and wet coating method. In particular, even when the curing time is short by the wet coating method, the above performance can be exhibited.
  • the coating agent composition of the present invention comprises a one-end hydrolyzable polymer represented by the following general formula (1): Both end hydrolyzable polymer represented by the following general formula (2) And the content ratio of the hydrolyzable polymer at both ends to the total mole of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends is more than 0 mol% and less than 20 mol%, preferably 0.1-18.
  • the coating composition is characterized in that it is a mol%, more preferably 0.5 to 15 mol%, still more preferably 1 to 10 mol% (that is, the one-terminal hydrolyzable polymer and the both-terminal hydrolyzed polymer).
  • the content ratio of the one-end hydrolyzable polymer with respect to the total moles of the two components with the degradable polymer is 80 mol% or more and less than 100 mol%, preferably 82 to 99.9 mol%, more preferably 85 to 99.5 mol%. And more preferably 90 to 99 mol%.
  • A is a monovalent fluorine-containing group having a terminal —CF 3 group, preferably 1-6 linear or branched perfluoroalkyl groups, specifically , Trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, 1- (trifluoromethyl) -1,2,2,2-tetrafluoroethyl group, nonafluorobutyl group, 1,1-di (trifluoro Methyl) -2,2,2-trifluoroethyl group, undecafluoropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, etc., among which trifluoromethyl group is preferred , Pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropenty
  • the Rf group is a group represented by — (CF 2 ) d — (OY) e —O (CF 2 ) d —, and each d is independently 0 Or an integer of 1 to 5, and OY is one selected from the group consisting of OCF 2 CF 2 CF 2 CF 2 , OCF 2 CF 2 CF 2 , OCF (CF 3 ) CF 2 , OCF 2 CF 2 and OCF 2.
  • the arrangement order may be random or block
  • e is an integer of 5 to 200.
  • Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond, and examples thereof include the following groups (each of the following groups). In the illustration, the left end is connected to the Rf group, and the right end is connected to Si).
  • c is an integer of 3 to 8, preferably an integer of 3 to 6.
  • X is a hydrolyzable group, for example, alkoxy group such as methoxy group, ethoxy group, propoxy group, trifluoromethoxy group, trifluoroethoxy group, trichloroethoxy.
  • Halogenated alkoxy groups such as groups, alkoxy group-substituted alkoxy groups such as methoxyethoxy groups, acetoxy groups, propionyloxy groups, acyloxy groups such as benzoyloxy groups, alkenyloxy groups such as isopropenyloxy groups, isobutenyloxy groups, Dimethyl ketoxime group, methyl ethyl ketoxime group, ketoxime group such as diethyl ketoxime group, imineoxy group such as cyclohexane oxime group, substituted amino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group, N-methylacetamide Group, N-E Amide groups such Ruamido group, dimethylamino group, a substituted amino group such as a diethylamino group, a halogen group such as chlorine atom.
  • a methoxy group, an ethoxy group, a trifluoroethoxy group, an acetoxy group, an isopropenyloxy group, a chlorine atom, a dimethylketoxime group, and a methylethylketoxime group are preferable, and a methoxy group, an ethoxy group, and an isopropenyloxy group. Is particularly preferred.
  • X can be included in the hydrolyzable polymer of the present invention as one type or a combination of two or more types.
  • the coating agent composition of the present invention (hereinafter also referred to as a fluorooxyalkylene group-containing polymer composition) is further represented by the following formula (3): A-Rf-A (3) (In the formula, Rf and A are the same as those described in the formulas (1) and (2).)
  • the polymer may contain a fluorooxyalkylene group-containing polymer represented by the following (hereinafter referred to as a non-functional polymer).
  • the fluorooxyalkylene group-containing polymer used in the present invention contains the above-mentioned non-functional polymer, the above-mentioned one-end hydrolyzable polymer, both-end hydrolyzable polymer, and the non-functional polymer of the three components
  • the ratio of the one-end hydrolyzable polymer to the total mole is 65 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and less than 100 mol%, and the ratio of the both-end hydrolyzable polymer Is more than 0 mol% and less than 20 mol%, preferably 0.1 to 18 mol%, more preferably 1 to 10 mol%.
  • the proportion of the non-functional polymer should be more than 0 mol% and less than 30 mol%, preferably 1 to 25 mol%, more preferably 5 to 20 mol%.
  • the above-mentioned fluorooxyalkylene group-containing polymer composition can be produced, for example, by the following steps (i) to (vi).
  • a fluorooxyalkylene group-containing polymer having a carboxylic acid group at one end (hereinafter referred to as a one-end carboxylic acid polymer) by partially fluorinating the end of a perfluorooxy compound having a carboxylic acid at both ends;
  • a mixture containing a fluorooxyalkylene group-containing polymer having carboxylic acid groups at both ends (hereinafter referred to as both-end carboxylic acid polymer) is produced.
  • the introduction rate of terminal —CF 3 groups can be appropriately adjusted by adjusting the amount of fluorine gas to be supplied and controlling fluorination.
  • the mixture obtained in this step may contain a fluorooxyalkylene group-containing polymer having no carboxylic acid group at the terminal (hereinafter referred to as a non-functional polymer).
  • a mixture containing a carboxylic acid polymer at one end and a carboxylic acid polymer at both ends is subjected to an adsorption treatment and / or a molecular distillation treatment, and contains a fluorooxyalkylene group-containing polymer having a carboxylic acid group at one end in a high concentration.
  • a three-component polymer composition is obtained.
  • the method of adsorption treatment and / or molecular distillation treatment may follow a known method. By this step, the content ratio of the both terminal hydrolyzable polymer with respect to the total mole of the one terminal hydrolyzable polymer and both terminal hydrolyzable polymers can be adjusted.
  • a terminal carboxylic acid group in the three-component polymer composition is modified to introduce a group having an aliphatic unsaturated group at the terminal.
  • the introduction method may follow a known method. For example, first, the terminal carboxylic acid group-containing three-component polymer composition is subjected to reduction using a metal hydride or catalytic hydrogenation using a noble metal catalyst, and the following terminal hydroxyl group (methylol group) is contained: (In the formula, the Rf group is the same as described above).
  • an aliphatic unsaturated group is introduced into the terminal hydroxyl group of the three-component polymer composition obtained above.
  • the introduction of the aliphatic unsaturated group into the terminal hydroxyl group may be performed according to a known method.
  • a three-component polymer composition containing a terminal aliphatic unsaturated group having an alkenyl group such as an allyl group introduced at the terminal, as shown below, is produced.
  • an organosilicon compound having one SiH group and three hydrolyzable groups on the terminal aliphatic unsaturated group of the above three-component polymer composition for example, trimethoxysilane is subjected to a hydrosilylation addition reaction.
  • the addition reaction may be performed under known reaction conditions, and may be performed in the presence of an addition reaction catalyst such as a platinum group compound.
  • an addition reaction catalyst such as a platinum group compound.
  • an organosilicon compound having an aliphatic unsaturated group at one end and a hydrolyzable silyl group at the other end is added to the SiH group in the three-component polymer composition.
  • the addition reaction may be performed under known reaction conditions, and may be performed in the presence of an addition reaction catalyst such as a platinum group compound.
  • an addition reaction catalyst such as a platinum group compound.
  • the number-average molecular weight in terms of polystyrene determined by gel permeation chromatography for the one-end and both-end hydrolyzable polymers used in the coating agent composition of the present invention is preferably 500 or more and 40,000 or less, particularly preferably 1. It is desirable to use a material in the range of 1,000 to 30,000, more preferably 1,000 to 20,000. If the number average molecular weight is less than 500, the water / oil repellency and antifouling characteristics of the fluorooxyalkylene group may not be fully exhibited. If the number average molecular weight exceeds 40,000, the concentration of the terminal functional group becomes small. Therefore, the reactivity and adhesion with the substrate may be reduced.
  • the number average molecular weight referred to in the present invention refers to the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) measured under the following conditions (hereinafter the same).
  • GPC gel permeation chromatography
  • the coating agent composition of the present invention may contain a solvent or a diluent.
  • solvents or diluents include alcohols (ethyl alcohol, isopropyl alcohol, etc.), hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.), ester solvents (ethyl acetate, isopropyl acetate, Butyl acetate, etc.), ether solvents (diethyl ether, isopropyl ether, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and polar solvents such as alcohols, esters, ethers, and ketones are used.
  • Fluorine solvents are also preferably used. Examples thereof include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, etc.), fluorinated aromatic hydrocarbon solvents (m-xylene hexafluoride, benzoate).
  • Fluorinated ether solvents are preferably used in terms of properties, wettability and the like.
  • the said solvent may be used individually by 1 type, or may mix and use 2 or more types, and it is preferable to use what dissolves the said component uniformly in any case.
  • the amount of solvent used is not particularly limited, and the optimum concentration varies depending on the processing method. In the case of vapor deposition, it is generally preferable to use an amount such that the solid content in the coating composition is 1 to 80% by mass, particularly 5 to 50% by mass. In the case of spray coating or dipping coating, it is preferable to use an amount such that the solid content in the composition is 0.05 to 20.0 mass%, particularly 0.1 to 1.0 mass%.
  • the solid content means the mass of the nonvolatile component.
  • a curing catalyst may be added as necessary.
  • curing catalysts include organotitanate esters, organotitanium chelate compounds, organoaluminum compounds, organozirconium compounds, organotin compounds, metal salts of organic carboxylic acids, amine compounds and salts thereof, quaternary ammonium compounds, and alkali metal compounds.
  • examples include lower fatty acid salts, dialkylhydroxyamines, guanidine group-containing organosilicon compounds, inorganic acids, perfluorocarboxylic acids, perfluoroalcohols, and the like.
  • perfluorocarboxylic acids are used.
  • the addition amount of the curing catalyst is a catalytic amount, and the fluorine-containing organosilane compound according to the present invention, a partially hydrolyzed product thereof or a partially hydrolyzed condensate thereof (that is, one-end and both-end hydrolyzable polymers and these portions).
  • the total amount of hydrolyzate and partially hydrolyzed condensate (total amount of polymer component) is preferably from 0.05 to 5 parts by weight, particularly preferably from 0.1 to 1 part by weight, based on 100 parts by weight.
  • wet coating methods such as brushing, dipping and spraying, and dry coating methods such as vapor deposition There are known methods.
  • the optimum processing temperature of the applied coating agent composition varies depending on the application method, but for example, in the case of spray coating or dipping, a range of 10 to 100 ° C. is desirable.
  • As the treatment humidity it is desirable to perform the treatment under humidification in order to promote the reaction.
  • the curing time of the conventional surface modifier is usually 12 to 24 hours. On the other hand, in the method of the present invention, the curing time may be 6 hours or less, particularly 1 to 4 hours, more preferably 1 to 3 hours.
  • the method of the present invention uses the surface modifier to form a cured film having excellent surface characteristics, particularly excellent low dynamic friction and scratch resistance, even with such short-time curing. Can be provided.
  • it is desirable to optimize the said process conditions suitably according to a base material, a curing catalyst, etc.
  • the substrate to be treated with the coating composition is not particularly limited, and may be made of various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, and quartz.
  • the coating agent composition of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface modifier for chemically strengthened glass, glass treated with SiO 2 or film.
  • the film thickness of the cured film of the coating composition formed on the surfaces of the various substrates or articles is appropriately selected depending on the type of the substrate, but is preferably 1 to 100 nm, more preferably 3 to 20 nm.
  • the resulting coating is water and oil repellency and high water slidability, and is excellent in durability such as heat resistance, chemical resistance and UV resistance compared to conventional products.
  • Such characteristics are effective for applications that are often exposed to water and ultraviolet rays and are not easy to maintain, and for oils and fingerprints, cosmetics, sunscreen, human and animal excrement, oils, etc.
  • window glass or tempered glass for automobiles, trains, ships, airplanes, high-rise buildings, head lamp covers, outdoor equipment, telephone boxes, outdoor large displays, sanitary products such as bathtubs and washstands, cosmetic tools, and kitchen use Examples include coatings that prevent fingerprint adhesion on building materials, water tanks, and art.
  • a fingerprint preventing coating for compact discs, DVDs, etc. is also useful as a mold release agent or paint additive for resin molds, and as a resin modifier.
  • medical devices such as car navigation systems, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, gastric cameras, copying machines, PCs And optical articles such as liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. Since the surface modifier of the present invention can prevent fingerprints and sebum from adhering to the article and can further provide scratch resistance, it is particularly useful as a water / oil repellent layer for touch panel displays, antireflection films, etc. It is.
  • X 1 in the formula (4) is a group represented by the following formula (a), and X 2 is a fluorine atom, one-end hydrolyzable polymer: 83 mol%
  • X 2 is a fluorine atom, one-end hydrolyzable polymer: 83 mol%
  • a polymer composition comprising:
  • the concentration of the polymer compositions 1 to 4 is 0.08% by mass using a fluorine-based solvent Novec7 (registered trademark) 200 (manufactured by 3M; ethyl perfluorobutyl ether) that has been dehydrated so as to have a water content of 10 ppm or less.
  • a coating composition was prepared by diluting and dissolving.
  • Comparative Example 1 having a cyclic siloxane structure is the structure described in Japanese Patent Application Laid-Open No. 2014-084405 and Japanese Patent Application Laid-Open No. 2014-077786, which is also inferior in wear durability as compared with the present example.

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Abstract

L'invention concerne une composition de matériau de revêtement qui comprend un polymère hydrolysable à une terminaison, de formule (1), et un polymère hydrolysable aux deux terminaisons, de formule (2), la proportion molaire du polymère hydrolysable aux deux terminaisons à la somme du polymère hydrolysable à une terminaison et du polymère hydrolysable aux deux terminaisons étant supérieure à 0% en moles mais inférieure à 20% en moles. La composition de l'invention peut conférer à une surface de base, en peu de temps, un excellent pouvoir hydrofuge et oléofuge, un faible frottement dynamique, et une excellente résistance aux rayures. [Dans lesdites formules, le groupe Rf est un groupe de -(CF2d-(OY)e-O(CF2)d- (d étant compris entre 0 et 5; OY étant un ou plusieurs groupes sélectionnés parmi OCF2CF2CF2CF2, OCF2CF2CF2, OCF(CF3)CF2, OCF2CF2 et OCF2; et e étant compris entre 5 et 200); A est un groupe fluoré monovalent terminé par un groupe -CF3; Q est un groupe hydrocarboné divalent; X est un groupe hydrolysable; et c est compris entre 3 et 8.]<sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb /> <sb />
PCT/JP2016/080666 2015-12-03 2016-10-17 Composition de matériau de revêtement WO2017094371A1 (fr)

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WO2019088116A1 (fr) * 2017-10-31 2019-05-09 ダイキン工業株式会社 Composition de traitement de surface
WO2019093259A1 (fr) * 2017-11-07 2019-05-16 住友化学株式会社 Stratifié
WO2019203320A1 (fr) * 2018-04-20 2019-10-24 Ａｇｃ株式会社 Composition et article
WO2021010448A1 (fr) * 2019-07-18 2021-01-21 Ａｇｃ株式会社 Article comportant une couche de surface
CN113891919A (zh) * 2019-05-31 2022-01-04 Ａｇｃ株式会社 带拒水拒油层的基材
WO2023132276A1 (fr) * 2022-01-05 2023-07-13 Ａｇｃ株式会社 Composition, procédé de production de composition, liquide de revêtement, article et procédé de production d'article

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CN117043209A (zh) 2021-03-25 2023-11-10 日产化学株式会社 含有两种全氟聚醚的固化性组合物

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WO2019088116A1 (fr) * 2017-10-31 2019-05-09 ダイキン工業株式会社 Composition de traitement de surface
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JP2021165409A (ja) * 2017-10-31 2021-10-14 ダイキン工業株式会社 表面処理組成物
JP7339555B2 (ja) 2017-10-31 2023-09-06 ダイキン工業株式会社 表面処理組成物
WO2019093259A1 (fr) * 2017-11-07 2019-05-16 住友化学株式会社 Stratifié
WO2019203320A1 (fr) * 2018-04-20 2019-10-24 Ａｇｃ株式会社 Composition et article
CN113891919A (zh) * 2019-05-31 2022-01-04 Ａｇｃ株式会社 带拒水拒油层的基材
WO2021010448A1 (fr) * 2019-07-18 2021-01-21 Ａｇｃ株式会社 Article comportant une couche de surface
WO2023132276A1 (fr) * 2022-01-05 2023-07-13 Ａｇｃ株式会社 Composition, procédé de production de composition, liquide de revêtement, article et procédé de production d'article

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KR102511340B1 (ko) 2023-03-17
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