WO2017094371A1 - Coating material composition - Google Patents
Coating material composition Download PDFInfo
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- 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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Classifications
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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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- 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
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- 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
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- 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
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- 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
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- 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.
Abstract
A coating material composition which comprises a one-terminal-hydrolyzable polymer of formula (1) and a both-terminal-hydrolyzable polymer of formula (2),
wherein the molar proportion of the both-terminal-hydrolyzable polymer to the sum of the one-terminal-hydrolyzable polymer and the both-terminal-hydrolyzable polymer is higher than 0 mol% but less than 20 mol%.
With the composition of the present invention, it is possible to impart excellent water and oil repellency, low dynamic friction, and excellent scratch resistance to a base surface in a short time.
[In the formulae, the group Rf is a group of -(CF2)d-(OY)e-O(CF2)d- (where d is 0-5, OY is one or more groups selected from among OCF2CF2CF2CF2, OCF2CF2CF2, OCF(CF3)CF2, OCF2CF2, and OCF2, and e is 5-200); A is a monovalent fluorine-containing group terminated by a -CF3 group; Q is a divalent hydrocarbon group; X is a hydrolyzable group; and c is 3-8.]
Description
本発明は、さまざまな基材の表面上に防汚、低摩擦（滑り性）などの機能を付与する層を形成するのに用いられる表面改質剤として有効なコーティング剤組成物、及び該コーティング剤組成物により処理されて該組成物の硬化被膜が表面に形成された物品、並びに該コーティング剤組成物を用いた物品の表面処理方法に関するものである。
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.
一般に、パーフルオロオキシアルキレン基含有化合物は、その表面自由エネルギーが非常に小さいために、撥水撥油性、耐薬品性、潤滑性、離型性、防汚性などを有する。その性質を利用して、工業的には紙・繊維などの撥水撥油防汚剤、磁気記録媒体の滑剤、精密機器の防油剤、離型剤、化粧料、保護膜など、幅広く利用されている。
Generally, 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.
しかし、その性質は同時に他の基材に対する非粘着性、非密着性であることを意味しており、基材表面に塗布することはできても、その被膜を密着させることは困難であった。
However, 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. .
一方、ガラスや布などの基材表面と有機化合物とを結合させる材料としては、シランカップリング剤が良く知られている。シランカップリング剤は、１分子中にアミノ基、エポキシ基、（メタ）アクリロキシ基等の有機官能基含有１価炭化水素基と反応性シリル基（一般にはアルコキシシリル基等の加水分解性シリル基など）を有する。アルコキシシリル基等の加水分解性シリル基は、空気中の水分（湿気）などによって自己縮合反応を起こしてシロキサンとなり被膜を形成する。それと同時に、アルコキシシリル基等の加水分解性シリル基がガラスや金属などの表面と化学的、物理的に結合することによって、耐久性を有する強固な被膜となる。シランカップリング剤はこの性質を利用して各種基材表面のコーティング剤として幅広く利用されており、パーフルオロオキシアルキレン基の特徴を基材表面に付与するためにシランカップリング剤を応用した化合物が提案されている。
On the other hand, 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. At the same time, 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.
特許文献１では、下記式で示されるフルオロアミノシラン化合物をガラスに塗布することで、高い撥水撥油性を実現している。しかし、該化合物はパーフルオロオキシアルキレン鎖が短く、潤滑性、離型性、防汚性を十分に出すことができない。
（式中、Ｒ6、Ｒ7は炭素数１～４のアルキル基、Ｒ5はＣＨ2ＣＨ2ＣＨ2又はＣＨ2ＣＨ2ＮＨＣＨ2ＣＨ2ＣＨ2、ｈは０～８の整数、ｉは２又は３である。）
In Patent Document 1, high water and oil repellency is realized by applying a fluoroaminosilane compound represented by the following formula to glass. However, the compound has a short perfluorooxyalkylene chain and cannot provide sufficient lubricity, releasability and antifouling properties.
Wherein 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, and i is 2 or 3.)
また、特許文献２は、下記式で示される分岐状の長鎖パーフルオロオキシアルキレン基を含有するパーフルオロポリエーテル変性アミノシランを記載している。該パーフルオロポリエーテル変性アミノシランは撥水撥油性が高いが、主鎖に分岐構造を有するため汚れ拭取り性や潤滑性が十分ではない。
（式中、Ｘは加水分解性基、Ｒ8は１価炭化水素基、Ｒ10は水素原子又は１価炭化水素基、Ｒ9はＮＨ基を介在してもよいアルキレン基を示す。ｊは１４～４９の整数、ｋは２又は３である。）
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.
(In the formula, X represents a hydrolyzable group, R 8 represents a monovalent hydrocarbon group, R 10 represents a hydrogen atom or a monovalent hydrocarbon group, and 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.)
特許文献３は、下記式で示される直鎖状のパーフルオロオキシアルキレン基を含有するパーフルオロポリエーテル変性シランを記載している。該パーフルオロポリエーテル変性シランで処理したレンズや反射防止膜は、滑り性、離型性、及び耐摩耗性に優れるが、両末端が基材に固定されるため潤滑性が不十分である。
（式中、Ｒｆは２価の直鎖型パーフルオロポリエーテル基、Ｒは炭素数１～４のアルキル基又はフェニル基、Ｘは加水分解性基、ｌは０～２、ｍは１～５の整数、ａは２又は３である。）
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.
(Wherein 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 is 0 to 2, m is 1 to 5) , A is 2 or 3.)
特許文献４は、潤滑性を向上させた処理剤として下記式に示されるパーフルオロポリエーテル変性シランを記載している。しかし、該化合物は末端にフッ素含有基を有さないため撥水撥油性、低動摩擦性、離型性に劣っている。
（Ｚ2Ｑ）βＲｆ（ＱＺ1Ａα）2-β
（式中、Ｒｆは２価のパーフロロエーテル残基を含む基、Ｑは２価の有機基、Ｚ1及びＺ2はオルガノポリシロキサン残基、Ａは末端反応性シリル基を有する１価の基を示す。αは１～８の整数、βは０より大きく２未満の数である。） 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.
(Z 2 Q) β Rf (QZ 1 A α ) 2-β
(In the formula, Rf is a group containing a divalent perfluoroether residue, Q is a divalent organic group, Z 1 and Z 2 are organopolysiloxane residues, and A is a monovalent having a terminal reactive silyl group. Α represents an integer of 1 to 8, and β is a number greater than 0 and less than 2.)
（Ｚ2Ｑ）βＲｆ（ＱＺ1Ａα）2-β
（式中、Ｒｆは２価のパーフロロエーテル残基を含む基、Ｑは２価の有機基、Ｚ1及びＺ2はオルガノポリシロキサン残基、Ａは末端反応性シリル基を有する１価の基を示す。αは１～８の整数、βは０より大きく２未満の数である。） 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.
(Z 2 Q) β Rf (QZ 1 A α ) 2-β
(In the formula, Rf is a group containing a divalent perfluoroether residue, Q is a divalent organic group, Z 1 and Z 2 are organopolysiloxane residues, and A is a monovalent having a terminal reactive silyl group. Α represents an integer of 1 to 8, and β is a number greater than 0 and less than 2.)
特許文献５は、－（ＣＦ2）d－（ＯＣ2Ｆ4）e（ＯＣＦ2）f－Ｏ（ＣＦ2）d－を主鎖構造とし、片末端に加水分解性シリル基を有する直鎖状フルオロオキシアルキレン基含有ポリマーと、－（ＣＦ2）d－（ＯＣ2Ｆ4）e（ＯＣＦ2）f－Ｏ（ＣＦ2）d－を主鎖構造とし、両末端に加水分解性シリル基を有する直鎖状フルオロオキシアルキレン基含有ポリマーとを含む組成物であって、片末端加水分解性ポリマーと両末端加水分解性ポリマーとの合計モルに対する両末端加水分解性ポリマーの含有量が０．１モル％以上１０モル％未満であるフルオロオキシアルキレン基含有ポリマー組成物を含有する表面処理剤を記載しているが、スプレー塗工等のウェット塗工のように、加熱時間が短い条件においては、硬化が不十分であり、十分な摩耗耐久性を発揮できない。
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. With a main chain structure, and a hydrolyzable silyl group at both ends of the polymer containing a fluorofluoroalkylene group and a — (CF 2 ) d — (OC 2 F 4 ) e (OCF 2 ) f —O (CF 2 ) d — The content of the hydrolyzable polymer at both ends with respect to the total mole of the hydrolyzable polymer at one end and the hydrolyzable polymer at both ends is 0. Although a surface treatment agent containing a fluorooxyalkylene group-containing polymer composition that is 1 mol% or more and less than 10 mol% is described, under conditions where the heating time is short, such as wet coating such as spray coating The curing is inadequate It can not exhibit a sufficient abrasion resistance.
特許文献６は、連結部位に環状シロキサン残基を有することで、耐アルカリ性、耐酸性が向上すると記載されているが、一方でスチールウール摩耗耐久性については、満足できる性能に達していない。
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.
特許文献７は、加水分解性シリル基の部位に、イソプロペノキシ基を導入することによって、スプレー塗工等のウェット塗工でも短時間硬化が可能であると記載されているが、こちらもスチールウール摩耗耐久性については、近年要求されるレベルを満足できる性能に達していない。
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.
近年、塗工メーカーから、基材に塗布した後、短時間で硬化して上述した表面特性（即ち、優れた耐擦傷性及び低動摩擦性）を発現できる表面処理材料の提供が望まれている。表面処理剤を基材に塗布する方法には、真空蒸着等のドライコーティング法と、ディップ塗工、スプレー塗工などのウェットコーティング法がある。
2. Description of the Related Art 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.
上記特許文献５は、ポリマーの末端がトリメトキシシリル基である上記表面処理剤を真空蒸着により基材表面に塗布し、その後４０℃、湿度８０％の雰囲気下で２時間硬化することにより、優れた耐擦傷性及び低動摩擦性を有する硬化被膜を提供できることを記載している。しかし、該表面処理剤をウェットコーティング法により基材表面に塗布すると、その後短時間の硬化では、優れた表面特性を有する硬化被膜を得ることができないという問題が生じた。これは、真空蒸着で塗工する場合は、基材表面のＳｉＯ2層を蒸着するため、短時間の硬化で優れた表面特性を有する硬化被膜を提供することが可能であるが、ウェットコーティング法で塗工する場合は、塗工時にＳｉＯ2層が蒸着されないためであると考えられる。
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. However, when 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.
その為、本発明は、ウェットコーティング法のように、塗布後の硬化時間が短くても、優れた表面特性、特には、優れた摩耗耐久性及び低動摩擦性を有する硬化被膜を提供することができる、コーティング剤組成物及び該組成物の硬化被膜が形成された各種物品、並びに該剤組成物を用いた物品の表面処理方法を提供することを目的とする。
Therefore, 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.
本発明者らは、上記課題を解決すべく鋭意検討した結果、一般式（１）及び一般式（２）で表されるように、途中の連結部位のＳｉ原子から、シロキサン結合を介して３つのＳｉ原子を経由して末端に３個の加水分解性シリル基を有し、且つ、加水分解性基に隣接するアルキレン基の炭素数が３個以上である場合に、短時間硬化性と摩耗耐久性に優れる硬化被膜を提供できることを見出し、本発明を成すに至った。なお、特許文献５、特許文献７には、本文及び実施例に本発明の構造は明示されていない。
As a result of intensive studies to solve the above-mentioned problems, the present inventors, as represented by the general formula (1) and the general formula (2), from the Si atom at the intermediate connection site through the siloxane bond 3 When there are 3 hydrolyzable silyl groups at the end via two Si atoms and the number of carbon atoms of the alkylene group adjacent to the hydrolyzable group is 3 or more, short-time curability and wear The present inventors have found that a cured coating having excellent durability can be provided, and have achieved the present invention. In Patent Document 5 and Patent Document 7, the structure of the present invention is not clearly shown in the text and examples.
即ち、本発明は、下記のコーティング剤組成物、及び該コーティング剤組成物（表面改質剤）で処理された表面を有する（即ち、該コーティング剤組成物の硬化被膜を表面に有する）各種物品、並びに該コーティング剤組成物を用いた物品の表面処理方法を提供するものである。
〔１〕
下記一般式（１）
（式中、Ｒｆ基は－（ＣＦ2）d－（ＯＹ）e－Ｏ（ＣＦ2）d－で表される基であり、ｄはそれぞれ独立に０又は１～５の整数であり、ＯＹはＯＣＦ2ＣＦ2ＣＦ2ＣＦ2、ＯＣＦ2ＣＦ2ＣＦ2、ＯＣＦ（ＣＦ3）ＣＦ2、ＯＣＦ2ＣＦ2及びＯＣＦ2よりなる群から選ばれる１種又は２種以上の基であり、配列順序はランダムでもブロックでもよく、ｅは５～２００の整数である。Ａは末端が－ＣＦ3基である１価のフッ素含有基、Ｑはエーテル結合を含んでいてもよい炭素数２～６の２価の炭化水素基であり、Ｘは加水分解性基であり、ｃは３～８の整数である。）
で表される直鎖状フルオロオキシアルキレン基含有ポリマー（以下、片末端加水分解性ポリマーと称す）と、下記一般式（２）
（式中、Ｒｆ、Ｑ、Ｘ、ｃは上記式（１）と同じである。）
で表される直鎖状フルオロオキシアルキレン基含有ポリマー（以下、両末端加水分解性ポリマーと称す）を含み、前記片末端加水分解性ポリマーと前記両末端加水分解性ポリマーとの合計モルに対する両末端加水分解性ポリマーの含有割合が０モル％を超え２０モル％未満であることを特徴とするコーティング剤組成物。
〔２〕
更に、下記式（３）
Ａ－Ｒｆ－Ａ （３）
（式中、Ｒｆ及びＡは前記と同じ。）
で表されるフルオロオキシアルキレン基含有ポリマー（以下、無官能性ポリマーと称す）を含有し、かつ、片末端加水分解性ポリマーと両末端加水分解性ポリマーと無官能性ポリマーとの合計モルに対する片末端加水分解性ポリマーの含有割合が６５モル％以上１００モル％未満であり、かつ両末端加水分解性ポリマーの含有割合が０モル％を超え２０モル％未満である〔１〕記載のコーティング剤組成物。
〔３〕
片末端加水分解性ポリマーと両末端加水分解性ポリマーと無官能性ポリマーとの合計モルに対する無官能性ポリマーの含有割合が０モル％を超え３０モル％未満である〔２〕記載のコーティング剤組成物。
〔４〕
更に、フッ素系溶剤を含有するものである〔１〕～〔３〕のいずれかに記載のコーティング剤組成物。
〔５〕
一般式（１）及び一般式（２）において、２価の炭化水素基Ｑが下記式で表される基である〔１〕～〔４〕のいずれかに記載のコーティング剤組成物。
－ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2－
（但し、左端がＲｆ基に連結し、右端がＳｉに連結している。）
〔６〕
一般式（１）及び一般式（２）において、加水分解性基Ｘが、メトキシ基、エトキシ基、イソプロペノキシ基、アセトキシ基から選ばれる少なくとも１種の基である〔１〕～〔５〕のいずれかに記載のコーティング剤組成物。
〔７〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する物品。
〔８〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する光学物品。
〔９〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有するタッチパネル。
〔１０〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する反射防止フイルム。
〔１１〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有するＳｉＯ2処理ガラス。
〔１２〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する強化ガラス。
〔１３〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する石英基板。
〔１４〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物を用いてドライコーティング法又はウェットコーティング法により物品の表面を処理する工程を含む物品の表面処理方法。 That is, 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.
[1]
The following general formula (1)
(In the formula, 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. (Wherein X is a hydrolyzable group, and c is an integer of 3 to 8.)
A linear fluorooxyalkylene group-containing polymer represented by the following (hereinafter referred to as a single-end hydrolyzable polymer), and the following general formula (2)
(In the formula, Rf, Q, X, and c are the same as in the above formula (1).)
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%.
[2]
Further, 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), and a piece with respect to the total mole of the one-end hydrolyzable polymer, the two-end hydrolyzable polymer, and the non-functional polymer. [1] The coating agent composition according to [1], wherein the content ratio of the terminal hydrolyzable polymer is 65 mol% or more and less than 100 mol%, and the content ratio of both terminal hydrolyzable polymers is more than 0 mol% and less than 20 mol%. object.
[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.
[4]
Furthermore, the coating agent composition according to any one of [1] to [3], which further contains a fluorinated solvent.
[5]
The coating agent composition according to any one of [1] to [4], wherein in the general formulas (1) and (2), 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.)
[6]
In the general formulas (1) and (2), 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] A coating agent composition according to claim 1.
[7]
An article having on its surface a cured film of the coating agent composition according to any one of [1] to [6].
[8]
An optical article having a cured film of the coating agent composition according to any one of [1] to [6] on its surface.
[9]
A touch panel having a cured film of the coating agent composition according to any one of [1] to [6] on a surface thereof.
[10]
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.
[12]
[1] A tempered glass having on its surface a cured film of the coating composition according to any one of [1] to [6].
[13]
A quartz substrate having on its surface a cured film of the coating agent composition according to any one of [1] to [6].
[14]
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].
〔１〕
下記一般式（１）
で表される直鎖状フルオロオキシアルキレン基含有ポリマー（以下、片末端加水分解性ポリマーと称す）と、下記一般式（２）
で表される直鎖状フルオロオキシアルキレン基含有ポリマー（以下、両末端加水分解性ポリマーと称す）を含み、前記片末端加水分解性ポリマーと前記両末端加水分解性ポリマーとの合計モルに対する両末端加水分解性ポリマーの含有割合が０モル％を超え２０モル％未満であることを特徴とするコーティング剤組成物。
〔２〕
更に、下記式（３）
Ａ－Ｒｆ－Ａ （３）
（式中、Ｒｆ及びＡは前記と同じ。）
で表されるフルオロオキシアルキレン基含有ポリマー（以下、無官能性ポリマーと称す）を含有し、かつ、片末端加水分解性ポリマーと両末端加水分解性ポリマーと無官能性ポリマーとの合計モルに対する片末端加水分解性ポリマーの含有割合が６５モル％以上１００モル％未満であり、かつ両末端加水分解性ポリマーの含有割合が０モル％を超え２０モル％未満である〔１〕記載のコーティング剤組成物。
〔３〕
片末端加水分解性ポリマーと両末端加水分解性ポリマーと無官能性ポリマーとの合計モルに対する無官能性ポリマーの含有割合が０モル％を超え３０モル％未満である〔２〕記載のコーティング剤組成物。
〔４〕
更に、フッ素系溶剤を含有するものである〔１〕～〔３〕のいずれかに記載のコーティング剤組成物。
〔５〕
一般式（１）及び一般式（２）において、２価の炭化水素基Ｑが下記式で表される基である〔１〕～〔４〕のいずれかに記載のコーティング剤組成物。
－ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2－
（但し、左端がＲｆ基に連結し、右端がＳｉに連結している。）
〔６〕
一般式（１）及び一般式（２）において、加水分解性基Ｘが、メトキシ基、エトキシ基、イソプロペノキシ基、アセトキシ基から選ばれる少なくとも１種の基である〔１〕～〔５〕のいずれかに記載のコーティング剤組成物。
〔７〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する物品。
〔８〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する光学物品。
〔９〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有するタッチパネル。
〔１０〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する反射防止フイルム。
〔１１〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有するＳｉＯ2処理ガラス。
〔１２〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する強化ガラス。
〔１３〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物の硬化被膜を表面に有する石英基板。
〔１４〕
〔１〕～〔６〕のいずれかに記載のコーティング剤組成物を用いてドライコーティング法又はウェットコーティング法により物品の表面を処理する工程を含む物品の表面処理方法。 That is, 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.
[1]
The following general formula (1)
A linear fluorooxyalkylene group-containing polymer represented by the following (hereinafter referred to as a single-end hydrolyzable polymer), and the following general formula (2)
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%.
[2]
Further, 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), and a piece with respect to the total mole of the one-end hydrolyzable polymer, the two-end hydrolyzable polymer, and the non-functional polymer. [1] The coating agent composition according to [1], wherein the content ratio of the terminal hydrolyzable polymer is 65 mol% or more and less than 100 mol%, and the content ratio of both terminal hydrolyzable polymers is more than 0 mol% and less than 20 mol%. object.
[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.
[4]
Furthermore, the coating agent composition according to any one of [1] to [3], which further contains a fluorinated solvent.
[5]
The coating agent composition according to any one of [1] to [4], wherein in the general formulas (1) and (2), 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.)
[6]
In the general formulas (1) and (2), 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] A coating agent composition according to claim 1.
[7]
An article having on its surface a cured film of the coating agent composition according to any one of [1] to [6].
[8]
An optical article having a cured film of the coating agent composition according to any one of [1] to [6] on its surface.
[9]
A touch panel having a cured film of the coating agent composition according to any one of [1] to [6] on a surface thereof.
[10]
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.
[12]
[1] A tempered glass having on its surface a cured film of the coating composition according to any one of [1] to [6].
[13]
A quartz substrate having on its surface a cured film of the coating agent composition according to any one of [1] to [6].
[14]
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].
本発明のコーティング剤組成物（表面改質剤）は、ドライコーティング法及びウェットコーティング法により基材表面に短時間で優れた撥水撥油性、低動摩擦性、かつ耐擦傷性を付与することができ、特にウェットコーティング法で硬化時間が短くても、上記の性能を発揮することができる。
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.
本発明のコーティング剤組成物は、下記一般式（１）で表される片末端加水分解性ポリマーと
下記一般式（２）で表される両末端加水分解性ポリマー
を含み、前記片末端加水分解性ポリマーと前記両末端加水分解性ポリマーとの合計モルに対する両末端加水分解性ポリマーの含有割合が０モル％を超え２０モル％未満、好ましくは０．１～１８モル％、より好ましくは０．５～１５モル％、更に好ましくは１～１０モル％であることを特徴とするコーティング剤組成物である（即ち、前記片末端加水分解性ポリマーと前記両末端加水分解性ポリマーとの２成分の合計モルに対する片末端加水分解性ポリマーの含有割合が８０モル％以上１００モル％未満、好ましくは８２～９９．９モル％、より好ましくは８５～９９．５モル％、更に好ましくは９０～９９モル％であることを特徴とするコーティング剤組成物である。）。
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%.
上記一般式（１）において、Ａは末端が－ＣＦ3基である１価のフッ素含有基、好ましくは１～６の直鎖状又は分岐鎖状のパーフルオロアルキル基であり、具体的には、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、１－（トリフルオロメチル）－１，２，２，２－テトラフルオロエチル基、ノナフルオロブチル基、１，１－ジ（トリフルオロメチル）－２，２，２－トリフルオロエチル基、ウンデカフルオロペンチル基、トリデカフルオロヘキシル基、ペンタデカフルオロヘプチル基、ヘプタデカフルオロオクチル基などが挙げられ、この中でも好ましくはトリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ノナフルオロブチル基、ウンデカフルオロペンチル基、トリデカフルオロヘキシル基であり、特に好ましくはトリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基である。
In the above general formula (1), 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, undecafluoropentyl group, tridecaful A Rohekishiru group, particularly preferably trifluoromethyl group, pentafluoroethyl group, a heptafluoropropyl group.
上記一般式（１）及び一般式（２）において、Ｒｆ基は－（ＣＦ2）d－（ＯＹ）e－Ｏ（ＣＦ2）d－で表される基であり、ｄはそれぞれ独立に０又は１～５の整数であり、ＯＹはＯＣＦ2ＣＦ2ＣＦ2ＣＦ2、ＯＣＦ2ＣＦ2ＣＦ2、ＯＣＦ（ＣＦ3）ＣＦ2、ＯＣＦ2ＣＦ2及びＯＣＦ2よりなる群から選ばれる１種又は２種以上の基であり、配列順序はランダムでもブロックでもよく、ｅは５～２００の整数である。
In the general formulas (1) and (2), 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. Or two or more groups, the arrangement order may be random or block, and e is an integer of 5 to 200.
上記一般式（１）及び一般式（２）において、Ｑはエーテル結合を含んでいてもよい炭素数２～６の２価の炭化水素基であり、例えば下記の基が挙げられる（下記の各例示において、左端がＲｆ基に連結し、右端がＳｉに連結している）。
In the above general formulas (1) and (2), 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).
上記一般式（１）及び一般式（２）において、ｃは３～８の整数、好ましくは３～６の整数である。
上記一般式（１）及び一般式（２）において、Ｘは加水分解性基であり、例えば、メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基、トリフルオロメトキシ基、トリフルオロエトキシ基、トリクロロエトキシ基等のハロゲン化アルコキシ基、メトキシエトキシ基等のアルコキシ基置換アルコキシ基、アセトキシ基、プロピオニルオキシ基、ベンゾイルオキシ基等のアシルオキシ基、イソプロペニルオキシ基、イソブテニルオキシ基等のアルケニルオキシ基、ジメチルケトキシム基、メチルエチルケトキシム基、ジエチルケトキシム基等のケトオキシム基、シクロヘキサンオキシム基等のイミンオキシ基、メチルアミノ基、エチルアミノ基、ジメチルアミノ基、ジエチルアミノ基等の置換アミノ基、Ｎ－メチルアセトアミド基、Ｎ－エチルアミド基等のアミド基、ジメチルアミノオキシ基、ジエチルアミノオキシ基等の置換アミノオキシ基、塩素原子等のハロゲン基などが挙げられる。Ｘの例の中では、メトキシ基、エトキシ基、トリフルオロエトキシ基、アセトキシ基、イソプロペニルオキシ基、塩素原子、ジメチルケトキシム基、メチルエチルケトキシム基が好ましく、メトキシ基、エトキシ基、イソプロペニルオキシ基が特に好ましい。Ｘは、１種又は２種以上の組合せとして、本発明の加水分解性ポリマーに含めることができる。 In the above general formulas (1) and (2), c is an integer of 3 to 8, preferably an integer of 3 to 6.
In the above general formula (1) and general formula (2), 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. Among the examples of X, 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.
上記一般式（１）及び一般式（２）において、Ｘは加水分解性基であり、例えば、メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基、トリフルオロメトキシ基、トリフルオロエトキシ基、トリクロロエトキシ基等のハロゲン化アルコキシ基、メトキシエトキシ基等のアルコキシ基置換アルコキシ基、アセトキシ基、プロピオニルオキシ基、ベンゾイルオキシ基等のアシルオキシ基、イソプロペニルオキシ基、イソブテニルオキシ基等のアルケニルオキシ基、ジメチルケトキシム基、メチルエチルケトキシム基、ジエチルケトキシム基等のケトオキシム基、シクロヘキサンオキシム基等のイミンオキシ基、メチルアミノ基、エチルアミノ基、ジメチルアミノ基、ジエチルアミノ基等の置換アミノ基、Ｎ－メチルアセトアミド基、Ｎ－エチルアミド基等のアミド基、ジメチルアミノオキシ基、ジエチルアミノオキシ基等の置換アミノオキシ基、塩素原子等のハロゲン基などが挙げられる。Ｘの例の中では、メトキシ基、エトキシ基、トリフルオロエトキシ基、アセトキシ基、イソプロペニルオキシ基、塩素原子、ジメチルケトキシム基、メチルエチルケトキシム基が好ましく、メトキシ基、エトキシ基、イソプロペニルオキシ基が特に好ましい。Ｘは、１種又は２種以上の組合せとして、本発明の加水分解性ポリマーに含めることができる。 In the above general formulas (1) and (2), c is an integer of 3 to 8, preferably an integer of 3 to 6.
In the above general formula (1) and general formula (2), 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. Among the examples of X, 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.
本発明のコーティング剤組成物（以下、フルオロオキシアルキレン基含有ポリマー組成物ともいう）は、更に下記式（３）
Ａ－Ｒｆ－Ａ （３）
（式中、Ｒｆ及びＡは前記式（１）及び（２）に記載したものと同じ。）
で表されるフルオロオキシアルキレン基含有ポリマー（以下、無官能性ポリマーと称す）を含有してもよい。 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).
Ａ－Ｒｆ－Ａ （３）
（式中、Ｒｆ及びＡは前記式（１）及び（２）に記載したものと同じ。）
で表されるフルオロオキシアルキレン基含有ポリマー（以下、無官能性ポリマーと称す）を含有してもよい。 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).
本発明に用いられるフルオロオキシアルキレン基含有ポリマーが上記無官能性ポリマーを含有する場合には、前述した片末端加水分解性ポリマー、両末端加水分解性ポリマー、及び当該無官能性ポリマーの３成分の合計モルに対する片末端加水分解性ポリマーの割合が６５モル％以上、好ましくは７０モル％以上、より好ましくは８０モル％以上であり、１００モル％未満であると共に、両末端加水分解性ポリマーの割合が０モル％を超え２０モル％未満、好ましくは０．１～１８モル％、より好ましくは１～１０モル％であることが望ましい。無官能性ポリマーの割合は０モル％を超え３０モル％未満、好ましくは１～２５モル％、より好ましくは５～２０モル％未満であるのがよい。
When 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%.
上記フルオロオキシアルキレン基含有ポリマー組成物は、例えば、下記（ｉ）～（ｖｉ）の工程により製造することができる。
The above-mentioned fluorooxyalkylene group-containing polymer composition can be produced, for example, by the following steps (i) to (vi).
（ｉ）両末端にカルボン酸を有するパーフルオロオキシ化合物の末端を部分フッ素化することにより、片末端にカルボン酸基を有するフルオロオキシアルキレン基含有ポリマー（以下、片末端カルボン酸ポリマーと称す）及び両末端にカルボン酸基を有するフルオロオキシアルキレン基含有ポリマー（以下、両末端カルボン酸ポリマーと称す）を含む混合物を製造する。当該部分フッ素化反応において、末端－ＣＦ3基の導入率は、供給するフッ素ガスの量を調整しフッ素化を制御することによって適宜調整することができる。該工程で得られる混合物は、末端にカルボン酸基を有しないフルオロオキシアルキレン基含有ポリマー（以下、無官能性ポリマーと称す）を含んでいてもよい。
(I) 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. In the partial fluorination reaction, 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).
（ｉｉ）片末端カルボン酸ポリマー及び両末端カルボン酸ポリマーを含む混合物を、吸着処理及び／又は分子蒸留処理に供し、片末端にカルボン酸基を有するフルオロオキシアルキレン基含有ポリマーを高濃度で含有する、基本的には３成分系のポリマー組成物を得る。吸着処理及び／又は分子蒸留処理の方法は公知の方法に従えばよい。該工程により、片末端加水分解性ポリマー及び両末端加水分解性ポリマーの合計モルに対する、両末端加水分解性ポリマーの含有比率を調整できる。
(Ii) 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. Basically, 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.
（ｉｉｉ）該３成分系ポリマー組成物中の末端カルボン酸基を変性して、末端に脂肪族不飽和基を有する基を導入する。導入方法は公知の方法に従えばよい。例えば、先ず、上記末端カルボン酸基含有の３成分系ポリマー組成物を、金属水素化物を用いた還元、あるいは貴金属触媒を用いた接触水素化に供し、下記に示す末端ヒドロキシル基（メチロール基）含有の３成分系ポリマー組成物とする（式中、Ｒｆ基は前記と同じである）。
(Iii) 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).
次に、上記で得られた３成分系ポリマー組成物の末端ヒドロキシル基に脂肪族不飽和基を導入する。末端ヒドロキシル基への脂肪族不飽和基の導入は公知の方法に従えばよい。該工程により、下記に示すような、末端にアリル基等のアルケニル基が導入された末端脂肪族不飽和基含有の３成分系ポリマー組成物が製造される。
Next, 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. By this step, 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.
（ｉｖ）次に、上記３成分系ポリマー組成物の末端脂肪族不飽和基にＳｉＨ基１個と加水分解性基３個を有する有機ケイ素化合物、例えばトリメトキシシランをヒドロシリル化付加反応させる。付加反応は公知の反応条件で行えばよく、付加反応触媒、例えば白金族化合物の存在下で行えばよい。該工程により、下記に示すような、末端に加水分解性シリル基を有する３成分系のポリマー組成物が製造される。
(Iv) Next, 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. By this step, a three-component polymer composition having a hydrolyzable silyl group at the terminal as shown below is produced.
（ｖ）次に、上記３成分系ポリマー組成物の加水分解性シリル基にテトラメチルジシロキサン（１，３－ジヒドロ－１，１，３，３－テトラメチルジシロキサン）を塩酸又は硫酸存在下で共加水分解させることにより、下記に示すような、末端にＳｉＨ基を３個有する３成分系のポリマー組成物が製造される。共加水分解の方法は、公知の方法に従えばよい。
(V) Next, tetramethyldisiloxane (1,3-dihydro-1,1,3,3-tetramethyldisiloxane) is added to the hydrolyzable silyl group of the three-component polymer composition in the presence of hydrochloric acid or sulfuric acid. As shown below, a three-component polymer composition having three SiH groups at the terminal is produced. The method of cohydrolysis may follow a well-known method.
（ｖｉ）次いで、上記３成分系ポリマー組成物中の該ＳｉＨ基に、一方の末端に脂肪族不飽和基を有し、他方の末端に加水分解性シリル基を有する有機ケイ素化合物を付加反応させる。付加反応は公知の反応条件で行えばよく、付加反応触媒、例えば白金族化合物の存在下で行えばよい。該工程により、３成分系のポリマー組成物として本発明のフルオロオキシアルキレン基含有ポリマー組成物を得ることができる。
(Vi) Next, 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. By this step, the fluorooxyalkylene group-containing polymer composition of the present invention can be obtained as a three-component polymer composition.
本発明のコーティング剤組成物に用いられる片末端及び両末端加水分解性ポリマーは、それぞれゲルパーミエーションクロマトグラフィによって求めたポリスチレン換算の数平均分子量が、好ましくは５００以上４０，０００以下、特に好ましくは１，０００以上３０，０００以下、更に好ましくは１，０００以上２０，０００以下の範囲であるものを用いることが望ましい。数平均分子量が５００未満ではフルオロオキシアルキレン基の特徴である撥水撥油性、防汚性などを十分に発揮することができない場合があり、４０，０００を超えると末端官能基の濃度が小さくなりすぎて、基材との反応性や密着性が低下する場合がある。
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.
本発明で言及する数平均分子量とは、下記条件で測定したゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算の数平均分子量を指す（以下、同じ）。
［測定条件］
展開溶媒：ハイドロクロロフルオロカーボン（ＨＣＦＣ）－２２５
流量：１ｍＬ／ｍｉｎ．
検出器：蒸発光散乱検出器
カラム：東ソー社製 ＴＳＫｇｅｌ Ｍｕｌｔｉｐｏｒｅ ＨＸＬ－Ｍ
７．８ｍｍφ×３０ｃｍ ２本使用
カラム温度：３５℃
試料注入量：１００μＬ（濃度０．３質量％のＨＣＦＣ－２２５溶液） 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).
[Measurement condition]
Developing solvent: Hydrochlorofluorocarbon (HCFC) -225
Flow rate: 1 mL / min.
Detector: Evaporative light scattering detector Column: Tosoh Corporation TSKgel Multipore HXL-M
7.8 mmφ × 30 cm 2 column temperature used: 35 ° C.
Sample injection amount: 100 μL (HCFC-225 solution with a concentration of 0.3 mass%)
［測定条件］
展開溶媒：ハイドロクロロフルオロカーボン（ＨＣＦＣ）－２２５
流量：１ｍＬ／ｍｉｎ．
検出器：蒸発光散乱検出器
カラム：東ソー社製 ＴＳＫｇｅｌ Ｍｕｌｔｉｐｏｒｅ ＨＸＬ－Ｍ
７．８ｍｍφ×３０ｃｍ ２本使用
カラム温度：３５℃
試料注入量：１００μＬ（濃度０．３質量％のＨＣＦＣ－２２５溶液） 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).
[Measurement condition]
Developing solvent: Hydrochlorofluorocarbon (HCFC) -225
Flow rate: 1 mL / min.
Detector: Evaporative light scattering detector Column: Tosoh Corporation TSKgel Multipore HXL-M
7.8 mmφ × 30 cm 2 column temperature used: 35 ° C.
Sample injection amount: 100 μL (HCFC-225 solution with a concentration of 0.3 mass%)
本発明のコーティング剤組成物は、溶剤もしくは希釈剤を含んでもよい。このような溶剤もしくは希釈剤としては、例えば、アルコール類（エチルアルコール、イソプロピルアルコールなど）、炭化水素系溶剤（石油ベンジン、ミネラルスピリッツ、トルエン、キシレンなど）、エステル系溶剤（酢酸エチル、酢酸イソプロピル、酢酸ブチルなど）、エーテル系溶剤（ジエチルエーテル、イソプロピルエーテルなど）、ケトン系溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトンなど）が挙げられ、アルコール、エステル、エーテル、ケトン類等の極性溶剤を用いることが好ましく、溶解性、濡れ性、安全性などの点で、特にイソプロピルアルコール、メチルイソブチルケトンが好ましい。フッ素系溶剤（パーフルオロ溶剤）も好ましく使用され、その例としては、フッ素化脂肪族炭化水素系溶剤（パーフルオロヘプタン等）、フッ素化芳香族炭化水素系溶剤（ｍ－キシレンヘキサフロライド、ベンゾトリフロライド等）、フッ素化エーテル系溶剤［メチルパーフルオロブチルエーテル、エチルパーフルオロブチルエーテル、パーフルオロ（２－ブチルテトラヒドロフラン）、エチルノナフルオロイソブチルエーテル、エチルノナフルオロブチルエーテル等］が挙げられ、中でも、溶解性、濡れ性等の点で、フッ素化エーテル系溶剤が好適に用いられる。
なお、上記溶剤は、１種を単独で用いても２種以上を混合して用いてもよく、いずれにしても上記成分を均一に溶解させるものを用いることが好ましい。 The coating agent composition of the present invention may contain a solvent or a diluent. Examples of such 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. In view of solubility, wettability, safety, etc., isopropyl alcohol and methyl isobutyl ketone are particularly preferable. Fluorine solvents (perfluoro solvents) are also preferably used. Examples thereof include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, etc.), fluorinated aromatic hydrocarbon solvents (m-xylene hexafluoride, benzoate). Trifluoride, etc.), fluorinated ether solvents [methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, etc.], among others Fluorinated ether solvents are preferably used in terms of properties, wettability and the like.
In addition, 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.
なお、上記溶剤は、１種を単独で用いても２種以上を混合して用いてもよく、いずれにしても上記成分を均一に溶解させるものを用いることが好ましい。 The coating agent composition of the present invention may contain a solvent or a diluent. Examples of such 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. In view of solubility, wettability, safety, etc., isopropyl alcohol and methyl isobutyl ketone are particularly preferable. Fluorine solvents (perfluoro solvents) are also preferably used. Examples thereof include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, etc.), fluorinated aromatic hydrocarbon solvents (m-xylene hexafluoride, benzoate). Trifluoride, etc.), fluorinated ether solvents [methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, etc.], among others Fluorinated ether solvents are preferably used in terms of properties, wettability and the like.
In addition, 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.
溶剤の使用量は特に制限されるものではなく、処理方法により最適濃度は異なる。蒸着用途の場合、一般にコーティング剤組成物中の固形分量が１～８０質量％、特に５～５０質量％となる量を用いることが好ましい。スプレー塗工やディッピング塗工の場合、該組成物中の固形分量が０．０５～２０．０質量％、特に０．１～１．０質量％となる量を用いることが好ましい。なお固形分量は不揮発成分の質量を意味する。
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.
上記コーティング剤組成物は、速い硬化速度を必要とする場合、必要に応じて硬化触媒を添加してもよい。硬化触媒の例としては、有機チタン酸エステル、有機チタンキレート化合物、有機アルミニウム化合物、有機ジルコニウム化合物、有機スズ化合物、有機カルボン酸の金属塩、アミン化合物及びその塩、４級アンモニウム化合物、アルカリ金属の低級脂肪酸塩、ジアルキルヒドロキシアミン、グアジニル基含有有機ケイ素化合物、無機酸、パーフルオロカルボン酸、パーフルオロアルコールなどが挙げられ、好ましくはパーフルオロカルボン酸が使用される。
When the coating agent composition requires a high curing speed, a curing catalyst may be added as necessary. Examples of 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. Preferably, perfluorocarboxylic acids are used.
硬化触媒の添加量は触媒量であり、本発明にかかる含フッ素有機シラン化合物、その部分加水分解物あるいはそれらの部分加水分解縮合物（即ち、片末端及び両末端加水分解性ポリマー並びにこれらの部分加水分解物及び部分加水分解縮合物の総量（ポリマー成分の総量））１００質量部に対して０．０５～５質量部、特に０．１～１質量部であることが好ましい。
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.
このようにして得られた本発明のコーティング剤組成物を表面改質剤として基材に施与する方法としては、刷毛塗り、ディッピング、スプレー等のウェットコーティング法や、蒸着処理等のドライコーティング法など公知の方法がある。
As a method of applying the coating composition of the present invention thus obtained to a substrate as a surface modifier, wet coating methods such as brushing, dipping and spraying, and dry coating methods such as vapor deposition There are known methods.
施与したコーティング剤組成物（表面改質剤）の処理温度は、施与方法によって最適な温度が異なるが、例えばスプレー塗工やディッピングの場合は、１０～１００℃の範囲が望ましい。処理湿度としては、加湿下で行うことが反応を促進する上で望ましい。
従来の表面改質剤の硬化時間は通常１２～２４時間である。これに対し本発明の方法では、硬化時間は６時間以下、特には１～４時間、更には１～３時間でよい。本発明の方法は、上記表面改質剤を使用することにより、このような短時間の硬化であっても、優れた表面特性、特には優れた低動摩擦性及び耐擦傷性を有する硬化被膜を提供することができる。なお、上記処理条件は、基材、硬化触媒等に応じて、適宜最適化することが望ましい。 The optimum processing temperature of the applied coating agent composition (surface modifier) 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. In addition, it is desirable to optimize the said process conditions suitably according to a base material, a curing catalyst, etc.
従来の表面改質剤の硬化時間は通常１２～２４時間である。これに対し本発明の方法では、硬化時間は６時間以下、特には１～４時間、更には１～３時間でよい。本発明の方法は、上記表面改質剤を使用することにより、このような短時間の硬化であっても、優れた表面特性、特には優れた低動摩擦性及び耐擦傷性を有する硬化被膜を提供することができる。なお、上記処理条件は、基材、硬化触媒等に応じて、適宜最適化することが望ましい。 The optimum processing temperature of the applied coating agent composition (surface modifier) 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. In addition, it is desirable to optimize the said process conditions suitably according to a base material, a curing catalyst, etc.
上記コーティング剤組成物で処理される基材は特に制限されず、紙、布、金属及びその酸化物、ガラス、プラスチック、セラミック、石英など各種材質のものであってよい。本発明のコーティング剤組成物は、前記基材に撥水撥油性を付与することができる。特に、化学強化ガラス、ＳｉＯ2処理されたガラスやフイルムの表面改質剤として好適に使用することができる。
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.
上記各種基材あるいは物品表面に形成されるコーティング剤組成物の硬化被膜の膜厚は、基材の種類により適宜選定されるが、好ましくは１～１００ｎｍ、より好ましくは３～２０ｎｍである。
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.
得られる被膜は、撥水撥油性、高滑水性である上に、従来品に比べて耐熱性、耐薬品性、耐ＵＶ性などの耐久性に優れる。かかる特性は、水や紫外線に晒されることが多く、メンテナンスが容易でない用途や、油脂や指紋、化粧品、日焼け止めクリーム、人や動物の***物、油等が付着し易い用途に有効であり、例えば自動車、電車、船舶、航空機、高層ビル等の窓ガラス又は強化ガラス、ヘッドランプカバー、アウトドア用品、電話ボックス、屋外用の大型ディスプレイ、浴槽、洗面台のようなサニタリー製品、化粧道具、台所用建材、水槽、美術品などの指紋付着防止付与のコーティング等が挙げられる。その他、コンパクトディスク、ＤＶＤなどの指紋付着防止コーティング、金型用に離型剤あるいは塗料添加剤、樹脂改質剤としても有用である。また、カーナビゲーション、携帯電話、デジタルカメラ、デジタルビデオカメラ、ＰＤＡ、ポータブルオーディオプレーヤー、カーオーディオ、ゲーム機器、眼鏡レンズ、カメラレンズ、レンズフィルター、サングラス、胃カメラ等の医療用器機、複写機、ＰＣ、液晶ディスプレイ、有機ＥＬディスプレイ、プラズマディスプレイ、タッチパネルディスプレイ、保護フイルム、反射防止フイルムなどの光学物品が挙げられる。本発明の表面改質剤は、前記物品に指紋及び皮脂が付着するのを防止し、更に傷つき防止性を付与することができるため、特にタッチパネルディスプレイ、反射防止フイルムなどの撥水撥油層として有用である。
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. For example, 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. In addition, it is also useful as a fingerprint preventing coating for compact discs, DVDs, etc., as a mold release agent or paint additive for resin molds, and as a resin modifier. In addition, 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.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
フルオロオキシアルキレン基含有ポリマー組成物
下記４種類のポリマー組成物を準備した。
［ポリマー組成物１］…（本発明組成物）
下記式（４）
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５。なお、ポリマー中に（ＯＣＦ2ＣＦ2ＣＦ2）単位及び（ＯＣＦ2ＣＦ2ＣＦ2ＣＦ2）単位を含んでいるが、微量であるため、化学式（４）の表記には加えていない）において、
（１ａ）：前記式（４）のＸ1が下記式（ａ）で示される基であり、Ｘ2がフッ素原子である片末端加水分解性ポリマー：８３モル％、
（１ｂ）：前記式（４）のＸ1、Ｘ2がいずれも下記式（ａ）で示される基である両末端加水分解性ポリマー：８モル％、
（１ｃ）：前記式（４）のＸ1、Ｘ2がいずれもフッ素原子である無官能性ポリマー：９モル％
からなるポリマー組成物。
Fluorooxyalkylene group-containing polymer composition The following four polymer compositions were prepared.
[Polymer Composition 1] (Invention Composition)
Following formula (4)
(P / q = 0.9, p + q≈45. The polymer contains (OCF 2 CF 2 CF 2 ) units and (OCF 2 CF 2 CF 2 CF 2 ) units. In the chemical formula (4) notation)
(1a): 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%,
(1b): Both terminal hydrolyzable polymers wherein X 1 and X 2 in the formula (4) are groups represented by the following formula (a): 8 mol%,
(1c): Nonfunctional polymer in which X 1 and X 2 in the formula (4) are both fluorine atoms: 9 mol%
A polymer composition comprising:
下記４種類のポリマー組成物を準備した。
［ポリマー組成物１］…（本発明組成物）
下記式（４）
（１ａ）：前記式（４）のＸ1が下記式（ａ）で示される基であり、Ｘ2がフッ素原子である片末端加水分解性ポリマー：８３モル％、
（１ｂ）：前記式（４）のＸ1、Ｘ2がいずれも下記式（ａ）で示される基である両末端加水分解性ポリマー：８モル％、
（１ｃ）：前記式（４）のＸ1、Ｘ2がいずれもフッ素原子である無官能性ポリマー：９モル％
からなるポリマー組成物。
[Polymer Composition 1] (Invention Composition)
Following formula (4)
(1a): 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%,
(1b): Both terminal hydrolyzable polymers wherein X 1 and X 2 in the formula (4) are groups represented by the following formula (a): 8 mol%,
(1c): Nonfunctional polymer in which X 1 and X 2 in the formula (4) are both fluorine atoms: 9 mol%
A polymer composition comprising:
［ポリマー組成物２］…（本発明組成物）
前記式（４）において、
（２ａ）：前記式（４）のＸ1が下記式（ｂ）で示される基であり、Ｘ2がフッ素原子である片末端加水分解性ポリマー：８３モル％、
（２ｂ）：前記式（４）のＸ1、Ｘ2がいずれも下記式（ｂ）で示される基である両末端加水分解性ポリマー：８モル％、
（２ｃ）：前記式（４）のＸ1、Ｘ2がいずれもフッ素原子である無官能性ポリマー：９モル％
からなるポリマー組成物。
[Polymer composition 2] (Invention composition)
In the formula (4),
(2a): One end hydrolyzable polymer in which X 1 in the formula (4) is a group represented by the following formula (b) and X 2 is a fluorine atom: 83 mol%,
(2b): Both end hydrolyzable polymers in which X 1 and X 2 in the formula (4) are groups represented by the following formula (b): 8 mol%,
(2c): Non-functional polymer in which X 1 and X 2 in formula (4) are both fluorine atoms: 9 mol%
A polymer composition comprising:
前記式（４）において、
（２ａ）：前記式（４）のＸ1が下記式（ｂ）で示される基であり、Ｘ2がフッ素原子である片末端加水分解性ポリマー：８３モル％、
（２ｂ）：前記式（４）のＸ1、Ｘ2がいずれも下記式（ｂ）で示される基である両末端加水分解性ポリマー：８モル％、
（２ｃ）：前記式（４）のＸ1、Ｘ2がいずれもフッ素原子である無官能性ポリマー：９モル％
からなるポリマー組成物。
In the formula (4),
(2a): One end hydrolyzable polymer in which X 1 in the formula (4) is a group represented by the following formula (b) and X 2 is a fluorine atom: 83 mol%,
(2b): Both end hydrolyzable polymers in which X 1 and X 2 in the formula (4) are groups represented by the following formula (b): 8 mol%,
(2c): Non-functional polymer in which X 1 and X 2 in formula (4) are both fluorine atoms: 9 mol%
A polymer composition comprising:
［ポリマー組成物３］…（比較用組成物）
前記式（４）において、
（３ａ）：前記式（４）のＸ1が下記式（ｃ）で示される基であり、Ｘ2がフッ素原子である片末端加水分解性ポリマー：８３モル％、
（３ｂ）：前記式（４）のＸ1、Ｘ2がいずれも下記式（ｃ）で示される基である両末端加水分解性ポリマー：８モル％、
（３ｃ）：前記式（４）のＸ1、Ｘ2がいずれもフッ素原子である無官能性ポリマー：９モル％
からなるポリマー組成物。
[Polymer Composition 3] (Comparative Composition)
In the formula (4),
(3a): One end hydrolyzable polymer in which X 1 in the formula (4) is a group represented by the following formula (c) and X 2 is a fluorine atom: 83 mol%,
(3b): Both terminal hydrolyzable polymers in which X 1 and X 2 in the formula (4) are groups represented by the following formula (c): 8 mol%,
(3c): Non-functional polymer in which X 1 and X 2 in formula (4) are both fluorine atoms: 9 mol%
A polymer composition comprising:
前記式（４）において、
（３ａ）：前記式（４）のＸ1が下記式（ｃ）で示される基であり、Ｘ2がフッ素原子である片末端加水分解性ポリマー：８３モル％、
（３ｂ）：前記式（４）のＸ1、Ｘ2がいずれも下記式（ｃ）で示される基である両末端加水分解性ポリマー：８モル％、
（３ｃ）：前記式（４）のＸ1、Ｘ2がいずれもフッ素原子である無官能性ポリマー：９モル％
からなるポリマー組成物。
In the formula (4),
(3a): One end hydrolyzable polymer in which X 1 in the formula (4) is a group represented by the following formula (c) and X 2 is a fluorine atom: 83 mol%,
(3b): Both terminal hydrolyzable polymers in which X 1 and X 2 in the formula (4) are groups represented by the following formula (c): 8 mol%,
(3c): Non-functional polymer in which X 1 and X 2 in formula (4) are both fluorine atoms: 9 mol%
A polymer composition comprising:
［ポリマー組成物４］…（比較用組成物）
前記式（４）において、
（４ａ）：前記式（４）のＸ1が下記式（ｄ）で示される基であり、Ｘ2がフッ素原子である片末端加水分解性ポリマー：８３モル％、
（４ｂ）：前記式（４）のＸ1、Ｘ2がいずれも下記式（ｄ）で示される基である両末端加水分解性ポリマー：８モル％、
（４ｃ）：前記式（４）のＸ1、Ｘ2がいずれもフッ素原子である無官能性ポリマー：９モル％
からなるポリマー組成物。
[Polymer composition 4] (comparison composition)
In the formula (4),
(4a): One end hydrolyzable polymer in which X 1 in the formula (4) is a group represented by the following formula (d) and X 2 is a fluorine atom: 83 mol%,
(4b): Both end hydrolyzable polymers in which X 1 and X 2 in the formula (4) are groups represented by the following formula (d): 8 mol%,
(4c): Nonfunctional polymer in which X 1 and X 2 in formula (4) are both fluorine atoms: 9 mol%
A polymer composition comprising:
前記式（４）において、
（４ａ）：前記式（４）のＸ1が下記式（ｄ）で示される基であり、Ｘ2がフッ素原子である片末端加水分解性ポリマー：８３モル％、
（４ｂ）：前記式（４）のＸ1、Ｘ2がいずれも下記式（ｄ）で示される基である両末端加水分解性ポリマー：８モル％、
（４ｃ）：前記式（４）のＸ1、Ｘ2がいずれもフッ素原子である無官能性ポリマー：９モル％
からなるポリマー組成物。
In the formula (4),
(4a): One end hydrolyzable polymer in which X 1 in the formula (4) is a group represented by the following formula (d) and X 2 is a fluorine atom: 83 mol%,
(4b): Both end hydrolyzable polymers in which X 1 and X 2 in the formula (4) are groups represented by the following formula (d): 8 mol%,
(4c): Nonfunctional polymer in which X 1 and X 2 in formula (4) are both fluorine atoms: 9 mol%
A polymer composition comprising:
［コーティング剤組成物の調製］
上記ポリマー組成物１～４を、水分含有量１０ｐｐｍ以下になるように脱水処理したフッ素系溶剤Ｎｏｖｅｃ７（登録商標）２００（３Ｍ社製；エチルパーフルオロブチルエーテル）で、濃度０．０８質量％になるように希釈溶解させてコーティング剤組成物を調製した。 [Preparation of coating agent composition]
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. Thus, a coating composition was prepared by diluting and dissolving.
上記ポリマー組成物１～４を、水分含有量１０ｐｐｍ以下になるように脱水処理したフッ素系溶剤Ｎｏｖｅｃ７（登録商標）２００（３Ｍ社製；エチルパーフルオロブチルエーテル）で、濃度０．０８質量％になるように希釈溶解させてコーティング剤組成物を調製した。 [Preparation of coating agent composition]
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. Thus, a coating composition was prepared by diluting and dissolving.
［ガラス基材上への硬化被膜の形成］
表面を化学強化処理したガラス（５０ｍｍ×１００ｍｍ、コーニング社製 Ｇｏｒｉｌｌａ３）の表面をプラズマ処理（Ａｒ：１０ｃｃ、Ｏ2：８０ｃｃ、出力：２５０Ｗ、時間：３０秒）で洗浄後、上記各コーティング剤組成物をスプレー塗工装置（株式会社ティーアンドケー製、ＮＳＴ－５１）でスプレー塗工し、８０℃、湿度８０％の雰囲気で１時間硬化させて膜厚７～８ｎｍの硬化被膜を形成した。 [Formation of cured coating on glass substrate]
After the surface of glass (50 mm × 100 mm, Gorilla 3 manufactured by Corning) whose surface has been chemically strengthened is cleaned by plasma treatment (Ar: 10 cc, O 2 : 80 cc, output: 250 W, time: 30 seconds), each coating composition described above The product was spray-coated with a spray coating apparatus (manufactured by T & K Co., Ltd., NST-51) and cured in an atmosphere of 80 ° C. and humidity of 80% for 1 hour to form a cured film having a thickness of 7 to 8 nm.
表面を化学強化処理したガラス（５０ｍｍ×１００ｍｍ、コーニング社製 Ｇｏｒｉｌｌａ３）の表面をプラズマ処理（Ａｒ：１０ｃｃ、Ｏ2：８０ｃｃ、出力：２５０Ｗ、時間：３０秒）で洗浄後、上記各コーティング剤組成物をスプレー塗工装置（株式会社ティーアンドケー製、ＮＳＴ－５１）でスプレー塗工し、８０℃、湿度８０％の雰囲気で１時間硬化させて膜厚７～８ｎｍの硬化被膜を形成した。 [Formation of cured coating on glass substrate]
After the surface of glass (50 mm × 100 mm, Gorilla 3 manufactured by Corning) whose surface has been chemically strengthened is cleaned by plasma treatment (Ar: 10 cc, O 2 : 80 cc, output: 250 W, time: 30 seconds), each coating composition described above The product was spray-coated with a spray coating apparatus (manufactured by T & K Co., Ltd., NST-51) and cured in an atmosphere of 80 ° C. and humidity of 80% for 1 hour to form a cured film having a thickness of 7 to 8 nm.
［撥水撥油性の評価］
接触角計Ｄｒｏｐ Ｍａｓｔｅｒ（協和界面科学社製）を用いて、硬化被膜の水に対する接触角（撥水性）及びオレイン酸に対する接触角（撥油性）を測定した。 [Evaluation of water and oil repellency]
Using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the cured coating with water (water repellency) and the contact angle with oleic acid (oil repellency) were measured.
接触角計Ｄｒｏｐ Ｍａｓｔｅｒ（協和界面科学社製）を用いて、硬化被膜の水に対する接触角（撥水性）及びオレイン酸に対する接触角（撥油性）を測定した。 [Evaluation of water and oil repellency]
Using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the cured coating with water (water repellency) and the contact angle with oleic acid (oil repellency) were measured.
［動摩擦係数の測定］
ベンコット（旭化成社製）に対する動摩擦係数を、表面性試験機１４ＦＷ（新東科学社製）を用いて下記条件で測定した。
接触面積：３５ｍｍ×３５ｍｍ
荷重：２００ｇ [Measurement of dynamic friction coefficient]
The dynamic friction coefficient with respect to Bencott (made by Asahi Kasei Co., Ltd.) was measured using a surface property tester 14FW (made by Shinto Kagaku Co., Ltd.) under the following conditions.
Contact area: 35mm x 35mm
Load: 200g
ベンコット（旭化成社製）に対する動摩擦係数を、表面性試験機１４ＦＷ（新東科学社製）を用いて下記条件で測定した。
接触面積：３５ｍｍ×３５ｍｍ
荷重：２００ｇ [Measurement of dynamic friction coefficient]
The dynamic friction coefficient with respect to Bencott (made by Asahi Kasei Co., Ltd.) was measured using a surface property tester 14FW (made by Shinto Kagaku Co., Ltd.) under the following conditions.
Contact area: 35mm x 35mm
Load: 200g
［摩耗耐久性の評価］
ラビングテスター（新東科学社製）を用いて、下記条件で、スチールウールにより硬化被膜の表面を擦った。３，０００回擦る毎に、擦った後の硬化被膜表面の水接触角を測定し、硬化被膜の水接触角が１００°以上を保持できる擦り回数を測定し、摩耗耐久回数とした。水接触角の測定は、接触角計Ｄｒｏｐ Ｍａｓｔｅｒ（協和界面科学社製）を用いて行った。上記試験環境条件は２５℃、湿度４０％である。
スチールウール：ＢＯＮＳＴＡＲ＃００００（日本スチールウール株式会社製）
移動距離（片道）３０ｍｍ
移動速度１，８００ｍｍ／分
荷重：１ｋｇ／ｃｍ2
なお、評価はＮ＝８で行った平均回数とした。
ポリマー組成物１，２を用いて形成された硬化被膜を実施例１，２、ポリマー組成物３，４を用いて形成された硬化被膜を比較例１，２とした。評価結果を表１に示す。 [Evaluation of wear durability]
Using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.), the surface of the cured coating was rubbed with steel wool under the following conditions. Each time rubbed 3,000 times, the water contact angle on the surface of the cured coating after rubbing was measured, and the number of rubs that could maintain the water contact angle of the cured coating at 100 ° or more was measured to determine the number of wear durability. The water contact angle was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). The test environmental conditions are 25 ° C. and humidity 40%.
Steel wool: BONSTAR # 0000 (manufactured by Nippon Steel Wool Co., Ltd.)
Travel distance (one way) 30mm
Movement speed 1,800mm / min Load: 1kg / cm 2
In addition, evaluation was made into the average frequency | count performed by N = 8.
The cured films formed using the polymer compositions 1 and 2 were designated as Examples 1 and 2, and the cured films formed using the polymer compositions 3 and 4 were designated as Comparative Examples 1 and 2. The evaluation results are shown in Table 1.
ラビングテスター（新東科学社製）を用いて、下記条件で、スチールウールにより硬化被膜の表面を擦った。３，０００回擦る毎に、擦った後の硬化被膜表面の水接触角を測定し、硬化被膜の水接触角が１００°以上を保持できる擦り回数を測定し、摩耗耐久回数とした。水接触角の測定は、接触角計Ｄｒｏｐ Ｍａｓｔｅｒ（協和界面科学社製）を用いて行った。上記試験環境条件は２５℃、湿度４０％である。
スチールウール：ＢＯＮＳＴＡＲ＃００００（日本スチールウール株式会社製）
移動距離（片道）３０ｍｍ
移動速度１，８００ｍｍ／分
荷重：１ｋｇ／ｃｍ2
なお、評価はＮ＝８で行った平均回数とした。
ポリマー組成物１，２を用いて形成された硬化被膜を実施例１，２、ポリマー組成物３，４を用いて形成された硬化被膜を比較例１，２とした。評価結果を表１に示す。 [Evaluation of wear durability]
Using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.), the surface of the cured coating was rubbed with steel wool under the following conditions. Each time rubbed 3,000 times, the water contact angle on the surface of the cured coating after rubbing was measured, and the number of rubs that could maintain the water contact angle of the cured coating at 100 ° or more was measured to determine the number of wear durability. The water contact angle was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). The test environmental conditions are 25 ° C. and humidity 40%.
Steel wool: BONSTAR # 0000 (manufactured by Nippon Steel Wool Co., Ltd.)
Travel distance (one way) 30mm
Movement speed 1,800mm / min Load: 1kg / cm 2
In addition, evaluation was made into the average frequency | count performed by N = 8.
The cured films formed using the polymer compositions 1 and 2 were designated as Examples 1 and 2, and the cured films formed using the polymer compositions 3 and 4 were designated as Comparative Examples 1 and 2. The evaluation results are shown in Table 1.
表１に示すように、本発明のポリマー組成物を使用して硬化被膜を形成した場合は、優れた摩耗耐久性を示す。一方、加水分解性シリル基に隣接するアルキレン基の炭素数が２個の場合（比較例１）は、十分な摩耗耐久性が発現しない。環状シロキサン構造を有する比較例２は、特開２０１４－０８４４０５号公報及び特開２０１４－０７７８３６号公報に記載の構造だが、こちらも本実施例に比べると摩耗耐久性に劣る。
As shown in Table 1, when a cured film is formed using the polymer composition of the present invention, excellent wear durability is exhibited. On the other hand, when the number of carbon atoms of the alkylene group adjacent to the hydrolyzable silyl group is 2 (Comparative Example 1), sufficient wear durability is not exhibited. Comparative Example 2 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.
Claims (14)
- 下記一般式（１）
で表される直鎖状フルオロオキシアルキレン基含有ポリマー（以下、片末端加水分解性ポリマーと称す）と、下記一般式（２）
で表される直鎖状フルオロオキシアルキレン基含有ポリマー（以下、両末端加水分解性ポリマーと称す）を含み、前記片末端加水分解性ポリマーと前記両末端加水分解性ポリマーとの合計モルに対する両末端加水分解性ポリマーの含有割合が０モル％を超え２０モル％未満であることを特徴とするコーティング剤組成物。 The following general formula (1)
A linear fluorooxyalkylene group-containing polymer represented by the following (hereinafter referred to as a single-end hydrolyzable polymer), and the following general formula (2)
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%. - 更に、下記式（３）
Ａ－Ｒｆ－Ａ （３）
（式中、Ｒｆ及びＡは前記と同じ。）
で表されるフルオロオキシアルキレン基含有ポリマー（以下、無官能性ポリマーと称す）を含有し、かつ、片末端加水分解性ポリマーと両末端加水分解性ポリマーと無官能性ポリマーとの合計モルに対する片末端加水分解性ポリマーの含有割合が６５モル％以上１００モル％未満であり、かつ両末端加水分解性ポリマーの含有割合が０モル％を超え２０モル％未満である請求項１記載のコーティング剤組成物。 Further, the following formula (3)
A-Rf-A (3)
(In the formula, Rf and A are the same as above.)
A piece containing a fluorooxyalkylene group-containing polymer represented by the formula (hereinafter referred to as a non-functional polymer), and a piece with respect to the total mole of the one-end hydrolyzable polymer, the two-end hydrolyzable polymer, and the non-functional polymer. The coating agent composition according to claim 1, wherein the content ratio of the terminal hydrolyzable polymer is 65 mol% or more and less than 100 mol%, and the content ratio of both terminal hydrolyzable polymers is more than 0 mol% and less than 20 mol%. object. - 片末端加水分解性ポリマーと両末端加水分解性ポリマーと無官能性ポリマーとの合計モルに対する無官能性ポリマーの含有割合が０モル％を超え３０モル％未満である請求項２記載のコーティング剤組成物。 The coating agent composition according to claim 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.
- 更に、フッ素系溶剤を含有するものである請求項１～３のいずれか１項記載のコーティング剤組成物。 The coating agent composition according to any one of claims 1 to 3, further comprising a fluorinated solvent.
- 一般式（１）及び一般式（２）において、２価の炭化水素基Ｑが下記式で表される基である請求項１～４のいずれか１項記載のコーティング剤組成物。
－ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2－
（但し、左端がＲｆ基に連結し、右端がＳｉに連結している。） The coating agent composition according to any one of claims 1 to 4, wherein in the general formula (1) and the general formula (2), 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.) - 一般式（１）及び一般式（２）において、加水分解性基Ｘが、メトキシ基、エトキシ基、イソプロペノキシ基、アセトキシ基から選ばれる少なくとも１種の基である請求項１～５のいずれか１項記載のコーティング剤組成物。 The hydrolyzable group X in the general formulas (1) and (2) is at least one group selected from a methoxy group, an ethoxy group, an isopropenoxy group, and an acetoxy group. The coating agent composition according to Item.
- 請求項１～６のいずれか１項記載のコーティング剤組成物の硬化被膜を表面に有する物品。 An article having on its surface a cured film of the coating composition according to any one of claims 1 to 6.
- 請求項１～６のいずれか１項記載のコーティング剤組成物の硬化被膜を表面に有する光学物品。 An optical article having on its surface a cured film of the coating composition according to any one of claims 1 to 6.
- 請求項１～６のいずれか１項記載のコーティング剤組成物の硬化被膜を表面に有するタッチパネル。 A touch panel having a cured film of the coating agent composition according to any one of claims 1 to 6 on its surface.
- 請求項１～６のいずれか１項記載のコーティング剤組成物の硬化被膜を表面に有する反射防止フイルム。 An antireflection film having on its surface a cured film of the coating agent composition according to any one of claims 1 to 6.
- 請求項１～６のいずれか１項記載のコーティング剤組成物の硬化被膜を表面に有するＳｉＯ2処理ガラス。 An SiO 2 -treated glass having a cured film of the coating agent composition according to any one of claims 1 to 6 on its surface.
- 請求項１～６のいずれか１項記載のコーティング剤組成物の硬化被膜を表面に有する強化ガラス。 A tempered glass having a cured film of the coating agent composition according to any one of claims 1 to 6 on its surface.
- 請求項１～６のいずれか１項記載のコーティング剤組成物の硬化被膜を表面に有する石英基板。 A quartz substrate having on its surface a cured film of the coating agent composition according to any one of claims 1 to 6.
- 請求項１～６のいずれか１項記載のコーティング剤組成物を用いてドライコーティング法又はウェットコーティング法により物品の表面を処理する工程を含む物品の表面処理方法。 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 claims 1 to 6.
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| CN116034123A (en) | 2020-08-13 | 2023-04-28 | 日产化学株式会社 | Curable composition for hard coating |
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| KR20180087283A (en) | 2018-08-01 |
| KR102511340B1 (en) | 2023-03-17 |
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| TW201736537A (en) | 2017-10-16 |
| TWI717417B (en) | 2021-02-01 |
| CN108368379A (en) | 2018-08-03 |
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| JP6497449B2 (en) | 2019-04-10 |
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