WO2012036053A1 - 防汚性物品及びその製造方法、並びに防汚層形成用塗布剤 - Google Patents

防汚性物品及びその製造方法、並びに防汚層形成用塗布剤 Download PDF

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WO2012036053A1
WO2012036053A1 PCT/JP2011/070431 JP2011070431W WO2012036053A1 WO 2012036053 A1 WO2012036053 A1 WO 2012036053A1 JP 2011070431 W JP2011070431 W JP 2011070431W WO 2012036053 A1 WO2012036053 A1 WO 2012036053A1
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antifouling
group
coating agent
antifouling layer
coating
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PCT/JP2011/070431
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English (en)
French (fr)
Japanese (ja)
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陽平 佐藤
濱口　滋生
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セントラル硝子株式会社
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Priority to CN2011800442073A priority Critical patent/CN103097475A/zh
Priority to KR1020137008949A priority patent/KR101485719B1/ko
Publication of WO2012036053A1 publication Critical patent/WO2012036053A1/ja

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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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

Definitions

  • the present invention forms an antifouling layer that hardly adheres to pollutants, is easy to remove adhering pollutants, and does not have an appearance of white turbidity appearing in the form of dots or streaks when exposed to steam such as water.
  • the present invention relates to a coating agent, an article having an antifouling layer formed using the coating agent, and a method for producing the same.
  • Metals, glass, plastics, ceramics and other base materials are widely used as automobile parts, household items, home appliances, and OA equipment.
  • the surface of these substrates is often contaminated with water droplets or scales due to rain, oily substances such as floating dust or cigarette dust, and fingerprints or sebum from human hands. Further, there is a demand for an antifouling function capable of easily removing dirt once adhered.
  • Patent Document 1 discloses an antifouling agent composition comprising a compound having a perfluoroalkyl ether group.
  • Patent Document 2 discloses a water-repellent treated glass in which a treated film mainly composed of an alkoxysilane compound having a perfluoropolyether group having excellent water repellency, antifouling properties and durability is formed on a substrate.
  • Patent Document 3 discloses a fluorine-containing polymer excellent in antifouling properties against oily contaminants, and particularly excellent in antifouling properties against fingerprints, and an antifouling substrate in which the polymer layer is formed on the substrate surface.
  • Patent Document 4 discloses a perfluoropoly-modified silane excellent in durability, antifouling property, particularly fingerprint wiping property, and a surface treatment agent containing this as a main component.
  • JP 2000-234071 A Japanese Patent Laid-Open No. 11-092177 International Publication No. 98/49218 JP 2003-238777 A
  • an antifouling layer when forming a coating layer (hereinafter referred to as an antifouling layer) that exhibits an antifouling function on the surface of a substrate, as a material constituting the antifouling layer, water and oil repellency
  • a fluorine-containing compound having a high value is used as a material constituting the antifouling layer.
  • the raw material for the antifouling layer is dissolved in a fluorine-based solvent, an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, a hydrocarbon-based solvent, or the like.
  • a method of applying a dispersed liquid has been generally used.
  • Patent Document 1 As a solvent for diluting the raw material of the antifouling layer, for example, in Patent Document 1, hexafluorobenzene, in Patent Document 2, isopropanol, in Patent Document 3, perfluorohexane, etc., in Patent Document 4, perfluoro ( 2-butyltetrahydrofuran) is used.
  • the coating solution obtained by diluting the antifouling layer raw material with an appropriate solvent is not applied to the substrate surface, the portion where the liquid level is raised by the aggregating action of the coating solution (hereinafter referred to as “liquid pool”) And the part which is not so tends to be in a mixed state on the substrate surface.
  • liquid pool the portion where the liquid level is raised by the aggregating action of the coating solution
  • the coating liquid does not sufficiently spread on the surface of the substrate.
  • coating unevenness tends to occur and the coating operation tends to be difficult.
  • the appearance and antifouling properties of the antifouling layer tend to be unstable for each substrate due to the change in the concentration of the coating agent.
  • the present invention provides a coating agent for forming an antifouling layer in which dot-like or streaky white turbidity does not appear on the surface even when exposed to steam such as water, and the coating agent.
  • An object of the present invention is to provide an antifouling article having an antifouling layer and a method for producing the same.
  • the present inventors have used a coating agent in which a perfluoropolyether group-containing silane is dissolved in a specific organic solvent, and forming a coating layer in which the perfluoropolyether group-containing silane is condensed, It has been found that the coating layer functions as an antifouling layer that exhibits an antifouling function and has an appearance that does not reveal dot-like or streaky white turbidity on the surface even when exposed to steam such as water. It came to.
  • the present invention is an organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C., in which a perfluoropolyether group-containing silane represented by the following general formula [1] is dissolved.
  • An antifouling layer-forming coating agent for an antifouling article used under steam is provided. (Wherein W represents a fluorine atom or a substituent represented by the structure of the following formula.
  • X is represented by the formula: — (O) g — (CF 2 ) h — (CH 2 ) i — (where g, h and i each independently represents an integer of 0 to 50, and g and The sum of h is 1 or more, and the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula.
  • Y represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms.
  • Z represents at least one hydrolyzable functional group selected from the group consisting of alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group.
  • R represents an alkyl group having 1 to 10 carbon atoms.
  • a represents an integer of 0 to 50
  • b represents an integer of 1 to 200
  • c represents an integer of 1 to 3
  • d represents an integer of 1 to 10
  • e and f are each independently 0
  • m and n are each independently an integer of 0 to 50, and the sum of m and n is 1 or more.
  • the fluorine-based solvent is preferably at least one selected from the group consisting of hydrofluorocarbon, perfluorocarbon, hydrofluoroether, and hydrochlorofluorocarbon, and at least one selected from the group consisting of perfluorocarbon and hydrofluoroether. More preferably.
  • the perfluoropolyether group-containing silane represented by the general formula [1] is contained in 100% by mass of the antifouling layer forming coating agent.
  • the present invention provides a method for producing an antifouling article using the above antifouling layer-forming coating agent, wherein (1) the holding member holding the coating agent is brought into contact with the substrate surface, Application A in which the coating agent is applied to the entire surface by reciprocating in a specific direction on the substrate surface, and then the holding member is brought into contact with the substrate surface again, and the holding member is applied on the substrate surface with the application A.
  • the antifouling layer-forming coating agent of the present invention is an organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C., which is a perfluoropolyether group represented by the following general formula [1].
  • W represents a fluorine atom or a substituent represented by the structure of the following formula.
  • X represents the formula: — (O) g — (CF 2 ) h — (CH 2 ) i — (wherein g, h and i each independently represents an integer of 0 to 50, and The sum of g and h is 1 or more, and the order of presence of each repeating unit in parentheses is arbitrary in the formula.
  • Y represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms
  • Z is selected from the group consisting of alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group
  • R represents an alkyl group having 1 to 10 carbon atoms.
  • a represents an integer of 0 to 50
  • b represents an integer of 1 to 200
  • c represents an integer of 1 to 3
  • d represents an integer of 1 to 10
  • e and f are each independently 0
  • m and n are each independently an integer of 0 to 50, and the sum of m and n is 1 or more.
  • — [CF 2 ] a —, — [C m F 2m OC n F 2n ] b —, [— (O) g — (CF 2 ) h — (CH 2 ) i —], - [CH 2] e - and, - [CH 2] f - can impart excellent antifouling performance and wear resistance moiety represented by. Therefore, the antifouling layer formed by condensation of the perfluoropolyether group-containing silane as represented by the general formula [1] is preferable because it can achieve both excellent antifouling performance and wear resistance.
  • the hydrolyzable functional group Z condenses to form an antifouling layer, thereby imparting excellent adhesion between the antifouling layer and the substrate surface. it can.
  • the hydrolyzable functional group Z is at least one selected from the group consisting of alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group Is preferred.
  • alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group Is preferred.
  • the hydrolyzable functional groups are preferably alkoxy groups, of which methoxy groups An ethoxy group is particularly preferred.
  • the perfluoropolyether group-containing silane represented by the general formula [1] is considered to be bonded to the substrate surface by Si—O— bonds by hydrolysis of the functional group represented by Z in the Si—Z site.
  • the mole number of fluorine in the perfluoropolyether group-containing silane is about 20 to 200 with respect to 1 mol of silicon contained in the bondable site (Si group-containing site) in the perfluoropolyether group-containing silane.
  • perfluoropolyether group-containing silanes represented by the general formula [1] perfluoropolyether group-containing silanes having a structure represented by the following general formula [2] and the general formula [3] are preferable compounds.
  • Rf 1 represents a linear perfluoroalkyl group having 1 to 100 carbon atoms
  • p represents an integer of 1 to 100
  • q represents an integer of 0 to 2.
  • Y, R, and d are the same as those in the general formula [1].
  • Rf 2 is a linear perfluoroalkylene ether containing a unit represented by the formula: — (C t F 2t O) — (t is an integer of 1 to 6) and having no branch.
  • R, Z, and c are the same as those in the general formula [1].
  • Examples of commercially available products containing such compounds include OPTOOL AES series such as OPTOOL DSX and OPTOOL AES4 manufactured by Daikin Industries, KY130 and KY108 manufactured by Shin-Etsu Chemical, and Fluorosurf FG-5020 manufactured by Fluoro Technology.
  • the solvent contained in this commercial item shall be contained as a part of solvent in the coating agent of this invention.
  • the organic solvent in the coating agent of the present invention has a surface tension of 20.0 mN / m or less.
  • the surface tension of the organic solvent is more than 20.0 mN / m, when the coating agent is applied to the base material, the coagulation action of the coating agent causes a state in which the liquid pool portion and the portion other than the liquid pool are mixed.
  • a more preferable organic solvent is a solvent having a surface tension of 19.5 mN / m or less, and more preferably a solvent having a surface tension of 19.3 mN / m or less.
  • the surface tension of the liquid can be measured by, for example, a plate method.
  • the boiling point of the organic solvent is 95 to 200 ° C.
  • the boiling point of the organic solvent is less than 95 ° C.
  • the drying speed after applying the chemical solution is too fast, and uneven coating tends to occur, or the chemical solution volatilizes during the application, and the substrate surface tends not to be completely spread.
  • the concentration of the perfluoropolyether group-containing silane in the coating agent increases as the organic solvent evaporates.
  • the soiling tends to be unstable for each substrate.
  • the boiling point of the organic solvent is more preferably 105 to 180 ° C.
  • the organic solvent contains 60 to 100% by mass of a fluorinated solvent.
  • concentration of the fluorinated solvent in the organic solvent is less than 60% by mass, the perfluoropolyether group-containing silane represented by the general formula [1] is not sufficiently dissolved, or the surface of the antifouling layer is in the form of dots or streaks. It is not preferable because the white turbidity easily occurs.
  • concentration of the fluorinated solvent in the organic solvent is 70 to 100% by mass, and further preferably 80 to 100% by mass.
  • the fluorinated solvent is preferably at least one selected from the group consisting of hydrofluorocarbons, perfluorocarbons, perfluoroethers, hydrofluoroethers, and hydrochlorofluorocarbons.
  • hydrofluorocarbons perfluorocarbons, perfluoroethers, hydrofluoroethers, and hydrochlorofluorocarbons.
  • perfluorocarbon and hydrofluoroether are more preferable.
  • hydrofluoroether having a smaller global warming potential is particularly preferable as the fluorinated solvent.
  • a fluorine-based solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C.
  • perfluorocarbons such as perfluorononane, perfluorodecane, fluorine-based inert liquids (for example, “Fluorinert FC40”, “Fluorinert FC43”, “Fluorinert FC3283” manufactured by Sumitomo 3M), 1,1,1,2, Hydrofluoroethers such as 3,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) -pentane (“Novec 7600” manufactured by Sumitomo 3M) can be used.
  • the organic solvent after mixing may have a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C.
  • a mixed solution can be used.
  • the above-mentioned fluorinated solvent and a mixture thereof may be added to 1,1,2,2,3,3,4,4-octafluorobutane, 1,3-bis (trifluoromethyl) benzene, heptafluorocyclopentane ( “Zeorolla H” from Nippon Zeon), 2H, 3H-decafluoropentane (“Bertrel XF” from DuPont), hydrofluorocarbons such as 1,1,1,3,3,3-hexafluoroisopropanol, perfluorohexane, Perfluoroalkanes represented by C n F 2n + 2 such as fluoroheptane and perfluorooctane (“Fluor
  • the concentration of the perfluoropolyether group-containing silane represented by the general formula [1] is preferably 0.01 to 5% by mass.
  • concentration is less than 0.01% by mass, it is not preferable because sufficient antifouling performance cannot be exhibited on the surface of the substrate or the antifouling layer becomes non-uniform. If the concentration exceeds 5% by mass, it is difficult to remove the surplus of the antifouling layer, or the surplus to be removed increases, resulting in high costs. From the viewpoint of antifouling performance, removal of surplus, and cost, a more preferable concentration range is 0.05 to 1% by mass, and a more preferable concentration range is 0.1 to 0.4% by mass.
  • a catalyst may be added to the antifouling layer forming coating agent for the purpose of promoting the hydrolysis reaction and condensation reaction of the perfluoropolyether group-containing silane represented by the general formula [1].
  • the catalyst include organic tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate, organic titanium compounds such as tetra n-butyl titanate, organic acids such as acetic acid and methanesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. Can be mentioned.
  • acetic acid, tetra n-butyl titanate, dibutyltin dilaurate and the like are preferable.
  • the amount added is preferably 0.01 to 5% by weight, particularly 0.05 to 1% by weight, based on the weight of the perfluoropolyether group-containing silane.
  • the antifouling layer-forming coating agent includes a surfactant, a crosslinking agent, an antioxidant, an ultraviolet absorber, an infrared absorber, a flame retardant, a hydrolysis inhibitor, an antibacterial agent as long as the object of the present invention is not impaired.
  • a glaze or the like may be added.
  • the antifouling article of the present invention is produced through at least the following steps using the coating agent for forming an antifouling layer.
  • the holding member holding the coating agent is brought into contact with the substrate surface, the holding member is reciprocated in a specific direction on the substrate surface, and applied to the entire surface, and then the holding member is again applied to the substrate surface.
  • the holding member is moved back and forth in one direction different from the coating direction in the coating A on the surface of the base material to apply the coating agent to the entire surface, and finally applied along the edge of the base material.
  • a drying step of drying the applied coating agent is a drying step of drying the applied coating agent.
  • the substrate is not particularly limited.
  • a float plate glass used for a window glass for buildings, or a plate glass having an inorganic transparency such as a soda lime glass manufactured by a roll-out method can be used.
  • Glass substrates such as displays, touch panels, showcases, etc., glass substrates such as pachinko machine front plates, reflective substrates such as mirrors, rubbed glass, and glass with patterns.
  • a translucent or opaque glass substrate such as can be used.
  • substrates made of ceramic materials used for tiles, tiles, sanitary ware, tableware, frames such as glass windows, cookers, scalpels, medical instruments such as scalpels, injection needles, sinks, automobiles
  • Metal materials such as stainless steel, aluminum, steel, etc. used in the body of plastics, plastic base materials such as polycarbonate resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polyethylene resin, polyvinyl chloride resin, other plastics
  • a substrate can be used.
  • the antifouling layer may be formed on the surface of the base material either entirely or partially on the base material surface.
  • a treatment for improving the adhesive strength between the base material and the antifouling layer can be performed on the base material surface in advance.
  • the treatment include polishing / washing / drying with various polishing liquids, surface modification treatment with acidic solution or basic solution, primer treatment, plasma irradiation, corona discharge, high-pressure mercury lamp irradiation, etc. Generation.
  • a bond formed between the hydrolyzable functional group represented by Z or a silanol group formed by hydrolysis thereof for example, a siloxane bond
  • Sufficient adhesion between the antifouling layer and the substrate surface can be imparted by metalloxane bonds and the like) and interactions (for example, van der Waals force and electrostatic interaction).
  • the coating agent can be spread over the entire surface of the substrate by coating A.
  • the coating surface can be uniformly leveled by coating B.
  • the reciprocating direction of the member for coating B is not particularly limited, but the angle ⁇ formed by the reciprocating direction of the member for coating A and the reciprocating direction of the member for coating B ( ⁇ is 0 ° or more and less than 180 °). Is preferably in the direction of an angle of 20 to 160 ° because it can be applied more uniformly. More preferably, the direction is an angle of 45 to 135 °.
  • the coating agent can be reliably applied to the end portion where forgetting to apply or lack of the coating agent is likely to occur.
  • a holding member for holding the coating agent there is a nonwoven fabric made of pulp, acrylic, PET, PP, nylon, rayon, etc., but a composite material of pulp and PP is particularly preferable from the viewpoint of strength and liquid absorbency. .
  • various coating methods such as brush coating, hand coating, robot coating, and combinations thereof can be used.
  • it can also apply
  • Hand coating is preferable.
  • an antifouling layer is formed by condensing the perfluoropolyether group-containing silane represented by the general formula [1], and the perfluoropolyether group-containing Sufficient adhesion between the antifouling layer and the substrate surface is expressed by the bond or interaction formed between the silanol group generated from silane and the active species on the substrate surface.
  • the drying step is preferably performed at 50 to 250 ° C., more preferably 100 to 200 ° C., and may be performed under normal pressure, increased pressure, reduced pressure, or inert atmosphere. Microwave heating is also effective.
  • An antifouling layer having a uniform surface can be obtained by wiping with a paper towel or cloth moistened with an organic solvent and / or a dry paper towel or cloth.
  • the appearance of white turbidity appear in the form of dots or streaks on the surface of the antifouling layer. This is because even if droplets adhere to the surface of the antifouling layer due to steam or the like, the antifouling article does not impair the appearance or design, or there is a difference in how the dirt is removed, resulting in an appearance or design. This is because there is no loss.
  • the fluorine count (fluorine concentration) of the antifouling article obtained by this production method varies depending on the composition of the coating agent used, coating conditions, etc., but usually it is sufficient if the fluorine count is 0.2 ⁇ g / cm 2 or more. Antifouling performance is obtained, more preferably 0.4 ⁇ g / cm 2 or more. Further, the obtained antifouling article can prevent dot-like or streaky white turbidity that appears on the surface of the antifouling layer as the fluorine count in the arbitrary portion has less variation.
  • the variation in the fluorine count is 1.6 ⁇ g / cm 2 or less, the appearance of the antifouling article when exposed to water vapor or the like and droplets adhere to it The design is not impaired, more preferably 1.3 ⁇ g / cm 2 or less.
  • the antifouling article obtained by this production method is suitable for use in an environment where antifouling properties are required, but it is particularly preferred to be used under steam.
  • Under steam is an environment that is often exposed to steam, and includes, for example, bathrooms and washstands where a large amount of steam is generated, and kitchen areas that are exposed to steam such as water and oil.
  • antifouling articles used under steam include, for example, bathroom faucets, mirrors, walls, partitions, windows, doors and washstand mirrors, cabinets, wash bowls, faucets, counters and around kitchens.
  • partitions can be used for partitions, kitchen hoods, ventilators, cooking ranges, heat sinks around the sinks and convenience stores, etc., and is especially suitable for water-partitions such as bathroom mirrors, mirrors for washstands, kitchens and washstands.
  • an antifouling layer-forming coating agent was prepared and applied on a substrate to produce an antifouling article.
  • the method for preparing the coating agent and the method for producing the antifouling article are as described below.
  • quality evaluation was performed by the method shown below about the surface tension of the organic solvent used for the coating agent and the antifouling layer of the obtained antifouling article.
  • the surface tension of the organic solvent was measured by a plate method using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.
  • the material of the plate was platinum, and the measurement temperature was 25 ⁇ 2 ° C.
  • Abrasion resistance (polishing resistance) A cotton cloth impregnated with a ceria suspension (10% by mass) in which glass abrasives Milleak A (T) (Mitsui Mining & Mining Co., Ltd.) is dispersed in tap water.
  • the surface of the antifouling layer is about 1.5 kg / Polished with a strength of cm 2 .
  • the number of times of polishing (reciprocation) until 70% of the polishing region became hydrophilic was evaluated.
  • the abrasion resistance (abrasion resistance) of the antifouling layer is less than 50 polishing times (represented as x in Table 1), more than 50 polishing times (represented as ⁇ in Table 1), Polishing frequency of 80 times or more was judged as good (indicated by “ ⁇ ” in Table 1).
  • Example 1 Preparation of coating agent for antifouling layer formation
  • OPTOOL DSX manufactured by Daikin Industries: Perfluoropolyether group-containing silane perfluorohexane solution (solid content concentration 20% by mass), and the estimated structure is represented by the general formula [2]
  • Novec 7600 manufactured by Sumitomo 3M: 1,1,1,2,3,3-hexafluoro-4- (1,1) having a surface tension of 17.7 mN / m and a boiling point of 131 ° C.
  • the antifouling layer of the obtained antifouling article has excellent antifouling performance and abrasion resistance, with antifouling property, ⁇ with water resistance, ⁇ with wear resistance, and ⁇ when cloudy.
  • the antifouling layer surface of the antifouling article was exposed to steam such as water, no dot-like or streak-like white turbidity was generated on the surface.
  • 10 sheets of the surface of the 300 mm x 300 mm size float glass substrate were able to be apply
  • the variation in fluorine count was 0.2 ⁇ g / cm 2 . Table 1 shows the quality evaluation results.
  • Examples 2-7 A transparent sample having a uniform surface by visual observation is obtained by appropriately changing the type, concentration, type of organic solvent, concentration of the fluorinated solvent in the organic solvent, and coating method of the perfluoropolyether group-containing silane of Example 1. Obtained.
  • Table 1 shows the quality evaluation results of each sample.
  • “KY130” in Table 1 is a metaxylene hexafluoride solution (solid content concentration 20% by mass) of a perfluoropolyether group-containing silane manufactured by Shin-Etsu Chemical Co., Ltd., and the estimated structure is the general formula [3]. .
  • the antifouling layer of the obtained antifouling article has a stain resistance of ⁇ , a stain resistance of ⁇ , an abrasion resistance of ⁇ , an appearance when cloudy, and an excellent antifouling performance and wear resistance. In addition, even when the surface of the antifouling layer of the antifouling article was exposed to water or the like, dot-like or streaky white turbidity did not occur on the surface.
  • Example 9 All samples were the same as in Example 1 except that the drying temperature was set to 100 ° C. and brush-coated (described in Table 1 as “suitable application by brush coating (90 °)”). Got.
  • the antifouling layer of the obtained antifouling article has excellent antifouling performance and abrasion resistance, with antifouling property, ⁇ with water resistance, ⁇ with wear resistance, and ⁇ when cloudy.
  • the antifouling layer surface of the antifouling article was exposed to steam such as water, no dot-like or streak-like white turbidity was generated on the surface. Moreover, there was no problem even if 100 sheets were produced continuously.
  • Example 10 Implemented except for coating B, which was applied to the entire surface by reciprocating in the direction of about 45 ° with respect to the coating direction of coating A (described in Table 1 as “suitable coating by hand (45 °)”)
  • a transparent sample having the same surface as in Example 1 was obtained by visual observation.
  • the antifouling layer of the obtained antifouling article has excellent antifouling performance and abrasion resistance, with antifouling property, ⁇ with water resistance, ⁇ with wear resistance, and ⁇ when cloudy.
  • the antifouling layer surface of the antifouling article was exposed to steam such as water, no dot-like or streak-like white turbidity was generated on the surface.
  • Example 11 Implementation was performed except that coating B was reciprocated in the direction of about 35 ° with respect to the coating direction of coating A and applied to the entire surface (described as “suitable coating by hand coating (35 °)” in Table 1).
  • a transparent sample having the same surface as in Example 1 was obtained by visual observation.
  • the antifouling layer of the obtained antifouling article has antifouling performance, wear resistance, o wear resistance, o appearance when cloudy, o antifouling performance, wear resistance
  • the antifouling layer surface of the antifouling article was exposed to steam such as water, no dot-like or streak-like white turbidity occurred on the surface. Moreover, there was no problem even if 100 sheets were produced continuously.
  • Comparative Example 1 All of the organic solvents were the same as in Example 1 except that isopropyl alcohol having a surface tension of 21.7 mN / m and a boiling point of 82 ° C. was used.
  • the prepared coating agent was a cloudy liquid, but a sample having a uniform surface was obtained by visual observation.
  • the antifouling layer of the obtained sample has a stain resistance of ⁇ , a water resistance of ⁇ , an abrasion resistance of ⁇ , and the appearance when clouded is a dot-like white turbidity as shown in FIG. It was. Further, the variation in fluorine count was 1.7 ⁇ g / cm 2 . Table 2 shows the quality evaluation results.
  • Comparative Example 2 Comparative Example 1 except that the coating method was only dip coating on the glass substrate at a pulling rate of 5 mm / sec (described as “Dip coating only” in Table 1), and then directly moved to the drying step. And the same.
  • the prepared coating agent was a cloudy liquid, but a sample having a uniform surface was obtained by visual observation.
  • the antifouling layer of the obtained sample had a stain resistance of x, a stain resistance of x, an abrasion resistance of x, and the appearance when clouded was a dot and streaky white turbidity and x.
  • the variation in fluorine count was 2.0 ⁇ g / cm 2 . Table 2 shows the quality evaluation results.
  • Comparative Example 3 The organic solvent was the same as in Example 1 except that Zeolora H (manufactured by ZEON Corporation: heptafluorocyclopentane) having a surface tension of 20.3 mN / m and a boiling point of 83 ° C. was used, and the surface was uniform by visual observation. A clear sample was obtained.
  • the antifouling layer of the obtained sample had a stain resistance of ⁇ , a water resistance of ⁇ , an abrasion resistance of ⁇ ⁇ , and the appearance when clouded was dot-like white turbidity and x.
  • the variation in fluorine count was 2.0 ⁇ g / cm 2 . Table 2 shows the quality evaluation results.
  • Comparative Example 4 As the coating method, all was the same as in Comparative Example 3 except that the coating was performed on the glass substrate by the Mayer bar method (described as “Meyer bar method only” in Table 1), and the drying process was directly performed. A transparent sample with a uniform surface was obtained by visual observation. The antifouling layer of the obtained sample had a stain resistance of ⁇ , a stain resistance of ⁇ , an abrasion resistance of ⁇ , and the appearance when clouded was dot and streak-like white turbidity occurred. Moreover, the variation in fluorine count was 2.1 ⁇ g / cm 2 . Table 2 shows the quality evaluation results.
  • Comparative Example 5 The organic solvent was the same as Example 1 except that PF5060 (Sumitomo 3M: perfluorohexane) having a surface tension of 11.7 mN / m and a boiling point of 57 ° C. was used. A sample was obtained. The antifouling layer of the obtained sample had a contamination resistance of ⁇ , a water resistance of ⁇ , an abrasion resistance of ⁇ , and an appearance when clouded. However, in the continuous production of up to 50 sheets, the solvent volatilizes and the solid content concentration of the coating agent becomes high. As a result, it becomes impossible to apply uniformly, and the appearance and antifouling property of the antifouling layer is different for each substrate. It became unstable.
  • PF5060 Suditomo 3M: perfluorohexane
  • productivity is x.
  • two surfaces of a 300 mm ⁇ 300 mm size float glass substrate could be applied using 10 ml of the antifouling layer forming coating agent.
  • the variation in fluorine count was 0.2 ⁇ g / cm 2 . Table 2 shows the quality evaluation results.
  • Comparative Example 6 The organic solvent is PF5060 (manufactured by Sumitomo 3M: perfluorohexane) having a surface tension of 11.7 mN / m and a boiling point of 57 ° C., and the flow coating method is used as the coating method (“flow coating method only” in Table 1).
  • the sample was completely the same as Example 1 except that the process was directly transferred to the drying step, and a transparent sample having a uniform surface was obtained by visual observation.
  • the antifouling layer of the obtained sample had a stain resistance of ⁇ , a stain resistance of ⁇ , an abrasion resistance of ⁇ , and an appearance when clouded.
  • Comparative Example 7 The organic solvent was the same as Example 1 except that the organic solvent was 1,3-bis (trifluoromethyl) benzene having a surface tension of 20.7 mN / m and a boiling point of 115 ° C., and the surface was uniformly transparent by visual observation. Sample was obtained. The antifouling layer of the obtained sample had a stain resistance of ⁇ , a water resistance of ⁇ , an abrasion resistance of ⁇ ⁇ , and the appearance when clouded was dot-like white turbidity and x. Further, the variation in fluorine count was 2.2 ⁇ g / cm 2 . Table 2 shows the quality evaluation results.
  • Comparative Example 8 The organic solvent in Example 5 was a mixture of Novec 7300 and hexane. The concentration of the fluorinated solvent in the mixed solution is 50% by mass. The mixed solution has a surface tension of about 16.7 mN / m and a boiling point of about 84 ° C. As a result, a transparent sample having a uniform surface was obtained by visual observation. The antifouling layer of the obtained antifouling article had a stain resistance of ⁇ , a water resistance of ⁇ , an abrasion resistance of ⁇ , and a cloudy appearance when the dot was cloudy. Further, the variation in fluorine count was 1.7 ⁇ g / cm 2 . Table 2 shows the quality evaluation results.
  • the antifouling article obtained by the present invention has excellent antifouling performance and wear resistance, and even when the antifouling layer surface of the antifouling article is exposed to steam such as water, Dot-like or streak-like white turbidity does not occur on the surface, and the appearance and design are not impaired.

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EP2647498A4 (en) * 2011-01-13 2016-02-24 Central Glass Co Ltd Antifungal article and method of production thereof
WO2016136817A1 (ja) * 2015-02-25 2016-09-01 株式会社ニコン 含フッ素組成物、パターン形成用基板、光分解性カップリング剤、パターン形成方法及びトランジスタの製造方法
JP2016157111A (ja) * 2015-02-25 2016-09-01 学校法人神奈川大学 含フッ素組成物、パターン形成用基板、光分解性カップリング剤、パターン形成方法及びトランジスタの製造方法

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JP6044211B2 (ja) * 2012-09-13 2016-12-14 ダイキン工業株式会社 フルオロオキシアルキレン基含有シラン化合物の製造方法
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US20160168397A1 (en) * 2013-07-17 2016-06-16 Jun Liu Substrate coating compositions and methods
CN109475900B (zh) * 2016-07-15 2022-09-02 日产自动车株式会社 防污结构体前体、防污结构体、表面改性组合物、及表面改性方法
JP6711489B2 (ja) * 2017-05-26 2020-06-17 株式会社フロロテクノロジー コーティング剤
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JP6529654B1 (ja) 2018-10-24 2019-06-12 デクセリアルズ株式会社 活性エネルギー線硬化性樹脂組成物、防曇防汚積層体、及びその製造方法、物品、並びに防曇方法
CN115803187B (zh) * 2020-07-13 2024-10-01 日东电工株式会社 带防污层的光学薄膜
WO2023026876A1 (ja) * 2021-08-26 2023-03-02 ダイキン工業株式会社 表面処理剤
WO2023136343A1 (ja) * 2022-01-17 2023-07-20 Toto株式会社 衛生陶器
JP2023104911A (ja) * 2022-01-17 2023-07-28 Toto株式会社 衛生陶器

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