WO2010038648A1 - Coating composition, method of antifouling treatment and antifouling substrate - Google Patents
Coating composition, method of antifouling treatment and antifouling substrate Download PDFInfo
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- WO2010038648A1 WO2010038648A1 PCT/JP2009/066520 JP2009066520W WO2010038648A1 WO 2010038648 A1 WO2010038648 A1 WO 2010038648A1 JP 2009066520 W JP2009066520 W JP 2009066520W WO 2010038648 A1 WO2010038648 A1 WO 2010038648A1
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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
- 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
- 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
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- C09D171/02—Polyalkylene oxides
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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
- 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
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
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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
- C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/17—Hygienic or sanitary devices on telephone equipment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
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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
- 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 relates to a coating composition, an antifouling treatment method, and an antifouling substrate, and more particularly to a coating composition capable of imparting antifouling properties, an antifouling treatment method, and a mobile phone treated with the antifouling method.
- an antifouling treatment may be performed as a surface treatment for making it difficult for dirt to adhere and easily wiping off the dirt.
- a thin film is coated on the surface of the substrate with a substance having antifouling properties.
- a fluoroalkyl resin or a silicone-based resin is often used as the raw material for the thin film.
- a compound containing a perfluoropolyether group has a small surface energy and a flexible molecular structure because it contains an ether bond. Therefore, it is known to exhibit excellent antifouling properties.
- a material in which a hydrolyzable group is introduced into the compound.
- Japanese Patent No. 3449070 proposes a method of coating perfluoropolyether-modified silane on a thin film by a vacuum deposition method.
- the vacuum deposition method has a problem that an expensive production facility is required and the productivity is low, resulting in a high production cost.
- the raw material that can be thinned by the vacuum deposition method is limited to those having a molecular weight of about 5000 or less, there is a problem that a highly functional long-chain type raw material cannot be used.
- wet coating methods such as dip method and spray method, which can be produced at low cost, are attracting attention.
- the target compound is dissolved in a soluble solvent to form a solution and applied to the surface of the substrate.
- the target compound contains a group that hydrolyzes, the solution is exposed to the atmosphere.
- water and compounds in the atmosphere react with each other, and the solution gels or the target compound particles.
- the dip method since the solution is exposed to the atmosphere for a long time, the deterioration of the solution is remarkable, causing problems in the use efficiency of the raw material and the quality of the coating, resulting in an increase in production cost. There was a problem that. Further, in the dip method, since the film formed in principle deposits only one molecular layer, it was difficult to form a film having practically sufficient durability.
- the present invention has been made to solve the above-mentioned problems, and is a coating capable of forming an antifouling film having excellent antifouling property, transparency, and practically sufficient durability at a low cost.
- An object of the present invention is to provide a composition, an antifouling treatment method, and an antifouling substrate.
- the coating composition of the present invention is a composition in which a compound containing a perfluoroalkylene ether group in a molecular main chain and a hydrolyzable group containing a silicon atom in a side chain is dissolved in a solvent.
- the solvent is a mixed solvent of fluorine-based solvents containing at least one of a fluorinated hydrocarbon and a fluorinated ether, and the fluorine-based solvent has a boiling point of 40 ° C. or higher and 70 ° C. or lower at 1 atm.
- the difference between the maximum value and the minimum value of the boiling point of the mixed fluorine-based solvent is 25 ° C. or less.
- the compound is a compound represented by the following formula (1).
- Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms
- Y is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 1 is a halogen atom, —OR 3 group, —OCOR 3 And at least one group selected from the group: —OC (R 3 ) ⁇ C (R 4 ) 2 group, —ON ⁇ C (R 3 ) 2 group, and —ON ⁇ C (R 5 ) 2 group
- 3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group
- R 4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 5 represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms.
- the fluorine-based solvent for dissolving the compound represented by the formula (1) is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4. , 5,5,5-undecafluoro-4- (trifluoromethyl) pentane or methyl nonafluorobutyl ether.
- the antifouling treatment method of the present invention is the above-mentioned inorganic antifouling treatment method in which antifouling treatment is performed by coating the surface of an inorganic substrate or the surface of an inorganic surface film formed on an inorganic or organic substrate.
- the coating on the surface of the substrate or the surface of the inorganic surface film is a coating in which the coating composition of the present invention is applied by a spray method.
- the inorganic surface film is an inorganic surface film formed by applying a polysilazane solution by a spray method.
- the antifouling substrate of the present invention is an antifouling substrate having an antifouling layer on the surface of the substrate or the surface of the inorganic surface film formed on the substrate, the antifouling layer of the present invention It is an antifouling layer formed by an antifouling treatment method.
- the antifouling base material is a mobile phone having an image display portion and having the antifouling layer formed on the surface of the image display portion.
- the compound represented by the formula (1) uses a plurality of mixed solvents having a specific structure and boiling point as a solvent. Therefore, the coating composition is excellent in antifouling property, transparent and practically sufficient. A durable coating can be formed at low cost.
- a compound containing a perfluoroalkylene ether group in the molecular main chain and a hydrolyzable group containing a silicon atom in a side chain which can be used in the present invention, is a compound that becomes a solute of the coating composition.
- the perfluoroalkylene ether group is represented by the following formula (1-1)
- the hydrolyzable group containing a silicon atom is represented by the following formula (1-2).
- n represents an integer of 1 to 5
- m represents an integer of 0 to 2
- R 1 represents a hydrolyzable group.
- the frequency of the ether bond in the perfluoroalkylene ether group is not particularly limited.
- As the repeating unit — (OCF 2 ) —, — (OC 2 F 4 ) —, — (OC 3 F 6 ) —, — ( A perfluoroalkylene ether group formed of OC 4 F 8 ) — etc. alone or in combination can be used.
- it is preferable that one end of the perfluoroalkylene ether group is a C n F 2n + 1 -group in which n is 1 or more.
- the hydrolyzable group containing a silicon atom in the side chain may be any group that can be decomposed by the action of water when a coating film is formed in the coating, and is represented by the above formula (1-2).
- R 1 include a halogen atom, —OR 3 group, —OCOR 3 group, —OC (R 3 ) ⁇ C (R 4 ) 2 group, —ON ⁇ C (R 3 ) 2 group, —ON ⁇ C ( R 5 ) 2 groups and the like.
- R 3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group
- R 4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 5 represents a divalent aliphatic group having 3 to 6 carbon atoms.
- R 1 is a chlorine atom, —OCH 3 group, —OC 2 H 5 which can further suppress the occurrence of cloudiness in the coating when the compound represented by the formula (1) is used as a solute. It is a group.
- Preferable examples of the compound that can be used in the present invention include a compound represented by the formula (1).
- Examples of the linear or branched perfluoroalkyl group having 1 to 16 carbon atoms represented by Rf include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoropentyl group.
- Examples of the alkyl group having 1 to 3 carbon atoms represented by Y include a methyl group, an ethyl group, and a propyl group.
- q represents an integer of 1 to 50, preferably 18 to 30, more preferably 22 to 26
- m represents an integer of 0 to 2, preferably 0, and r represents an integer of 1 to 10, preferably 1 to 5.
- the fluorine compound represented by the formula (1) can be obtained by silane treatment of a commercially available perfluoropolyether. This method is disclosed in, for example, Japanese Patent Laid-Open No. 1-294709.
- the fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether constituting the component of the mixed solvent that can be used in the present invention has a boiling point of 40 ° C. or higher and 70 ° C. or lower at 1 atm. Further, the difference between the maximum value and the minimum value of the boiling point of the fluorinated solvent in the mixed solvent is within 25 ° C, preferably within 20 ° C.
- a preferred mixed solvent structure is a mixture of a fluorine-based solvent 1 having a boiling point of 40 ° C. or more and 70 ° C. or less under 1 atm and a fluorine-based solvent 2 having a boiling point difference within 20 ° C. with respect to the boiling point of the solvent 1. It is a solvent. It was found that when the coating agent in which two or more kinds of solvents satisfying the above boiling point conditions were mixed by spray coating, unevenness in film thickness was suppressed and a transparent film was obtained.
- Solvents that can be used in the present invention include 1,1,1,3,3-pentafluorobutane (boiling point: 40 ° C.), perfluorohexane (boiling point: 40 ° C.) in consideration of environmental impact, safety during production, availability, and the like. (Boiling point 56 ° C.), 1,1,1,2,2,3,3,4,5,5,5-undecafluoro-4- (trifluoromethyl) pentane (boiling point 56 ° C.), methyl nonafluorobutyl ether ( A mixture of two or more solvents selected from a boiling point of 61 ° C. is preferable.
- a mixture obtained by selecting and mixing two or more solvents having a difference in boiling point of 20 ° C. or less is preferable.
- the mixing ratio of the mixed solvent is such that at least one component is mixed by 1 wt% or more, preferably 2 wt% or more with respect to the entire mixed solvent.
- the said solvent can be mixed with the adjuvant which adjusts various characteristics, such as wettability.
- the coating composition of the present invention includes a dipping method in which a substrate is immersed in the coating composition, a spray method in which the coating composition is sprayed onto the substrate, and the coating composition is dropped while rotating the substrate.
- An antifouling layer can be formed on the surface by coating by a known method such as a wet process such as a spin coating method or a dry process such as a vacuum deposition method using a solute of a coating composition.
- a wet process such as a spin coating method
- a dry process such as a vacuum deposition method using a solute of a coating composition.
- Examples of the substrate on which the antifouling layer is formed include an inorganic substrate or an organic substrate.
- Examples of the inorganic substrate include glass, metal, and ceramics. Of these, transparent or translucent glass, ceramics and the like are preferable.
- Examples of the organic substrate include plastics, rubber, and elastomer. Among these, transparent or translucent plastics are preferable, and acrylic resins and polycarbonate resins are particularly preferable.
- a transparent or translucent base material is often used for a display unit such as a mobile phone or various displays, and is for a base material that particularly requires the formation of an antifouling layer.
- the shape of the substrate is preferably a film or a sheet, but is not particularly limited, and can be used as a substrate for forming an antifouling layer as long as the coating surface is flat or a smooth curved surface. Moreover, other surface treatments such as hard coating, antireflection coating, and antiglare coating may be applied in advance to the substrate.
- an inorganic surface film on the surface of an inorganic substrate or an organic substrate.
- an inorganic surface film on the surface of the organic substrate.
- the inorganic surface film can be selected from a metal film, a semiconductor film, an oxide film, a nitride film, an oxynitride film, and the like according to the required specifications of the product.
- the thickness of the inorganic surface film should be the minimum necessary to ensure the adhesion of the antifouling coating layer, and is in the range of 0.01 to 1 ⁇ m, more preferably 0.05 to 0.2 ⁇ m. It is preferable to form in a range. However, if an inorganic film outside this range is required based on the required specifications of the product other than the antifouling property, the film thickness may naturally be adapted to it.
- the inorganic surface film can be formed on the surface of the base material by a known forming method such as a spray method, a sol-gel method, a sputtering method, or a CVD method.
- a spray method a sol-gel method
- a sputtering method a CVD method.
- an inorganic surface film coated by a spray method using a polysilazane solution and dried can provide practically sufficient wear resistance.
- the inorganic surface film forming method in which the polysilazane solution is applied by a spray method is equivalent to or superior to other methods, and therefore the inorganic surface film is preferably formed by this method. .
- the polysilazane solution is commercially available from AZ Electronic Materials, and the concentration and the type of solvent may be appropriately diluted and concentrated according to the type of substrate, film thickness, spray conditions, and the like.
- the carrier gas used when spraying the polysilazane solution is a gas containing as little water as possible, and nitrogen gas is most suitable from the viewpoint of cost.
- the antifouling substrate of the present invention is the antifouling treatment described above on the surface of a substrate to which sebum, fingerprints, sweat, cosmetics, etc. are likely to adhere, such as a display surface of a mobile phone, a display surface of a liquid crystal panel or a touch panel, and a glass lens Is given.
- a mobile phone in which an antifouling layer is formed using the coating composition of the present invention will be described with reference to the drawings.
- FIG. 1 shows an entire mobile phone, various operation keys 1 used for a call, various information related to the telephone (telephone number, radio wave state, remaining battery level, etc.) and an image display device 2 which is an image display unit. It consists of a microphone 3 and a speaker 4.
- Specific examples of the image display device 2 include a liquid crystal display (LCD) and an organic electroluminescence display (organic EL display).
- FIG. 2 shows a cross section AA ′ of FIG.
- the image display device 2 is provided inside a casing 5 of the mobile phone, and a transmission window member 6 is provided on the image display device 2.
- the transmission window member 6 is generally made of resin having a good light transmittance, and the material thereof is made of acrylic, polycarbonate, or the like.
- the transparent window member 6 is provided with the inorganic surface film 6a and the antifouling layer 6b of the compound represented by the formula (1) in this order.
- the transparent inorganic surface film 6a is formed on the transmission window member 6 by a sputtering method.
- a material for the inorganic surface film 6a a polysilazane-based inorganic film can be used.
- the antifouling layer 6b on the surface can be formed by applying and drying by a spray method using a coating composition having a compound represented by the formula (1) as a solute.
- the base material after antifouling treatment was evaluated by the following method.
- the evaluation items and methods are described.
- (Evaluation 1) Appearance An evaluation sample was visually observed in a dark room under an illuminance of 500 lux or more of fluorescent lamps, and the presence or absence of coating cloudiness or unevenness was determined.
- (Evaluation 3) Sebum removability The evaluation sample shown below (Evaluation 4) was lightly rubbed 10 times with a cellulose nonwoven fabric (Bencot manufactured by Asahi Kasei Co., Ltd.), and the remaining sebum was visually observed. The evaluation criteria were good when almost no sebum remained, and poor when clearly remained. (Evaluation 4) Abrasion resistance A copy paper (ASKUL Super White) was pressed against the sample with a load of 9.8 N / cm 2 and slid back and forth, and the contact angle of the sliding part against water was measured. The number of times of sliding until less than 90 ° was measured. The test was performed 3 times or more, and the average value was evaluated.
- this test method has a wear resistance of about 50,000 times, it is considered that the wear resistance is practically sufficient.
- the film thicknesses described in the following Examples and Comparative Examples were measured with an ellipsometer (DHA-FR manufactured by Mizoji Optical Co., Ltd.) on the film on the Si (100) substrate formed simultaneously with the evaluation sample.
- the contact angle measured the contact angle with respect to the water of the evaluation sample surface with the contact angle meter (DM100 by Kyowa Interface Science Co., Ltd.).
- Example 1 As a coating composition, 1 part by weight of a compound represented by the following formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 1,1,1,3,3-pentafluorobutane (boiling point 40 ° C.). ) A composition dissolved in a mixed solvent with 195 parts by weight was prepared. This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes. The formed antifouling layer had a film thickness of 8.4 nm and a contact angle of 116 °.
- the appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties.
- the abrasion resistance was 95,763 times.
- Table 1 the repeating number 1-10 of the repeating unit having trimethoxysilane in the side chain represents a mixture having a repeating number of 1 to 10.
- Example 2 As a coating composition, 1 part by weight of the compound represented by the above formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 1,1,1,2,2,3,3,4,5, A composition dissolved in a mixed solvent of 195 parts by weight of 5,5-undecafluoro- (trifluoromethyl) pentane (boiling point 56 ° C.) was prepared.
- This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes.
- the formed antifouling layer had a thickness of 9.2 nm and a contact angle of 115 °.
- the appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties.
- the abrasion resistance was 88,140 times. The results are shown in Table 1.
- Example 3 As a coating composition, 1 part by weight of the compound represented by the above formula (2) is dissolved in a mixed solvent of 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of methyl nanofluorobutyl ether (boiling point 61 ° C.). A prepared composition was prepared. This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes. The formed antifouling layer had a film thickness of 8.8 nm and a contact angle of 116 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The wear resistance was 92,598 times. The results are shown in Table 1.
- Example 4 A polysilazane solution (Aquamica NL120A-05 manufactured by AZ Electronic Materials Co., Ltd.) is applied to an acrylic substrate with hard coat (Acrylite MR-200 manufactured by Mitsubishi Rayon Co., Ltd.) by a spray method, and left for a day and night in an air atmosphere to form a polysilazane thin film (film) A thickness of 93 nm) was formed. Thereafter, the coating composition used in Example 2 was coated by the spray method under the same conditions as in Example 2. The film thickness of the antifouling layer was 8.5 nm and the contact angle was 117 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The abrasion resistance was 66,031 times.
- Comparative Example 1 As a coating composition, 1 part by weight of a compound represented by the above formula (2) was prepared by dissolving in 199 parts by weight of perfluorohexane (boiling point 56 ° C.). This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. The appearance of the coating was clearly cloudy. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.
- Comparative Example 2 As a coating composition, 1 part by weight of the compound represented by the above formula (2) is dissolved in a mixed solvent of 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of Asahi Glass Novec HFE 7200 (boiling point 76 ° C.). Got ready. This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. Although the appearance of the film was transparent, a circular pattern (unevenness) that could be recognized visually was generated. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.
- Comparative Example 3 As a coating composition, 1 part by weight of the compound represented by the above formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of Fluorinert FC-40 (boiling point 155 ° C.) manufactured by Sumitomo 3M Limited. Prepared by dissolving in a solvent.
- This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. The appearance of the film was transparent, but irregular irregularities (amoeba-like) that could be recognized visually were generated. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.
- Example 4 The coating composition used in Example 2 was coated directly on the hard-coated acrylic substrate used in Example 4 by a spray method.
- the film thickness of the antifouling layer was 9.9 nm, and the contact angle was 116 °.
- the appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was as low as 7,379 times.
- Comparative Example 5 The coating composition solute used in Example 2 was deposited on the glass substrate used in Example 2 by vacuum deposition.
- the background pressure of vacuum deposition was on the order of 10 ⁇ 3 Pa, and the solute of the coating composition placed in a glass crucible was heated from room temperature to 500 ° C. over about 30 minutes.
- the formed film had a thickness of 7.2 nm and a contact angle of 117 °.
- the appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was 42,217 times, which was lower than that of Example 2.
- Example 6 The coating composition used in Example 2 was formed into a film on the glass substrate used in Example 2 by the dip method.
- the dip was immersed for 24 hours at room temperature and pulled up at a speed of about 10 mm / second.
- the film thickness of the formed film was 5 nm or less and could not be measured.
- the contact angle was 117 °.
- the appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was as low as 4,701 times.
- Comparative Example 7 A SiO 2 thin film (film thickness: 101 nm) was formed on the acrylic substrate with hard coat used in Example 4 by sputtering. Sputtering was performed by an ion beam method, a background pressure was set to 10 ⁇ 3 Pa, and a fused silica target was irradiated with a 700 eV Ar ion beam. Thereafter, the coating agent used in Example 2 was coated by a spray method. The film thickness of the antifouling layer was 8.9 nm and the contact angle was 115 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was 20,558 times, which was lower than that of Example 4.
- solvent A is perfluorohexane (boiling point 56 ° C.)
- solvent B is 1,1,1,3,3-pentafluorobutane (boiling point 40 ° C.)
- solvent C is 1,1,1, 2,2,3,3,4,5,5,5-undecafluoro- (trifluoromethyl) pentane (boiling point 56 ° C.)
- solvent D is methyl nanofluorobutyl ether (boiling point 61 ° C.)
- solvent E is Asahi Glass Co., Ltd. NovecHFE7200 (boiling point 76 ° C.)
- solvent F represents Sumitomo 3M Fluorinert FC-40 (boiling point 155 ° C.).
- the coating composition and the surface treatment method of the present invention it is possible to form an antifouling film having excellent antifouling property, transparency, and practically sufficient durability at a low cost. It can be used for display devices.
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Abstract
Description
防汚処理は、基材の表面に防汚性を有する物質を薄膜にコーティングするものである。薄膜の原料としては、フルオロアルキル樹脂あるいはシリコーン系樹脂を利用することが多いが、中でもペルフルオロポリエーテル基を含む化合物は、その表面エネルギーが小さく、またエーテル結合を含むために分子構造が柔軟であることから、優れた防汚性を発揮することが知られている。これを薄膜にコーティングする際には、基材と薄膜の密着性を確保するため、同化合物中に加水分解が可能な基を導入したものを原料とするのが一般的である。 Sebum, fingerprints, sweat, cosmetics, and the like adhere to the display surface of a mobile phone, the display surface of a liquid crystal panel or touch panel, and eyeglass lenses when used by a person. Therefore, an antifouling treatment may be performed as a surface treatment for making it difficult for dirt to adhere and easily wiping off the dirt.
In the antifouling treatment, a thin film is coated on the surface of the substrate with a substance having antifouling properties. As the raw material for the thin film, a fluoroalkyl resin or a silicone-based resin is often used. Among them, a compound containing a perfluoropolyether group has a small surface energy and a flexible molecular structure because it contains an ether bond. Therefore, it is known to exhibit excellent antifouling properties. When coating this on a thin film, in order to ensure adhesion between the base material and the thin film, it is common to use a material in which a hydrolyzable group is introduced into the compound.
しかし、従来のウエットコーティング法では、目的の化合物を可溶溶媒に溶かして溶液化し、基材表面に塗布するが、目的の化合物が加水分解する基を含んでいるため、溶液を大気中に曝すと大気中の水分と化合物が反応して、溶液がゲル化したり、目的の化合物が粒子化したりする問題がある。
また、ディップ法においては、溶液が大気に曝される時間が長いため、溶液の変質が顕著であり、原料の利用効率、被膜の品質上の問題が発生し、結果的に生産コストが高くなってしまうという問題があった。またディップ法では、原理的に形成される被膜が分子1層しか堆積しないため、実用上十分な耐久性を持つ被膜を形成することが困難であった。 Therefore, wet coating methods such as dip method and spray method, which can be produced at low cost, are attracting attention.
However, in the conventional wet coating method, the target compound is dissolved in a soluble solvent to form a solution and applied to the surface of the substrate. However, since the target compound contains a group that hydrolyzes, the solution is exposed to the atmosphere. There is a problem that water and compounds in the atmosphere react with each other, and the solution gels or the target compound particles.
In the dip method, since the solution is exposed to the atmosphere for a long time, the deterioration of the solution is remarkable, causing problems in the use efficiency of the raw material and the quality of the coating, resulting in an increase in production cost. There was a problem that. Further, in the dip method, since the film formed in principle deposits only one molecular layer, it was difficult to form a film having practically sufficient durability.
しかしながら、スプレーノズルから噴射された液滴が基材表面に付着し、濡れ拡がり、溶媒が乾燥して目的の化合物が表面で薄膜化する過程で、原料高分子が粒子化して被膜が白濁する問題があった。
However, the droplet sprayed from the spray nozzle adheres to the substrate surface, spreads wet, the solvent dries, and the target compound becomes a thin film on the surface. was there.
特に上記化合物が下記式(1)で表される化合物であることを特徴とする。
また、式(1)で表される化合物を溶解するフッ素系溶媒が1,1,1,3,3-ペンタフルオロブタン、ペルフルオロヘキサン、1,1,1,2,2,3,3,4,5,5,5-ウンデカフルオロ-4-(トリフルオロメチル)ペンタン、または、メチルノナフルオロブチルエーテルであることを特徴とする。 The coating composition of the present invention is a composition in which a compound containing a perfluoroalkylene ether group in a molecular main chain and a hydrolyzable group containing a silicon atom in a side chain is dissolved in a solvent. In this composition, the solvent is a mixed solvent of fluorine-based solvents containing at least one of a fluorinated hydrocarbon and a fluorinated ether, and the fluorine-based solvent has a boiling point of 40 ° C. or higher and 70 ° C. or lower at 1 atm. The difference between the maximum value and the minimum value of the boiling point of the mixed fluorine-based solvent is 25 ° C. or less.
In particular, the compound is a compound represented by the following formula (1).
Further, the fluorine-based solvent for dissolving the compound represented by the formula (1) is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4. , 5,5,5-undecafluoro-4- (trifluoromethyl) pentane or methyl nonafluorobutyl ether.
特に、上記無機表面膜は、ポリシラザン溶液をスプレー法で塗布することにより形成した無機表面膜であることを特徴する。 The antifouling treatment method of the present invention is the above-mentioned inorganic antifouling treatment method in which antifouling treatment is performed by coating the surface of an inorganic substrate or the surface of an inorganic surface film formed on an inorganic or organic substrate. The coating on the surface of the substrate or the surface of the inorganic surface film is a coating in which the coating composition of the present invention is applied by a spray method.
In particular, the inorganic surface film is an inorganic surface film formed by applying a polysilazane solution by a spray method.
特に、上記防汚性基材は、画像表示部を有し、該画像表示部の表面に上記防汚層が形成された携帯電話であることを特徴とする。 The antifouling substrate of the present invention is an antifouling substrate having an antifouling layer on the surface of the substrate or the surface of the inorganic surface film formed on the substrate, the antifouling layer of the present invention It is an antifouling layer formed by an antifouling treatment method.
In particular, the antifouling base material is a mobile phone having an image display portion and having the antifouling layer formed on the surface of the image display portion.
上記ペルフルオロアルキレンエーテル基は、下記式(1-1)で表され、上記シリコン原子を含む加水分解性基は下記式(1-2)で表される。
The perfluoroalkylene ether group is represented by the following formula (1-1), and the hydrolyzable group containing a silicon atom is represented by the following formula (1-2).
R1としては、例えばハロゲン原子、-OR3基、-OCOR3基、-OC(R3)=C(R4)2基、-ON=C(R3)2基、-ON=C(R5)2基等が挙げられる。ここで、R3は脂肪族炭化水素基または芳香族炭化水素基を表し、R4は水素原子または炭素数1~3のアルキル基を表し、R5は炭素数3~6の2価の脂肪族炭化水素基を表す。
本発明において、好ましいR1としては、式(1)で表される化合物を溶質として用いた場合に、被膜の白濁発生をより抑えることができる塩素原子、-OCH3基、-OC2H5基である。 The hydrolyzable group containing a silicon atom in the side chain may be any group that can be decomposed by the action of water when a coating film is formed in the coating, and is represented by the above formula (1-2).
Examples of R 1 include a halogen atom, —OR 3 group, —OCOR 3 group, —OC (R 3 ) ═C (R 4 ) 2 group, —ON═C (R 3 ) 2 group, —ON═C ( R 5 ) 2 groups and the like. Here, R 3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R 4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 represents a divalent aliphatic group having 3 to 6 carbon atoms. Represents a group hydrocarbon group.
In the present invention, preferable R 1 is a chlorine atom, —OCH 3 group, —OC 2 H 5 which can further suppress the occurrence of cloudiness in the coating when the compound represented by the formula (1) is used as a solute. It is a group.
Rfとして表される炭素数1~16の直鎖状または分岐状ペルフルオロアルキル基としては、トリフルオロメチル基、ペルフルオロエチル基、ペルフルオロプロピル基、ペルフルオロブチル基、ペルフルオロペンチル基等が挙げられる。
Yとして表される炭素数1~3のアルキル基としては、メチル基、エチル基、プロピル基が挙げられる。
qは1~50、好ましくは18~30、より好ましくは22~26の整数、mは0~2、好ましくは0の整数、rは1~10、好ましくは1~5の整数を表す。
式(1)で表されるフッ素化合物は市販のパーフルオロポリエーテルをシラン処理することによって得ることができる。その方法は、例えば、特開平1-294709号公報に開示されている。 Preferable examples of the compound that can be used in the present invention include a compound represented by the formula (1).
Examples of the linear or branched perfluoroalkyl group having 1 to 16 carbon atoms represented by Rf include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoropentyl group.
Examples of the alkyl group having 1 to 3 carbon atoms represented by Y include a methyl group, an ethyl group, and a propyl group.
q represents an integer of 1 to 50, preferably 18 to 30, more preferably 22 to 26, m represents an integer of 0 to 2, preferably 0, and r represents an integer of 1 to 10, preferably 1 to 5.
The fluorine compound represented by the formula (1) can be obtained by silane treatment of a commercially available perfluoropolyether. This method is disclosed in, for example, Japanese Patent Laid-Open No. 1-294709.
好ましい混合溶媒の構成は、1気圧下での沸点が40℃以上70℃以下のフッ素系溶媒1と、該溶媒1の沸点に対して20℃以内の沸点差を有するフッ素系溶媒2との混合溶媒である。
上述の沸点条件を満たす2種類以上の溶媒を混合したコーティング剤をスプレーコーティングした場合には、膜厚のムラが抑制され、また透明な被膜が得られることが分かった。 The fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether constituting the component of the mixed solvent that can be used in the present invention has a boiling point of 40 ° C. or higher and 70 ° C. or lower at 1 atm. Further, the difference between the maximum value and the minimum value of the boiling point of the fluorinated solvent in the mixed solvent is within 25 ° C, preferably within 20 ° C.
A preferred mixed solvent structure is a mixture of a fluorine-based
It was found that when the coating agent in which two or more kinds of solvents satisfying the above boiling point conditions were mixed by spray coating, unevenness in film thickness was suppressed and a transparent film was obtained.
また、混合溶媒の混合割合は、混合溶媒全体に対して、少なくとも1つの成分が1重量%以上、好ましくは2重量%以上混合されていることが好ましい。
なお、上記溶媒には濡れ性などの諸特性を調整する助剤を混合することができる。 Solvents that can be used in the present invention include 1,1,1,3,3-pentafluorobutane (boiling point: 40 ° C.), perfluorohexane (boiling point: 40 ° C.) in consideration of environmental impact, safety during production, availability, and the like. (Boiling point 56 ° C.), 1,1,1,2,2,3,3,4,5,5,5-undecafluoro-4- (trifluoromethyl) pentane (boiling point 56 ° C.), methyl nonafluorobutyl ether ( A mixture of two or more solvents selected from a boiling point of 61 ° C. is preferable. In particular, a mixture obtained by selecting and mixing two or more solvents having a difference in boiling point of 20 ° C. or less is preferable.
The mixing ratio of the mixed solvent is such that at least one component is mixed by 1 wt% or more, preferably 2 wt% or more with respect to the entire mixed solvent.
In addition, the said solvent can be mixed with the adjuvant which adjusts various characteristics, such as wettability.
これらの中で、スプレー法で形成した防汚層は、他の方法よりも耐磨耗性に優れることが分かった。また、材料の利用効率、生産性の観点からも、スプレー法は他の方法よりも有利である。したがって、コーティング方法としてはスプレー法が最も好ましい。 The coating composition of the present invention includes a dipping method in which a substrate is immersed in the coating composition, a spray method in which the coating composition is sprayed onto the substrate, and the coating composition is dropped while rotating the substrate. An antifouling layer can be formed on the surface by coating by a known method such as a wet process such as a spin coating method or a dry process such as a vacuum deposition method using a solute of a coating composition.
Among these, it was found that the antifouling layer formed by the spray method is more excellent in abrasion resistance than other methods. The spray method is more advantageous than other methods from the viewpoint of material utilization efficiency and productivity. Therefore, the spray method is most preferable as the coating method.
無機基材としては、ガラス、金属、セラミックスなどが挙げられる。これらの中で、透明もしくは半透明のガラス、セラミックスなどが好ましい。
有機基材としては、プラスチックス、ゴム、エラストマーなどが挙げられる。これらの中で、透明もしくは半透明のプラスチックスが好ましく、特にアクリル系樹脂、ポリカーボネート樹脂などが好ましい。
透明もしくは半透明の基材は、携帯電話、各種表示器などの表示部に用いられる場合が多く、防汚層の形成を特に必要とされる基材のためである。 Examples of the substrate on which the antifouling layer is formed include an inorganic substrate or an organic substrate.
Examples of the inorganic substrate include glass, metal, and ceramics. Of these, transparent or translucent glass, ceramics and the like are preferable.
Examples of the organic substrate include plastics, rubber, and elastomer. Among these, transparent or translucent plastics are preferable, and acrylic resins and polycarbonate resins are particularly preferable.
A transparent or translucent base material is often used for a display unit such as a mobile phone or various displays, and is for a base material that particularly requires the formation of an antifouling layer.
無機表面膜としては、金属膜、半導体膜、酸化膜、窒化膜、酸窒化膜などから、製品の要求仕様に応じて選択することができる。無機表面膜の厚さは、防汚コーティング層の密着性が確保される必要最小限の厚さにすべきであり、0.01~1μmの範囲、より好ましくは0.05~0.2μmの範囲で形成するのが好ましい。ただし、防汚性以外の製品の要求仕様からこの範囲外の無機膜が必要な場合には、当然それに適合した膜厚としてもよい。 It is preferable to provide an inorganic surface film on the surface of an inorganic substrate or an organic substrate. In particular, it is preferable to provide an inorganic surface film on the surface of the organic substrate. By providing the inorganic surface film, the adhesion of the antifouling layer is improved.
The inorganic surface film can be selected from a metal film, a semiconductor film, an oxide film, a nitride film, an oxynitride film, and the like according to the required specifications of the product. The thickness of the inorganic surface film should be the minimum necessary to ensure the adhesion of the antifouling coating layer, and is in the range of 0.01 to 1 μm, more preferably 0.05 to 0.2 μm. It is preferable to form in a range. However, if an inorganic film outside this range is required based on the required specifications of the product other than the antifouling property, the film thickness may naturally be adapted to it.
式(1)で表される化合物の防汚層を形成する場合、ポリシラザン溶液を用いてスプレー法で塗布して乾燥した無機表面膜が実用上十分な耐摩耗性が得られることが分かった。また、生産コスト、生産性の観点からも、ポリシラザン溶液をスプレー法で塗布する無機表面膜形成方法は他の方法と同等もしくは優れていることから、無機表面膜はこの方法で形成するのが好ましい。 The inorganic surface film can be formed on the surface of the base material by a known forming method such as a spray method, a sol-gel method, a sputtering method, or a CVD method.
When forming the antifouling layer of the compound represented by the formula (1), it was found that an inorganic surface film coated by a spray method using a polysilazane solution and dried can provide practically sufficient wear resistance. Also, from the viewpoint of production cost and productivity, the inorganic surface film forming method in which the polysilazane solution is applied by a spray method is equivalent to or superior to other methods, and therefore the inorganic surface film is preferably formed by this method. .
以下、本発明のコーティング用組成物を用いて防汚層が形成された携帯電話の例について、図面を用いて説明する。
図1および図2は、携帯電話の一例を示す図である。
図1は携帯電話の全体を示し、通話等に使用する各種の操作キー1、電話に関する各種の情報(電話番号、電波状態、バッテリーの残量等)や画像表示部である画像表示装置2、マイク3、スピーカー4から構成されている。画像表示装置2は具体的には液晶ディスプレイ(LCD)や有機エレクトロルミネッセンスディスプレイ(有機ELディスプレイ)などが挙げられる。 The antifouling substrate of the present invention is the antifouling treatment described above on the surface of a substrate to which sebum, fingerprints, sweat, cosmetics, etc. are likely to adhere, such as a display surface of a mobile phone, a display surface of a liquid crystal panel or a touch panel, and a glass lens Is given.
Hereinafter, an example of a mobile phone in which an antifouling layer is formed using the coating composition of the present invention will be described with reference to the drawings.
1 and 2 are diagrams illustrating an example of a mobile phone.
FIG. 1 shows an entire mobile phone,
本発明は、透過窓部材6に無機表面膜6aおよび式(1)で表される化合物による防汚層6bを順に設けるものである。 FIG. 2 shows a cross section AA ′ of FIG. The
In the present invention, the transparent window member 6 is provided with the
また、表面の防汚層6bとしては、式(1)で表される化合物を溶質とするコーティング用組成物を用いてスプレー法で塗布・乾燥して形成できる。 The transparent
Further, the
(評価1)外観
評価サンプルを、暗室内で蛍光灯500ルクス以上の照度の下、目視観察し、被膜の白濁、ムラの有無を判定した。
(評価2)皮脂付着性
評価サンプルを頬に押し当て、皮脂の付着状態を目視観察した。評価基準は、未処理の青板ガラスの付着状態を不良とし、これに比較して皮脂の付着が明らかに少ないものを良好とした。
(評価3)皮脂除去性
下記(評価4)の評価サンプルをセルロース製不織布(旭化成社製ベンコット)で軽く10往復擦り、皮脂の残り方を目視観察した。評価基準は、皮脂がほとんど残らないものを良好、明らかに残るものを不良とした。
(評価4)耐摩耗性
コピー用紙(アスクル製スーパーホワイト)を9.8N/cm2の荷重でサンプルに押し当て、往復摺動させ、摺動部の水に対する接触角を測定し、接触角が90°を下回るまでの摺動回数を測定した。試験は3回以上行ない、その平均値で評価した。なお、この試験方法で5万回程度の耐摩耗性があれば、実用上十分な耐摩耗性を有すると考えられる。
なお、以下の実施例、比較例に記載している膜厚は、評価サンプルと同時に形成したSi(100)基板上の被膜を、エリプソメーター(溝尻光学社製DHA-FR)により測定した。また接触角は、評価サンプル表面の水に対する接触角を接触角計(協和界面科学社社製DM100)により測定した。 The base material after antifouling treatment was evaluated by the following method. The evaluation items and methods are described.
(Evaluation 1) Appearance An evaluation sample was visually observed in a dark room under an illuminance of 500 lux or more of fluorescent lamps, and the presence or absence of coating cloudiness or unevenness was determined.
(Evaluation 2) Sebum Adhesion The evaluation sample was pressed against the cheek, and the state of sebum adhesion was visually observed. As the evaluation criteria, the untreated soda sheet glass was considered to be poor in adhesion, and in comparison with this, the sebum was clearly less adhered.
(Evaluation 3) Sebum removability The evaluation sample shown below (Evaluation 4) was lightly rubbed 10 times with a cellulose nonwoven fabric (Bencot manufactured by Asahi Kasei Co., Ltd.), and the remaining sebum was visually observed. The evaluation criteria were good when almost no sebum remained, and poor when clearly remained.
(Evaluation 4) Abrasion resistance A copy paper (ASKUL Super White) was pressed against the sample with a load of 9.8 N / cm 2 and slid back and forth, and the contact angle of the sliding part against water was measured. The number of times of sliding until less than 90 ° was measured. The test was performed 3 times or more, and the average value was evaluated. If this test method has a wear resistance of about 50,000 times, it is considered that the wear resistance is practically sufficient.
The film thicknesses described in the following Examples and Comparative Examples were measured with an ellipsometer (DHA-FR manufactured by Mizoji Optical Co., Ltd.) on the film on the Si (100) substrate formed simultaneously with the evaluation sample. Moreover, the contact angle measured the contact angle with respect to the water of the evaluation sample surface with the contact angle meter (DM100 by Kyowa Interface Science Co., Ltd.).
コーティング用組成物として、下記の式(2)で表される化合物1重量部を、ペルフルオロヘキサン(沸点56℃)4重量部と1,1,1,3,3-ペンタフルオロブタン(沸点40℃)195重量部との混合溶媒に溶解した組成物を準備した。このコーティング組成物をガラス基板(アズワン社製スライドガラスS1225)にスプレー法でコーティングして、50℃で30分間乾燥した。形成された防汚層の膜厚は8.4nm、接触角は116°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。また耐摩耗性は95,763回だった。結果を表1に示す。
As a coating composition, 1 part by weight of a compound represented by the following formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 1,1,1,3,3-pentafluorobutane (boiling point 40 ° C.). ) A composition dissolved in a mixed solvent with 195 parts by weight was prepared. This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes. The formed antifouling layer had a film thickness of 8.4 nm and a contact angle of 116 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The abrasion resistance was 95,763 times. The results are shown in Table 1.
コーティング用組成物として、上記式(2)で表される化合物1重量部を、ペルフルオロヘキサン(沸点56℃)4重量部と1,1,1,2,2,3,3,4,5,5,5-ウンデカフルオロ-(トリフルオロメチル)ペンタン(沸点56℃)195重量部との混合溶媒に溶解した組成物を準備した。このコーティング組成物をガラス基板(アズワン社製スライドガラスS1225)にスプレー法でコーティングして、50℃で30分間乾燥した。形成された防汚層の膜厚は9.2nm、接触角は115°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。また耐摩耗性は88,140回だった。結果を表1に示す。 Example 2
As a coating composition, 1 part by weight of the compound represented by the above formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 1,1,1,2,2,3,3,4,5, A composition dissolved in a mixed solvent of 195 parts by weight of 5,5-undecafluoro- (trifluoromethyl) pentane (boiling point 56 ° C.) was prepared. This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes. The formed antifouling layer had a thickness of 9.2 nm and a contact angle of 115 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The abrasion resistance was 88,140 times. The results are shown in Table 1.
コーティング用組成物として、上記式(2)で表される化合物1重量部を、ペルフルオロヘキサン(沸点56℃)4重量部とメチルナノフルオロブチルエーテル(沸点61℃)195重量部との混合溶媒に溶解した組成物を準備した。このコーティング組成物をガラス基板(アズワン社製スライドガラスS1225)にスプレー法でコーティングして、50℃で30分間乾燥した。形成された防汚層の膜厚は8.8nm、接触角は116°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。また耐摩耗性は92,598回だった。結果を表1に示す。 Example 3
As a coating composition, 1 part by weight of the compound represented by the above formula (2) is dissolved in a mixed solvent of 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of methyl nanofluorobutyl ether (boiling point 61 ° C.). A prepared composition was prepared. This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes. The formed antifouling layer had a film thickness of 8.8 nm and a contact angle of 116 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The wear resistance was 92,598 times. The results are shown in Table 1.
ハードコート付きアクリル基板(三菱レイヨン社製アクリライトMR-200)に、スプレー法でポリシラザン溶液(AZエレクトロニックマテリアル社製アクアミカNL120A-05)を塗布し、大気雰囲気に1昼夜放置してポリシラザン薄膜(膜厚93nm)を形成した。その後、実施例2で使用したコーティング組成物を実施例2と同じ条件でスプレー法でコーティングした。防汚層の膜厚は8.5nm、接触角は117°だった。
被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。また耐摩耗性は66,031回だった。 Example 4
A polysilazane solution (Aquamica NL120A-05 manufactured by AZ Electronic Materials Co., Ltd.) is applied to an acrylic substrate with hard coat (Acrylite MR-200 manufactured by Mitsubishi Rayon Co., Ltd.) by a spray method, and left for a day and night in an air atmosphere to form a polysilazane thin film (film) A thickness of 93 nm) was formed. Thereafter, the coating composition used in Example 2 was coated by the spray method under the same conditions as in Example 2. The film thickness of the antifouling layer was 8.5 nm and the contact angle was 117 °.
The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The abrasion resistance was 66,031 times.
コーティング組成物として、上記式(2)で表される化合物1重量部を、ペルフルオロヘキサン(沸点56℃)199重量部に溶解して準備した。このコーティング組成物をガラス基板(アズワン社製スライドガラスS1225)に実施例1と同じ条件でスプレー法でコーティングした。被膜の外観は、明らかに白濁していた。被膜の外観が不良であったため、皮脂付着性、皮脂除去性および耐摩耗性の評価を中止した。 Comparative Example 1
As a coating composition, 1 part by weight of a compound represented by the above formula (2) was prepared by dissolving in 199 parts by weight of perfluorohexane (boiling point 56 ° C.). This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. The appearance of the coating was clearly cloudy. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.
コーティング組成物として、上記式(2)で表される化合物1重量部を、ペルフルオロヘキサン(沸点56℃)4重量部と旭硝子社製NovecHFE7200(沸点76℃)195重量部の混合溶媒に溶解して準備した。このコーティング組成物をガラス基板(アズワン社製スライドガラスS1225)に実施例1と同じ条件でスプレー法でコーティングした。被膜の外観は透明だったが、目視で認識できる円形の模様(ムラ)が発生した。被膜の外観が不良であったため、皮脂付着性、皮脂除去性および耐摩耗性の評価を中止した。 Comparative Example 2
As a coating composition, 1 part by weight of the compound represented by the above formula (2) is dissolved in a mixed solvent of 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of Asahi Glass Novec HFE 7200 (boiling point 76 ° C.). Got ready. This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. Although the appearance of the film was transparent, a circular pattern (unevenness) that could be recognized visually was generated. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.
コーティング組成物として、上記式(2)で表される化合物1重量部を、ペルフルオロヘキサン(沸点56℃)4重量部と住友スリーエム社製フロリナートFC-40(沸点155℃)195重量部との混合溶媒に溶解して準備した。このコーティング組成物をガラス基板(アズワン社製スライドガラスS1225)に実施例1と同じ条件でスプレー法でコーティングした。被膜の外観は透明だったが、目視で認識できる不定形(アメーバ状)のムラが発生した。被膜の外観が不良であったため、皮脂付着性、皮脂除去性および耐摩耗性の評価を中止した。 Comparative Example 3
As a coating composition, 1 part by weight of the compound represented by the above formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of Fluorinert FC-40 (boiling point 155 ° C.) manufactured by Sumitomo 3M Limited. Prepared by dissolving in a solvent. This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. The appearance of the film was transparent, but irregular irregularities (amoeba-like) that could be recognized visually were generated. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.
実施例2で使用したコーティング組成物を、実施例4で使用したハードコート付きアクリル基板に直接スプレー法でコーティングした。防汚層の膜厚は9.9nm、接触角は116°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。しかし、耐摩耗性は7,379回と低かった。 Comparative Example 4
The coating composition used in Example 2 was coated directly on the hard-coated acrylic substrate used in Example 4 by a spray method. The film thickness of the antifouling layer was 9.9 nm, and the contact angle was 116 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was as low as 7,379 times.
実施例2で使用したコーティング組成物の溶質を、実施例2で使用したガラス基板に真空蒸着法で成膜した。真空蒸着の背景圧力は10-3Pa台とし、ガラス製坩堝に入れたコーティング組成物の溶質を室温から500℃まで約30分かけて昇温した。形成された被膜の膜厚は7.2nm、接触角は117°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。しかし、耐摩耗性は42,217回であり、実施例2と比較すると低かった。 Comparative Example 5
The coating composition solute used in Example 2 was deposited on the glass substrate used in Example 2 by vacuum deposition. The background pressure of vacuum deposition was on the order of 10 −3 Pa, and the solute of the coating composition placed in a glass crucible was heated from room temperature to 500 ° C. over about 30 minutes. The formed film had a thickness of 7.2 nm and a contact angle of 117 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was 42,217 times, which was lower than that of Example 2.
実施例2で使用したコーティング組成物を、実施例2で使用したガラス基板にディップ法で成膜した。ディップは、室温で24時間浸漬し、10mm/秒程度の速さで引き上げた。形成された被膜の膜厚は5nm以下で、測定できなかった。また、接触角は117°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。しかし、耐摩耗性は4,701回と低かった。 Comparative Example 6
The coating composition used in Example 2 was formed into a film on the glass substrate used in Example 2 by the dip method. The dip was immersed for 24 hours at room temperature and pulled up at a speed of about 10 mm / second. The film thickness of the formed film was 5 nm or less and could not be measured. The contact angle was 117 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was as low as 4,701 times.
実施例4で使用したハードコート付きアクリル基板に、スパッタ法でSiO2薄膜(膜厚101nm)を形成した。スパッタはイオンビーム方式で行い、背景圧力を10-3Pa台とし、溶融石英ターゲットに700eVのArイオンビームを照射した。その後、実施例2で使用したコーティング剤をスプレー法でコーティングした。防汚層の膜厚は8.9nm、接触角は115°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。しかし、耐摩耗性は20,558回と実施例4と比較すると低かった。 Comparative Example 7
A SiO 2 thin film (film thickness: 101 nm) was formed on the acrylic substrate with hard coat used in Example 4 by sputtering. Sputtering was performed by an ion beam method, a background pressure was set to 10 −3 Pa, and a fused silica target was irradiated with a 700 eV Ar ion beam. Thereafter, the coating agent used in Example 2 was coated by a spray method. The film thickness of the antifouling layer was 8.9 nm and the contact angle was 115 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was 20,558 times, which was lower than that of Example 4.
2 画像表示装置
3 マイク(送話口)
4 スピーカー(受話口)
5 筐体
6 透過窓部材
6a 無機表面膜
6b 防汚層 1
4 Speaker (Entrance)
5 Housing 6
Claims (10)
- ペルフルオロアルキレンエーテル基を分子主鎖内に含み、シリコン原子を含む加水分解性基を側鎖に含む化合物を溶媒に溶解してなるコーティング用組成物であって、
前記溶媒がフッ素化炭化水素およびフッ素化エーテルの少なくとも1つを含むフッ素系溶媒同士の混合溶媒であり、前記フッ素系溶媒は1気圧下での沸点が40℃以上70℃以下であり、前記混合溶媒中の前記フッ素系溶媒の沸点の最大値と最小値の差が25℃以内であることを特徴とするコーティング用組成物。 A coating composition comprising a compound containing a perfluoroalkylene ether group in a molecular main chain and a hydrolyzable group containing a silicon atom in a side chain dissolved in a solvent,
The solvent is a mixed solvent of fluorine-based solvents including at least one of a fluorinated hydrocarbon and a fluorinated ether, and the fluorine-based solvent has a boiling point of 40 ° C. or more and 70 ° C. or less under 1 atm, and the mixture The coating composition, wherein the difference between the maximum value and the minimum value of the boiling point of the fluorinated solvent in the solvent is within 25 ° C. - 前記ペルフルオロアルキレンエーテル基が下記式(1-1)で表され、前記シリコン原子を含む加水分解性基が下記式(1-2)で表されることを特徴とする請求項1記載のコーティング用組成物。
- 前記化合物が下記式(1)で表される化合物であることを特徴とする請求項2記載のコーティング用組成物。
- 前記R1が塩素原子、-OCH3基、および-OC2H5基から選ばれる少なくとも1つの基であることを特徴とする請求項3記載のコーティング用組成物。 4. The coating composition according to claim 3, wherein R 1 is at least one group selected from a chlorine atom, —OCH 3 group, and —OC 2 H 5 group.
- 前記フッ素系溶媒が1,1,1,3,3-ペンタフルオロブタン、ペルフルオロヘキサン、1,1,1,2,2,3,3,4,5,5,5-ウンデカフルオロ-4-(トリフルオロメチル)ペンタン、または、メチルノナフルオロブチルエーテルであることを特徴とする請求項1記載のコーティング用組成物。 The fluorine-based solvent is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4,5,5,5-undecafluoro-4- The coating composition according to claim 1, which is (trifluoromethyl) pentane or methyl nonafluorobutyl ether.
- 前記混合溶媒が1,1,1,3,3-ペンタフルオロブタン、ペルフルオロヘキサン、1,1,1,2,2,3,3,4,5,5,5-ウンデカフルオロ-4-(トリフルオロメチル)ペンタン、および、メチルノナフルオロブチルエーテルから選ばれた2種類のフッ素系溶媒の混合溶媒であることを特徴とする請求項1記載のコーティング用組成物。 The mixed solvent is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4,5,5,5-undecafluoro-4- ( The coating composition according to claim 1, which is a mixed solvent of two kinds of fluorine-based solvents selected from (trifluoromethyl) pentane and methyl nonafluorobutyl ether.
- 無機基材の表面、または無機もしくは有機基材に形成された無機表面膜の表面にコーティングを施すことにより、防汚処理を行なう防汚処理方法において、
前記無機基材の表面または無機表面膜の表面へのコーティングが請求項1記載のコーティング用組成物をスプレー法で塗布されたコーティングであることを特徴とする防汚処理方法。 In the antifouling treatment method for carrying out the antifouling treatment by coating the surface of the inorganic substrate or the surface of the inorganic surface film formed on the inorganic or organic substrate,
An antifouling treatment method, wherein the coating on the surface of the inorganic substrate or the surface of the inorganic surface film is a coating obtained by applying the coating composition according to claim 1 by a spray method. - 前記無機表面膜は、ポリシラザン溶液をスプレー法で塗布することにより形成した無機表面膜であることを特徴する請求項7記載の防汚処理方法。 The antifouling treatment method according to claim 7, wherein the inorganic surface film is an inorganic surface film formed by applying a polysilazane solution by a spray method.
- 基材の表面、または基材に形成された無機表面膜の表面に防汚層を有する防汚性基材であって、
前記防汚層が請求項7記載の防汚処理方法により形成された防汚層であることを特徴とする防汚性基材。 An antifouling substrate having an antifouling layer on the surface of the substrate or the surface of the inorganic surface film formed on the substrate,
The antifouling substrate, wherein the antifouling layer is an antifouling layer formed by the antifouling treatment method according to claim 7. - 前記防汚性基材は、画像表示部を有し、該画像表示部の表面に請求項9記載の耐防汚層が形成された携帯電話であることを特徴とする防汚性基材。 The antifouling substrate is a mobile phone having an image display portion, and the antifouling layer according to claim 9 formed on the surface of the image display portion.
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Also Published As
Publication number | Publication date |
---|---|
JPWO2010038648A1 (en) | 2012-03-01 |
TW201020300A (en) | 2010-06-01 |
CN102171299B (en) | 2013-10-16 |
JP5655215B2 (en) | 2015-01-21 |
TWI449761B (en) | 2014-08-21 |
HK1159152A1 (en) | 2012-07-27 |
KR101587308B1 (en) | 2016-01-20 |
KR20110063850A (en) | 2011-06-14 |
CN102171299A (en) | 2011-08-31 |
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