WO2017179678A1 - 超撥液性被膜及び超撥液性硬化性被膜形成用組成物 - Google Patents
超撥液性被膜及び超撥液性硬化性被膜形成用組成物 Download PDFInfo
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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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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- 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
- C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3072—Treatment with macro-molecular organic compounds
Definitions
- the present invention relates to a super-liquid-repellent coating capable of imparting to a surface a coating, particularly super-water repellency and super-oil repellency (hereinafter sometimes collectively referred to as “super-liquid repellency”).
- the present invention also relates to a curable film-forming composition that can form a curable film.
- Patent Document 1 a method of imparting super liquid repellency by chemically bonding a fluoroalkylsilane compound to a surface to be treated on which a cured coating film containing silica fine particles or the like is formed.
- Patent Document 2 A method of forming a film by hydrolyzing alkoxysilane in a mixed state of alkoxysilane, perfluoroalkylsilane and silica fine particles has also been proposed (Patent Document 2).
- Non-patent Document 1 a coating obtained by copolymerizing fine particles having radical polymerizable groups on the surface and a fluorine-containing monomer has been proposed.
- an object of the present invention is to provide a super-liquid-repellent film that achieves both super-liquid repellency, which is the original performance, and wear resistance.
- the inventors of the present invention have made extensive studies, and are coating films having a fluorine atom content of 1 to 60 wt%, an average surface roughness Ra of 0.5 to 20 ⁇ m, and a specific surface area ratio of 1.7.
- the contact angle of water after the contact angle of water is 150 ° or more
- the contact angle of n-hexadecane is 80 ° or more
- the PET film is applied 100 times with a load of 100 g / cm 2. It has been found that the above problem can be solved by using a coating film having a surface of 150 ° or more.
- the present invention has been completed by further trial and error, and includes the following embodiments.
- Item 1 A coating, The fluorine atom content is 1 to 60 wt%, The average surface roughness Ra is 0.5 to 20 ⁇ m, The specific surface area ratio is 1.7-5, The water contact angle is 150 ° or more, A coating film having a surface where the contact angle of n-hexadecane is 80 ° or more, and the contact angle of water after the PET film is rubbed 100 times with a load of 100 g / cm 2 is 150 ° or more.
- a curable film-forming composition containing a fluorine compound The film after curing is The average surface roughness Ra is 0.5 to 20 ⁇ m, The specific surface area ratio is 1.7-5, The water contact angle is 150 ° or more, The contact angle of n-hexadecane is 80 ° or more, and the contact angle of water after the PET film is rubbed 100 times with a load of 100 g / cm 2 is 150 ° or more.
- a coating film having excellent liquid repellency and wear resistance can be provided.
- Conventional super-liquid-repellent coatings could not be applied to the surface of articles that require wear resistance, but the scope of application can be extended to articles that require wear resistance by using the present invention.
- Coating The coating of the present invention is
- the fluorine atom content is 1 to 60 wt%
- the average surface roughness Ra is 0.5 to 20 ⁇ m
- the specific surface area ratio is 1.7-5
- the water contact angle is 150 ° or more
- the contact angle of n-hexadecane is 80 ° or more
- the contact angle of water after the PET film is rubbed 100 times with a load of 100 g / cm 2 is 150 ° or more. It is a film.
- the film of the present invention has a fluorine atom content of 1 to 60 wt%, more preferably 1.5 to 55 wt%, and further preferably 2 to 50 wt% with respect to the entire film.
- the amount of fluorine atoms in the coating is relatively large (10 wt% or more as a guide), it is possible to analyze using an automatic sample combustion apparatus.
- the automatic sample combustion apparatus for example, AQF-100 manufactured by MITSUBISHI CHEMICAL COPOLATION, or an equivalent product thereof can be used. If the amount of fluorine atoms in the coating is relatively small (as a guide, less than 10 wt%), the sample can be burned using a flask and analyzed using an ion meter.
- X-ray photoelectron spectroscopy energy dispersive X-ray fluorescence analysis using a scanning electron microscope, or the like. Any one is appropriately selected according to the state of the coating.
- the coating film of the present invention contains a fluorine compound, and it is considered that when the fluorine atom content is within the above range, stronger liquid repellency and wear resistance are exhibited.
- examples of the fluorine compound include fluoroalkyl (meth) acrylates having 1 to 8 carbon atoms in the fluoroalkyl group, triacryloylheptadecafluorononenylpentaerythritol, 1,2-diaacryloxymethyl-perfluorocyclohexane, and OPTOOL
- examples thereof include compounds having structural units based on DAC-HP and the like.
- fluorine compounds include fluoroalkyl (meth) acrylates having 1 to 6 carbon atoms in the fluoroalkyl group, triacryloylheptadecafluorononenyl pentaerythritol, and 1,2-diaacryloxymethyl-perfluorocyclohexane.
- the compound which has a structural unit based on is more preferable, and the compound which has a structural unit based on perfluorohexyl methyl (meth) acrylate and triacryloyl heptadecafluorononenyl pentaerythritol is further more preferable.
- the average surface roughness Ra of the surface of the coating of the present invention is 0.5 to 20 ⁇ m, more preferably 0.6 to 17.5 ⁇ m, still more preferably 0.7 to 15 ⁇ m.
- the coating film of the present invention is considered to exhibit stronger liquid repellency and wear resistance when the average surface roughness Ra of the surface is within the above range.
- the average surface roughness Ra of the coating surface is the average surface roughness Ra measured in the long side direction (702.801 ⁇ m) set at five points in a region of 526.929 ⁇ m ⁇ 702.801 ⁇ m square. It is average. Specifically, the measurement is performed using VK-9710 manufactured by KEYENCE CORPORATION, or an equivalent thereof, and a MUL00201 microscope manufactured by Nikon, attached to VK-9710, or an equivalent thereof.
- the film of the present invention has a specific surface area ratio of 1.7 to 5, more preferably 1.75 to 4.5, and still more preferably 1.8 to 4.
- the coating film of the present invention is considered to exhibit stronger liquid repellency and wear resistance when the specific surface area ratio of the surface is within the above range.
- the specific surface area ratio of the coating surface is calculated by comparing the surface area ratio of the surface to be measured to the surface area of the true smooth surface by comparing the surface areas in the 351.4 ⁇ m ⁇ 351.4 ⁇ m square area with each other. Specifically, measurement is performed using VK-9710 manufactured by Keyence Corporation or an equivalent thereof, and a microscope of MUL00201 manufactured by Nikon Inc. attached to VK-9710 or an equivalent thereof.
- the film of the present invention exhibits super liquid repellency.
- the static contact angle of water during film formation is 150 ° or more
- the static contact angle of n-hexadecane (hereinafter sometimes referred to as n-HD) is 80 ° or more. It is.
- the static contact angle of water and the static contact angle of n-HD are measured as follows.
- the apparatus uses a contact angle meter Drop Master 701 or an equivalent thereof to measure water at 5 points per sample with a droplet volume of 2 ⁇ l for both water and n-HD.
- the static contact angle becomes 150 ° or more, depending on the conditions, the liquid cannot stand on the surface of the base material. Therefore, in such a case, the static contact angle is measured using the needle of the syringe as a support, and the value obtained at that time is taken as the static contact angle.
- the coating film of the present invention has a static contact angle of water of 150 ° or more after a PET film (trade name: U-46 manufactured by Toray Industries, Inc.) or its equivalent is applied 100 times with a load of 100 g / cm 2 .
- this parameter is measured as follows. Holder (area in contact with the sample: 1 cm 2) of the rubbing tester (Imoto Seisakusho rubbing tester "abrasion tester 151E 3 consecutive Specifications" or its equivalent) to the PET film (trade name: U-46, manufactured by Toray Industries, or Equivalent product) is mounted, the sample surface is wiped 100 times with a load of 100 g, and the contact angle with water is then measured.
- the static contact angle of water after the coating is 150 ° or more, and the static contact angle of n-hexadecane is 60 ° or more. More preferably, the static contact angle of water after the coating is 150 ° or more, and the static contact angle of n-hexadecane is 80 ° or more.
- the coating of the present invention is preferably used for imparting water repellency and / or oil repellency to the surface to be treated.
- Curable film-forming composition The curable film-forming composition of the present invention is not particularly limited as long as it contains a fluorine compound and the cured film has the above-mentioned properties.
- the curable film-forming composition of the present invention may contain fine particles (A) and / or a polyfunctional crosslinkable compound (B) described below as a fluorine compound.
- Fine particles in which at least one fluorine-containing modifying compound is bonded to the surface (A) are not particularly limited.
- organic fine particles such as carbon black, fullerene and carbon nanotubes can be widely used.
- the size of the fine particles is preferably 0.5 nm to 1000 nm, preferably 1 nm to 100 nm, more preferably 5 nm to 70 nm, as the average particle size at the time of primary dispersion defined by DIN 53206.
- the particle diameter is within this range, it is easy to obtain surface roughness necessary for imparting a super-repellent state to the surface to be treated. It is expected that the surface roughness constructed from fine particles having an average particle diameter of 0.5 nm or more has a higher ratio to the roughness of the smooth plane.
- the roughness of the surface constructed from an average particle diameter of 1000 nm or less does not become a large unevenness that should be called a surface shape as compared with the diameter of a droplet.
- Measurement of the average particle size during primary dispersion of the fine particles can be performed using a transmission electron microscope or a scanning electron microscope. More specifically, the average particle diameter is obtained by photographing with a transmission electron microscope or a scanning electron microscope, measuring the diameter of 200 or more particles on the photograph, and calculating the arithmetic average value thereof. Can do.
- higher-order aggregation states such as secondary aggregation defined by DIN 53206 may be imparted to the liquid repellency. If this higher-order aggregate is present at a certain ratio, it is easier to construct a pseudo-fractal state, so that the surface roughness becomes more rough, thereby improving the liquid repellency.
- the ratio of the higher-order aggregation state appears in the apparent density.
- the apparent density is obtained by measuring the volume when 0.2 g of powder is put into a 10 ml measuring cylinder.
- the apparent density is preferably 0.01 ⁇ 0.5g / cm 3, more preferably 0.015 ⁇ 0.3g / cm 3, even more preferably at 0.02 ⁇ 0.05g / cm 3 .
- a polymerizable group is present at at least one molecular terminal of the modifying compound, and at least one of the modifying compounds is a fluorine-containing compound.
- the polymerizable group is present in a polymerizable state at the molecular end of the modifying compound.
- the polymerizable group is not particularly limited, and examples thereof include a radical polymerizable group, a cationic polymerizable group, and an anion polymerizable group.
- a radical polymerizable group is preferable in terms of versatility and reactivity.
- the radical polymerizable group is not particularly limited, and examples thereof include a vinyl group, a (meth) acryl group, a styryl group, and a maleimide group.
- radical polymerizable group a (meth) acryl group and a styryl group are preferable in view of versatility and reactivity.
- the manner in which the modifying compound is bonded to the surface of the fine particle is not particularly limited, and examples thereof include covalent bond, coordination bond, ionic bond, hydrogen bond, and bond by van der Waals force.
- the method for producing the fine particles (A) in which the modifying compound is bonded to the surface is not particularly limited, but generally, a method of reacting a compound having a polymerizable group and a reactive surface with the particle surface to the fine particles, etc. Is mentioned.
- the site showing reactivity with the particle surface can be appropriately selected depending on the state of the particle surface.
- the reaction is performed using silane coupling.
- a compound is chemically bonded to the fine particles, it is difficult to select the number of compounds to be reacted.
- a plurality of compounds exist in a chemically bonded state on the surface of the fine particles.
- the coating film of the present invention can be obtained by performing a polymerization reaction described later using at least one of the fine particles (A).
- At least one of the modifying compounds is a fluorine-containing compound, and preferably has a fluoroalkyl group.
- the “fluoroalkyl group” means an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and includes a fluoropolyether group unless otherwise specifically used.
- the coating film of the present invention can exhibit excellent liquid repellency. The presence of fluorine atoms on the surface of the fine particles is considered to provide strong liquid repellency.
- a perfluoroalkyl group is preferable from the viewpoint of liquid repellency.
- the fine particles (A) can be used singly or in combination of two or more.
- the content ratio of the fine particles (A) to the entire curable film-forming composition of the present invention is not particularly limited, but is usually preferably about 1 to 15% by weight, and preferably about 2 to 10% by weight. It is more preferable.
- the composition for forming a curable coating film of the present invention has a compound containing two or more crosslinkable groups in the molecule (polyfunctional crosslinkable compound), so that the coating film after curing has excellent wear resistance. Is considered to be granted.
- the polyfunctional crosslinkable compound is not particularly limited, but in terms of abrasion resistance, any compound having 2 to 8 crosslinkable groups in the molecule is preferable, and any compound having 3 to 6 crosslinkable groups is preferable. It is more preferable if it has three crosslinkable groups.
- the crosslinkable group is not particularly limited, and examples thereof include a radical polymerizable group, a cationic polymerizable group, an anion polymerizable group, an epoxy group, an amine group, and an isocyanate group.
- a radical polymerizable group and an isocyanate group are preferable in terms of versatility and reactivity.
- the radical polymerizable group is not particularly limited, and examples thereof include a vinyl group, a (meth) acryl group, a styryl group, and a maleimide group.
- radical polymerizable group a (meth) acryl group and a styryl group are preferable in view of versatility and reactivity.
- the compound (B-1) having a radical polymerizable group is not particularly limited, and examples thereof include those represented by the following general formula (1).
- X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (where X 1 and X 2 are the same or different and represent a hydrogen atom, a fluorine atom or a chlorine atom)
- Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH 2 CH 2 N (R 1 ) SO 2 — group (provided that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Z 1 and the left
- Z 1 is a residue obtained by removing i + 1 hydrogen atoms from a hydrocarbon optionally having an oxygen atom and / or a fluorine atom, or a carbon atom or an oxygen atom
- Z 2 is A residue obtained by removing j hydrogen atoms from a hydrocarbon optionally having an oxygen atom and / or a fluorine atom, or a carbon atom or an oxygen atom
- i is an integer of 1 to 3
- j is 1 to (It is an integer of 4 and the number obtained by multiplying i and j is 2 or more.)
- the hydrocarbon may be either cyclic or non-cyclic, and may be linear or branched.
- the hydrocarbon preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 2 carbon atoms.
- acrylic acid ester represented by the above general formula (1) are as follows.
- acrylic esters represented by the general formula (1) examples include A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-TMPT, and the like. And DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- the compound (B-1) having a radical polymerizable group may be a fluorine-containing compound.
- the coating film of the present invention can exhibit more excellent liquid repellency.
- the compound (B-1) having a radical polymerizable group which is a fluorine-containing compound, is not particularly limited and can be widely selected.
- Rf 1 is a linear or branched monovalent or 2 which may have at least one carbon atom substituted with a heteroatom and may have a carbon-carbon unsaturated bond.
- Valent perfluorocarbon group In R 1 , at least one carbon atom may be substituted with a hetero atom, at least one hydrogen atom may be substituted with a halogen atom, and may have a carbon-carbon unsaturated bond.
- a branched or cyclic trivalent or higher hydrocarbon group or carbonyl group, Z 3 has a polymerizable group at at least one terminal, at least one carbon atom may be substituted with a hetero atom, at least one hydrogen atom may be substituted with a halogen atom, and carbon-carbon A linear or branched monovalent hydrocarbon group or carbonyl group optionally having an intersaturation bond, k is an integer of 1 or more, and l is an integer of 2 or more.
- Rf 1 may be a perfluoroalkyl group, a perfluoroalkenyl group or a perfluoroalkynyl group, or a perfluoropolyether group (may be referred to as PFPE).
- Rf 1 preferably has 1 to 200 carbon atoms, more preferably 2 to 150 carbon atoms, and still more preferably 3 to 100 carbon atoms.
- R 1 preferably has 1 to 100 carbon atoms, more preferably 1 to 75 carbon atoms, and still more preferably 1 to 50 carbon atoms.
- Z 3 preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.
- the compound which has a structure represented by General formula (2) Although it does not specifically limit as an example of the compound which has a structure represented by General formula (2), for example, the compound which has a pentaerythrole skeleton, the compound which has a dipentaerystol skeleton, the compound which has a trimethylol propane skeleton, isocyanurate Examples thereof include compounds having a skeleton and compounds having a linear skeleton. These compounds are known as described in, for example, JP2009-198627A and JP2003-509007A, and are not particularly limited. It can also be used by appropriately selecting from among them.
- a compound having a pentaerythrole skeleton a compound having three Z 3 having a vinyl group at the terminal can be given. Specific examples of such compounds include the following.
- Examples of commercially available compounds represented by the general formula (2) include LINC-3A (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Z 4 has a polymerizable group at at least one terminal, at least one carbon atom may be substituted with a hetero atom, and at least one hydrogen atom may be substituted with a halogen atom.
- Rf 2 is a branched or cyclic divalent or higher-valent perfluorocarbon group in which at least one carbon atom may be substituted with a heteroatom and may have a carbon-carbon unsaturated bond
- m is an integer of 2 or more.
- Rf 2 can be a perfluoroalkyl group, a perfluoroalkenyl group or a perfluoroalkynyl group, or a perfluoropolyether group.
- Rf 2 preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.
- Z 4 preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.
- Examples of the compound having the structure represented by the general formula (2) are not particularly limited, and examples thereof include a compound having a cyclohexyl skeleton.
- a compound having a cyclohexyl skeleton a compound having two Z 4 having a vinyl group at the terminal can be given. Specific examples of such compounds include the following.
- Examples of commercially available compounds represented by the general formula (3) include LINC-102A (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Z 5 has a perfluoroethylene group at least at one terminal, at least one carbon atom may be substituted with a hetero atom, and at least one hydrogen atom is substituted with a halogen atom. It is a linear or branched monovalent hydrocarbon group or carbonyl group which may have a carbon-carbon unsaturated bond, R 2 may have at least one carbon atom substituted with a heteroatom, at least one hydrogen atom may be substituted with a halogen atom, or at least one carbon atom may be substituted with a heteroatom.
- R 2 preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.
- Z 5 preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.
- the compound which has a structure represented by General formula (4) Although it does not specifically limit as an example of the compound which has a structure represented by General formula (4), for example, the compound which has a pentaerythrole skeleton, the compound which has a dipentaerystol skeleton, the compound which has a trimethylol propane skeleton, and a straight chain And compounds having a skeleton.
- the coating of the present invention has structural features that can be obtained by copolymerization using fine particles having the polymerizable group on the surface and the polyfunctional polymerizable compound, This seems to have led to the acquisition of excellent wear resistance.
- the compound having an isocyanate group (B-2) is not particularly limited, and examples thereof include those represented by the following general formula (5).
- Z 6 has an isocyanate group at at least one terminal, at least one carbon atom may be substituted with a hetero atom, and at least one hydrogen atom may be substituted with a halogen atom;
- at least one carbon atom may be substituted with a heteroatom, at least one hydrogen atom may be substituted with a halogen atom, or at least one carbon atom may be substituted with a heteroatom.
- R 3 preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.
- Z 6 is preferably 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms.
- the compound (B-2) having an isocyanate group (—NCO group) may be used alone or in combination of two or more.
- Examples of the compound (B-2) having an isocyanate group include polyisocyanate.
- polyisocyanate means a compound having two or more isocyanate groups in the molecule.
- Compound (B-2) may be a polyisocyanate obtained by trimerizing diisocyanate.
- the polyisocyanate obtained by trimerizing such a diisocyanate can be a triisocyanate.
- the polyisocyanate that is a trimer of diisocyanate may exist as a polymer obtained by polymerizing these.
- the diisocyanate is not particularly limited, but an isocyanate group such as trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate is bonded to an aliphatic group.
- an isocyanate group such as trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate is bonded to an aliphatic group.
- Diisocyanate diisocyanate having an isocyanate group bonded to an aromatic group, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate.
- aromatic group such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate.
- polyisocyanate examples include, but are not limited to, compounds having the following structure.
- polyisocyanates may exist as polymers.
- an isocyanurate type polyisocyanate of hexamethylene diisocyanate it may have a polymer having the following structure.
- the compound (B-2) is an isocyanurate type polyisocyanate.
- the isocyanurate type polyisocyanate may be a polymer obtained by polymerizing these.
- the isocyanurate type polyisocyanate may be a monocyclic compound having only one isocyanurate ring, or may be a polycyclic compound obtained by polymerizing this monocyclic compound.
- a mixture containing a monocyclic compound having only one isocyanurate ring can be used.
- a mixture containing the compound (B-2) which is an isocyanurate type polyisocyanate can be used.
- the isocyanurate type polyisocyanate may be, for example, a triisocyanate, specifically, a triisocyanate obtained by trimerizing diisocyanate.
- examples of the mixture of two or more compounds (B-2) include Sumidur (registered trademark) N3300 (manufactured by Sumika Covestro Urethane Co., Ltd.), Death Module (Registered trademark) N3600 (manufactured by Sumika Covestrourethane Co., Ltd.), Death Module T, L, IL, HL series (manufactured by Sumika Covestrourethane Co., Ltd.), Death Module (registered trademark) 2460M (Sumitomo Covestrourethane) Sumijoule (registered trademark) 44 series (manufactured by Sumika Covestrourethane Co., Ltd.), SBU isocyanate group (manufactured by Sumika Covestrourethane Co., Ltd.), Death Module (registered trademark) E, M series (manufactured by Sumika Co., Ltd.) Chemical Cobestrourethane Co., Ltd.), Sumijoule
- the composition when the curable film-forming composition of the present invention contains the compound (B-2) having an isocyanate group, the composition further contains a compound having a functional group capable of reacting with the isocyanate group and a radical polymerizable group.
- a compound having a radical polymerizable group as shown below may be generated at the time of curing.
- the composition for curable film formation of this invention may contain the compound which has the radical polymerizable group produced
- PFPE represents a perfluoropolyether group.
- the polyfunctional crosslinkable compound (B) can be used alone or in combination of two or more.
- At least one compound having one reactive group in the molecule (also referred to as a monofunctional reactive polymerizable compound). May be a further constituent component.
- These preferably have a structure capable of reacting with (A) or (B) by applying ultraviolet rays or heat.
- preferred embodiments of the curable film-forming composition of the present invention include the following. (A) fine particles in which at least one fluorine-containing modified compound is bonded to the surface; and (B) a compound containing two or more crosslinkable groups in the molecule, The film after curing is The surface having an average surface roughness Ra of 0.5 to 20 ⁇ m and a specific surface area ratio of 1.7 to 5; A curable film-forming composition.
- composition for curable film formation of this invention (A) fine particles in which at least one fluorine-containing modifying compound is bonded to the surface; and (B) a compound containing two or more polymerizable groups in the molecule,
- the film after curing is
- the average surface roughness Ra is 0.5 to 20 ⁇ m, and the specific surface area ratio is 1.7 to 5,
- the water contact angle is 150 ° or more, n-hexadecane has a surface with a contact angle of 80 ° or more,
- a curable film-forming composition (A) fine particles in which at least one fluorine-containing modifying compound is bonded to the surface; and (B) a compound containing two or more polymerizable groups in the molecule,
- the film after curing is
- the average surface roughness Ra is 0.5 to 20 ⁇ m, and the specific surface area ratio is 1.7 to 5,
- the water contact angle is 150 ° or more
- n-hexadecane has a surface with a contact angle
- the fine particles (A) and the polyfunctional crosslinking compound (B) are as described above.
- composition for curable film formation of this invention may contain the polymerization initiator further as needed.
- (B-1) when used as a polyfunctional crosslinking compound, it is preferably used.
- radicals and cations are generated only when irradiated with electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, ⁇ -rays, and the like. It serves as a catalyst for initiating the curing (crosslinking reaction) of the carbon double bond, and it is usually preferable to use one that generates radicals and cations with ultraviolet light, particularly one that generates radicals. For example, the following can be illustrated.
- Acetophenone series acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, ⁇ -aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinepropan-1-one, etc.
- Benzoin series benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, and the like.
- Benzophenone series benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, etc.
- Thioxanthones thioxanthone, chlorothioxanthone, methylxanthone, diethylthioxanthone, dimethylthioxanthone and the like.
- an initiator that generates radicals by thermal energy may be used.
- the amount of the polymerization initiator that generates radicals by the above-mentioned light energy is not particularly limited, but it is usually preferably about 0.01 to 20 parts by weight with respect to 100 parts by weight of the monomer component. More preferably, it is about 1 to 10 parts by weight.
- any known polymerization initiator for thermal radical polymerization reaction can be used without particular limitation.
- azo initiators such as azobisisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile; benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivatives, phosphine oxide derivatives, benzoketone derivatives, phenylthioether derivatives, Azide derivatives, diazo derivatives, disulfide derivatives and the like can be used.
- azo initiators such as azobisisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile
- benzoyl peroxide potassium persulfate, ammonium persulfate
- benzophenone derivatives phosphine oxide derivatives
- benzoketone derivatives benzoketone derivatives
- phenylthioether derivatives Azide derivatives, diazo
- the amount of the polymerization initiator used is not particularly limited, but usually it is preferably about 0.01 to 10 parts by weight and preferably about 3 to 7 parts by weight with respect to 100 parts by weight of the monomer component. More preferred.
- the curable film-forming composition of the present invention may further contain a catalyst activator for hydroxyl groups and isocyanate groups, if necessary.
- a catalyst activator for hydroxyl groups and isocyanate groups when (B-2) is used as a polyfunctional crosslinkable compound, it is preferably used.
- titanium tetra-2-ethylhexoxide which is an organic titanium compound
- zirconium tetraacetylacetonate zirconium dibutoxybis (ethyl)
- ethyl which is an organic zirconia compound, and the like.
- Acetoacetate can be used.
- ORGATIX TA-30 manufactured by Matsumoto Fine Chemical Co., Ltd.
- TC-750 manufactured by Matsumoto Fine Chemical Co., Ltd.
- ZC-580 manufactured by Matsumoto Fine Chemical Co., Ltd.
- ZC-700 manufactured by Matsumoto Fine Chemical Co., Ltd. Matsumoto Fine Chemical Co., Ltd.
- the curable film-forming composition of the present invention can further dissolve each component including a polymerization initiator uniformly or a mixed solvent.
- a system may be included.
- a fluorine-based solvent (C) can be used.
- what contains a fluorine-type solvent (C) can be used as a mixed solvent.
- fluorinated solvent / IPA 50/50 (w / w)) mixed solution
- fluorinated solvent / IPA 75/25 (w / w)) mixed solution
- fluorinated solvent / IPA 95/5 (w / w)) w)
- fluorinated solvent / butyl acetate 80/20
- fluorinated solvent / butyl acetate 67/33 mixed solvent
- fluorinated solvent (50/50) mixed solvent and the like fluorinated solvent / IPA (50/50 (w / w) mixed solution
- fluorinated solvent / IPA 75/25 (w / w) mixed solution
- fluorinated solvent / IPA 95/5 (w / w)) w)
- the fluorine-based solvent may be any of hydrocarbon compounds, alcohols, ethers, etc., as long as it has a fluorine atom in the molecule and the formed fluorine-containing polymer has good solubility. Any of aliphatic and aromatic may be used.
- chlorinated fluorinated hydrocarbons particularly, having 2 to 5 carbon atoms
- HCFC225 diichloropentafluoropropane
- HCFC141b diichlorofluoroethane
- CFC316 2, 3,3-tetrachlorohexafluorobutane
- Vertrel XF chemical formula C 5 H 2 F 10
- AC-6000 chemical name tridecafluorooctane
- hydrofluoroether is a solvent having low chemical erosion with respect to various materials, and is a particularly suitable solvent as a solvent for forming a coating on an electronic component that is strongly required to eliminate the adverse effects of the solvent. Further, hydrofluoroether is an ideal solvent having excellent performance such as quick drying, low environmental pollution, nonflammability, and low toxicity.
- hydrofluoroether a hydrofluoroether having a boiling point of 100 ° C. or less under atmospheric pressure is preferably used.
- hydrofluoroether is represented by the following general formula (6)
- x is a number from 1 to 6, and y is a number from 1 to 6.
- the compound shown by these is preferable.
- examples of such a hydrofluoroether include Novec (trademark) 7100 (chemical formula C 4 F 9 OCH 3 ) (boiling point 61 ° C.) manufactured by Sumitomo 3M Limited, and Novec (trademark) 7200 (chemical formula expressed by Sumitomo 3M Limited).
- C 4 F 9 OC 2 H 5 (boiling point 76 ° C.)
- Novec TM 7300 chemical formula C 6 F 13 OCH 3 ) (boiling point 98 ° C.) manufactured by Sumitomo 3M Limited can be used.
- the curable film-forming composition of the present invention is a composition used for forming the film of the present invention on a surface to be treated.
- the surface to be processed can be coated by forming the film of the present invention on the surface to be processed using the composition for forming a curable film of the present invention.
- the solid component in the composition is preferably about 0.01 to 10% by weight, more preferably about 1 to 6% by weight.
- the surface of the film obtained thereby has a static contact angle with water of 150 ° or more, and the n-HD has a static contact angle of 80 ° or more.
- the surface of the film obtained thereby has a static contact angle with water of 150 ° or more, and the n-HD static contact angle is 90 ° or more.
- the falling angle with respect to water is 10 ° or less and the falling angle with respect to n-HD is 30 ° or less. More preferably, the static contact angle with respect to water on the surface of the resulting coating is 150 ° or more, and the n-HD static The static contact angle is 120 ° or more, the falling angle with respect to water is 5 ° or less, and the falling angle with respect to n-HD is 20 ° or less. Is 150 ° or more, n-HD has a static contact angle of 150 ° or more, a tumbling angle with respect to water of 3 ° or less, and a tumbling angle with respect to n-HD of 5 ° or less. It is a thing. In addition, the value of the above-mentioned falling angle is an average value obtained by measuring three points with a contact angle meter Drop Master 701 or an equivalent thereof, with 20 ⁇ l of water and n-HD.
- the application target of the curable film-forming composition of the present invention is not particularly limited, and may be, for example, glass, resin (natural or synthetic resin, for example, a general plastic material, in a plate shape, a film, or other forms. May be a metal (aluminum, copper, iron, etc.) or ceramic (semiconductor, silicon, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather,
- the present invention can be applied to any appropriate material such as wood, ceramics, stone, and building materials.
- a film having liquid repellency can be formed on these treated surfaces.
- a film having good durability against at least one kind of stimulus selected from the group consisting of solvent immersion, immersion in water, wiping, abrasion, high temperature and high humidity and the like is formed.
- composition for forming a curable film of the present invention is not particularly limited.
- water / oil repellent protein / cell / microbe non-adhesive agent
- frost formation delay / anti-icing / snow-proofing agent
- fingerprint adhesion prevention Agents fingerprint recognizing agents, low friction agents and lubricants.
- the film of the present invention can be obtained by curing a curable component contained in the curable film forming composition on the surface to be treated.
- a curable component contained in the curable film forming composition
- at least one polymerizable compound can be used, and it can be cured by polymerizing the polymerizable compound.
- the method for applying the curable film-forming composition of the present invention to the surface to be treated is not particularly limited, and the curable film-forming composition of the present invention is applied to the object to be treated by brushing, spraying, spin coating, dispenser, etc. It is also possible to apply a contact method by the above method. Moreover, in order to make it easier to apply, if necessary, various primer treatments may be performed on the surface to be treated.
- the film of this invention can be manufactured by hardening a curable component.
- the curable film-forming composition of the present invention contains the compound (B-1) having a radical polymerizable group among the fine particles (A) and the polyfunctional crosslinkable compound (B) as fine particles (A ) And the compound (B-1) having a radical polymerizable group can be polymerized to produce the coating film of the present invention.
- the fine particles (A) and the compound (B-1) having a radical polymerizable group are (I) It can superpose
- the polymerization reaction can be performed in the presence or absence of a polymerization initiator.
- polymerization can also be performed using heat and electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, ⁇ rays, and the like.
- the polymerization method when polymerizing on the object to be processed without using a polymerization initiator is not particularly limited, and examples thereof include a method of polymerization using heat, electron beam, ⁇ -ray, and the like.
- the polyfunctional polymerizable compound (B) it is preferable to polymerize at least one kind of the polyfunctional polymerizable compound (B) on the article to be treated in the second stage or later. More preferably, at least one of the polyfunctional polymerizable compound (B) is preferably polymerized on the object to be treated in the final stage. Specifically, the polyfunctional polymerizable compound (B) is polymerized on the fine particles (A) or a polymer obtained by previously polymerizing the fine particles (A) and the compound having one polymerizable group in the molecule. it can.
- the polyfunctional polymerizable compound to be used is not particularly limited as long as the polymerization proceeds, but the polymerizable group is preferably a radical polymerizable group, and more preferably (meth) acrylate.
- the polyfunctional polymerizable compound is not particularly limited as long as the polymerization proceeds, but preferably has a fluorine atom as a constituent atom from the viewpoint of liquid repellency of the coating.
- the polymerization conditions such as the polymerization temperature and the polymerization time may be appropriately adjusted according to the type of monomer component, the amount used thereof, the type of polymerization initiator, the amount used, etc., but usually about 50 to 100 ° C.
- the polymerization reaction may be performed at a temperature for 4 to 10 hours.
- the film of the present invention can be produced by curing the curable component after bringing the composition for forming a curable film of the present invention into contact with an object to be treated.
- the curable film-forming composition of the present invention contains the compound (B-2) having an isocyanate group among the fine particles (A) and the polyfunctional crosslinkable compound (B) as the curable component, the fine particles (A)
- the coating of the present invention can be manufactured by preparing a solution in which (A) coexists with the compound (B-2) having an isocyanate group, and developing the solution on the object to be processed.
- the composition for forming a curable film of the present invention is cured using (A) and (B-2), it is preferable to apply heat, although not particularly limited.
- the temperature and time at this time are not particularly limited.
- the temperature is preferably about 30 ° C. to 300 ° C., more preferably about 40 ° C. to 270 ° C.
- the time is preferably 1 second to 2 hours, more preferably about 5 seconds to 1 hour 30. In any case, an appropriate time may be set as appropriate for the set temperature.
- the base material is acetone, isopropyl alcohol ( It is preferable to dry after washing with a solvent such as IPA) or hydrofluoroether or a mixed solvent thereof.
- IPA isopropyl alcohol
- hydrofluoroether or a mixed solvent thereof.
- the substrate is made of silicon or metal, chemical cleaning such as acid (hydrochloric acid, nitric acid, hydrogen fluoride, etc.), UV ozone, sandblasting, glass beads, plasma, etc. Removing the oxide film formed on the surface by physical cleaning is also useful for improving durability. Even more preferably, the wear resistance is further improved by surface-modifying a compound having a site that chemically adsorbs to the washed substrate and can also chemically react with the curable film-forming composition in the structure. .
- C 6 F 13 CH 2 CH 2 OCOC (CH 3 ) CH 2 [hereinafter sometimes abbreviated as Rf (C6) methacrylate] 25.46 g, having a radical reactive group on the surface
- 12.70 g of silica fine particles having an average primary particle diameter of 12 nm and 663.49 g of perfluorobutyl ethyl ether were charged, purged with nitrogen, and heated to 70 ° C.
- the photosensitive solution was treated on a silicon substrate by a dip method. Then, the treated acrylic base material is put into a metal box that can flow gas, and the inside of the box is flown with nitrogen at a flow rate of 10 L / min for 3 minutes, and then the whole box is put into a belt conveyor type UV irradiation device. UV of 1,800 mJ / cm 2 was irradiated. The content of fluorine atoms in the prepared coating is 41.5 wt% with respect to all coating components.
- the photosensitive solution was treated on a silicon substrate by a dip method. Thereafter, heat treatment was performed at 130 ° C. for 1 hour.
- the content of fluorine atoms in the prepared coating is 35.1 wt% with respect to all coating components.
- HEMA hydroxyethyl methacrylate
- a silicon substrate was immersed in the solution and air-dried at room temperature for 30 minutes to produce a coating.
- the content of fluorine atoms in the prepared coating is 57.2 wt% with respect to all coating components.
- Test Examples 1-14 The test pieces obtained in Examples 1 to 11 and Comparative Examples 1 to 3 were measured for contact angles with water and n-HD. The contact angle measurement and apparatus were in accordance with the method described in the text.
- Test Examples 15 to 42 The test pieces obtained in Examples 1 to 11 and Comparative Examples 1 to 3 were obtained by the following method using the following information.
- Ra Arithmetic average roughness Ra of 702.801 ⁇ m on one side was calculated using VK-9710 manufactured by KEYENCE CORPORATION. The above Ra was calculated 5 times at random from the observation range of 526.929 ⁇ m ⁇ 702.801 ⁇ m, and the average was obtained. The results are shown in Table 2.
- Test Examples 43 to 54 Rubbing test Examples 1 to 11 and each test piece obtained in Comparative Example 2 were measured for water contact angle to obtain an initial contact angle, and then a rubbing tester (rubbing tester “Ibrasion Tester 151E manufactured by Imoto Seisakusho” A triple film ”)" holder (area contacting the sample: 1 cm 2 ) is attached with PET film (trade name: U-46, manufactured by Toray), and the surface is wiped a predetermined number of times with a load of 100 g. The water contact angle was measured and the abrasion resistance against wiping was evaluated.
- a rubbing tester rubbing tester “Ibrasion Tester 151E manufactured by Imoto Seisakusho” A triple film ”
- PET film trade name: U-46, manufactured by Toray
- the wear resistance performance here is the number of wears that can maintain a super water-repellent state (the average value of the static contact angle of five times is 150 ° or more, or 150 ° or more when the average deviation is 140 ° or more and the standard deviation is combined). Defined. Table 3 shows the results of the rubbing test.
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Abstract
Description
被膜であって、
フッ素原子の含有量が、1~60wt%であり、
平均表面粗さRaが、0.5~20μmであり、
比表面積比が、1.7~5であり、
水の接触角が、150°以上であり、
n-ヘキサデカンの接触角が、80°以上であり、かつ
PETフィルムを荷重100g/cm2で100回塗擦した後の水の接触角が、150°以上である表面を有する、被膜。
項2.
フッ素化合物を含む、硬化性被膜形成用組成物であって、
硬化後の被膜が、
平均表面粗さRaが、0.5~20μmであり、
比表面積比が、1.7~5であり、
水の接触角が、150°以上であり、
n-ヘキサデカンの接触角が、80°以上であり、かつ
PETフィルムを荷重100g/cm2で100回塗擦した後の水の接触角が、150°以上である表面を有する、
硬化性被膜形成用組成物。
項3.
さらに、フッ素系溶剤を含む、項2に記載の硬化性被膜形成用組成物。
本発明の被膜は、
フッ素原子の含有量が、1~60wt%であり、
平均表面粗さRaが、0.5~20μmであり、
比表面積比が、1.7~5であり、
水の接触角が、150°以上であり、
n-ヘキサデカンの接触角が、80°以上であり、かつ
PETフィルムを荷重100g/cm2で100回塗擦した後の水の接触角が、150°以上である表面を有する、
被膜である。
本発明の硬化性被膜形成用組成物は、フッ素化合物を含み、硬化後の被膜が、上記特性を有するものであればよく、特に限定されない。
微粒子としては、特に限定されず、例えば、シリカ微粒子、金属酸化物微粒子等の無機微粒子のほか、カーボンブラック、フラーレン及びカーボンナノチューブ等の有機微粒子を幅広く用いることができる。
本発明の硬化性被膜形成用組成物が、分子内に2つ以上の架橋性基を含む化合物(多官能架橋性化合物)を有していることにより、硬化後の被膜に優れた耐摩耗性が付与されると考えられる。
上記一般式(1)において、炭化水素は、環状又は非環状のいずれであってもよく、また直鎖状又は分岐状のいずれであってもよい。特に限定されないが、上記一般式(1)において、炭化水素は、好ましくは炭素数1~10であり、より好ましくは炭素数1~6であり、さらに好ましくは炭素数1~2である。
R1は、少なくとも一つの炭素原子がヘテロ原子で置換されていてもよく、少なくとも一つの水素原子がハロゲン原子で置換されていてもよく、炭素-炭素間不飽和結合を有していてもよい、分岐状又は環状の3価以上の炭化水素基又はカルボニル基であり、
Z3は、少なくとも一つの末端に重合性基を有する、少なくとも一つの炭素原子がヘテロ原子で置換されていてもよく、少なくとも一つの水素原子がハロゲン原子で置換されていてもよく、炭素-炭素間不飽和結合を有していてもよい、直鎖状又は分岐状の1価の炭化水素基又はカルボニル基であり、
kは、1以上の整数であり、かつ
lは2以上の整数である。)
Rf1は、パーフルオロアルキル基、パーフルオロアルケニル基若しくはパーフルオロアルキニル基、又はパーフルオロポリエーテル基(PFPEと表記することがある。)でありうる。
Rf2は、少なくとも一つの炭素原子がヘテロ原子で置換されていてもよく、炭素-炭素間不飽和結合を有していてもよい、分岐状又は環状の2価以上のパーフルオロカーボン基であり、かつ
mは2以上の整数である。)
Rf2は、パーフルオロアルキル基、パーフルオロアルケニル基若しくはパーフルオロアルキニル基、又はパーフルオロポリエーテル基でありうる。
R2は、少なくとも一つの炭素原子がヘテロ原子で置換されていてもよく、少なくとも一つの水素原子がハロゲン原子で置換されていてもよく、少なくとも一つの炭素原子がヘテロ原子で置換されていてもよく、炭素-炭素間不飽和結合を有していてもよい、分岐状又は環状の2価以上の炭化水素基又はカルボニル基であり、かつ
nは2以上の整数である。)
R2は、好ましくは、炭素数1~20であり、より好ましくは炭素数2~15であり、さらに好ましくは炭素数3~10である。
R3は、少なくとも一つの炭素原子がヘテロ原子で置換されていてもよく、少なくとも一つの水素原子がハロゲン原子で置換されていてもよく、少なくとも一つの炭素原子がヘテロ原子で置換されていてもよく、炭素-炭素間不飽和結合を有していてもよい、分岐状又は環状の2価以上の炭化水素基又はカルボニル基であり、かつ
oは2以上の整数である。)
R3は、好ましくは、炭素数1~20であり、より好ましくは炭素数2~15であり、さらに好ましくは炭素数3~10である。
特に限定されないが、本発明の硬化性被膜形成用組成物の好ましい態様として、以下が挙げられる。
(A)少なくとも一種の含フッ素修飾化合物が表面に結合した微粒子;及び
(B)分子内に2つ以上の架橋性基を含む化合物
を含有し、
硬化後の被膜が、
平均表面粗さRaが、0.5~20μmであり、かつ
比表面積比が、1.7~5である表面を有する、
硬化性被膜形成用組成物。
(A)少なくとも一種の含フッ素修飾化合物が表面に結合した微粒子;及び
(B)分子内に2つ以上の重合性基を含む化合物
を含有し、
硬化後の被膜が、
平均表面粗さRaが、0.5~20μmであり、かつ
比表面積比が、1.7~5であり、
水の接触角が、150°以上であり、
n-ヘキサデカンの接触角が、80°以上である表面を有する、
硬化性被膜形成用組成物。
2.4.1 重合開始剤
本発明の硬化性被膜形成用組成物は、必要に応じてさらに、重合開始剤を含んでいてもよい。特に(B-1)を多官能架橋性化合物として用いる際には、使用することが好ましい。特に限定されないが、例えば、350nm以下の波長領域の電磁波、つまり紫外光線、電子線、X線、γ線等が照射されることによって初めてラジカルやカチオン等を発生し、含フッ素重合体の炭素-炭素二重結合の硬化(架橋反応)を開始させる触媒として働くものであり、通常、紫外光線でラジカルやカチオンを発生させるもの、特にラジカルを発生するものを使用することが好ましい。例えば次のものが例示できる。
本発明の硬化性被膜形成用組成物は、必要に応じてさらに、水酸基とイソシアネート基に対する触媒活性剤を含んでいてもよい。特に(B-2)を多官能架橋性化合物として用いる際には、使用することが好ましい。
特に限定されないが、有機チタン化合物であるチタンテトラ-2-エチルヘキソキシド、チタンジイソブロボキシビス(エチルアセトアセテート)などや、有機ジルコニア化合物であるジルコニウムテトラアセチルアセトネート、ジルコニウムジブトキシビス(エチルアセトアセテート)を使用できる。市販の化合物としては、例えば、オルガチックスTA-30(マツモトファインケミカル(株)製)、TC-750(マツモトファインケミカル(株)製)、ZC-580(マツモトファインケミカル(株)製)、ZC-700(マツモトファインケミカル(株)製)などが挙げられる。
本発明の硬化性被膜形成用組成物は、上記成分(A)及び(B)に加えて、さらに、重合開始剤をはじめとする各成分を均一に溶解させることができる単一溶媒もしくは混合溶媒系を含んでいてもよい。単一溶媒としては、例えば、フッ素系溶剤(C)等が使用できる。また、混合溶媒としては、フッ素系溶剤(C)を含むものが使用できる。例えば、フッ素系溶剤/IPA(50/50(w/w))混合溶液、フッ素系溶剤/IPA(75/25(w/w))混合溶液、フッ素系溶剤/IPA(95/5(w/w))混合溶液、フッ素系溶剤/酢酸ブチル(80/20)混合溶剤、フッ素系溶剤/酢酸ブチル(67/33)混合溶剤、フッ素系溶剤(50/50)混合溶剤などが挙げられる。
で示される化合物が好ましい。この様なハイドロフルオロエーテルとしては、例えば、住友スリーエム株式会社製のNovec(商標)7100(化学式C4F9OCH3)(沸点61℃),住友スリーエム株式会社製のNovec(商標)7200(化学式C4F9OC2H5)(沸点76℃),住友スリーエム株式会社製のNovec(商標)7300(化学式C6F13OCH3)(沸点98℃)などを用いることができる。
本発明の硬化性被膜形成用組成物は、本発明の被膜を被処理面で形成するために用いられる組成物である。本発明の硬化性被膜形成用組成物を用いて、被処理面上で本発明の被膜を形成することにより、被処理面をコーティングすることができる。
本発明の硬化性被膜形成用組成物による被膜の製造方法について説明する。
(i)被処理面上で同時に重合するか、又は
(ii)少なくとも二段階に分けて逐次的に重合する
ことができる。
[[Rf(C6)メタクリレート/微粒子]共重合体溶液の調製]
枝付試験管に、C6F13CH2CH2OCOC(CH3)=CH2[以下、Rf(C6)メタクリレートと略することがある]25.46 g、ラジカル反応性基を表面に有し平均一次粒子径が12 nmのシリカ微粒子シリカ微粒子12.70 g、及びパーフルオロブチルエチルエーテル663.49gを仕込み、窒素バージし、70℃に加熱した。これにAIBN 1.26516 gを投入し、6時間反応した。重合後、固形分濃度を算出した。
バイアルにトリアクリロイルヘプタデカフルオロノネニルペンタエリスリトール(以下、TAHFNHAと略すことがある)0.3256 g、アルキルフェノン系光重合開始剤0.0413 g、IPA 1.0949 g、パーフルオロブチルエチルエーテル7.4783 gを投入し、超音波洗浄機で超音波を照射した後、上記、固形分4.19%の共重合体溶液11.8650 gを投入し、超音波洗浄機で超音波を照射し、感光性溶液とした。
上記、感光性溶液をシリコン基材にディップ法によって処理をした。その後、気体をフロー可能な金属製ボックスに処理したアクリル基材を投入し、10 L/minの流量で3分間ボックス内を窒素フローし、その後、ベルトコンベアー式のUV照射装置にボックスごと投入し1,800 mJ/cm2のUVを照射した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して41.5wt%である。
(感光性溶液の調製)の項目のTAHFNHAを0.4157 g、アルキルフェノン系光重合開始剤を0.0404 g、IPAを1.0675 g、パーフルオロブチルエチルエーテルを9.5001 g、共重合体溶液を9.6917 gとした以外は実施例1と同じ方法で調製した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して42.3wt%である。
(感光性溶液の調製)の項目のTAHFNHAを0.4817 g、アルキルフェノン系光重合開始剤を0.0402 g、IPAを1.1468 g、パーフルオロブチルエチルエーテルを11.5713 g、共重合体溶液を8.0478 gとした以外は実施例1と同じ方法で調製した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して43.3wt%である。
(感光性溶液の調製)の項目のTAHFNHAを0.5889 g、アルキルフェノン系光重合開始剤を0.0429 g、IPAを1.0454 g、パーフルオロブチルエチルエーテルを13.4581 g、共重合体溶液を5.8905 gとした以外は実施例1と同じ方法で調製した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して44.1wt%である。
(感光性溶液の調製)の項目のTAHFNHAの代わりにトリメチロールプロパントリアクリレート(以下、TMPTAと略すことがある。)を0.3213 g、アルキルフェノン系光重合開始剤を0.0415 g、IPAを1.0969 g、パーフルオロブチルエチルエーテルを7.3269 g、共重合体溶液を12.0015 gとした以外は実施例1と同じ方法で調製した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して22.9wt%である。
(感光性溶液の調製)の項目のTAHFNHAの代わりにTMPTAを0.4015 g、アルキルフェノン系光重合開始剤を0.0403 g、IPAを1.0668 g、パーフルオロブチルエチルエーテルを8.8769 g、共重合体溶液を9.7518 gとした以外は実施例1と同じ方法で調製した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して19.1wt%である。
(感光性溶液の調製)の項目のTAHFNHAの代わりにTMPTAを0.4858 g、アルキルフェノン系光重合開始剤を0.0427 g、IPAを1.1095 g、パーフルオロブチルエチルエーテルを11.6517 g、共重合体溶液を7.8134 gとした以外は実施例1と同じ方法で調製した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して15.2wt%である。
[[Rf(C6)メタクリレート/微粒子]共重合体溶液の調製]
実施例1と同様にして作製した。
バイアルにTC-750 0.025 g、スミジュールN3300 0.483 g、酢酸ブチル 9.730 gを投入し、超音波洗浄機で超音波を照射した後、上記、固形分5.19%の共重合体溶液14.390 g、パーフルオロブチルエチルエーテル5.754 gを投入し、超音波洗浄機で超音波を照射し、感光性溶液とした。
上記、感光性溶液をシリコン基材にディップ法によって処理をした。その後、130℃にて1時間熱処理を施した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して35.1wt%である。
(溶液の調製)の項目のTC-750を0.030g、スミジュールN3300を0.599g、酢酸ブチルを9.760g、共重合体溶液を11.938g、パーフルオロブチルエチルエーテルを8.055gとした以外は実施例8と同様である。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して29.4wt%である。
(溶液の調製)の項目のTC-750を0.037g、スミジュールN3300を0.721g、酢酸ブチルを9.583 g、共重合体溶液を9.278 g、パーフルオロブチルエチルエーテルを11.879 gとした以外は実施例8と同様である。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して15.5wt%である。
[[Rf(C6)メタクリレート/微粒子]共重合体溶液の調製]
枝付試験管に、Rf(C6)メタクリレート7.98g、ヒドロキシエチルメタクリレート(HEMAと略すことがある。)2.07 g、ラジカル反応性基を表面に有し平均一次粒子径が12 nmのシリカ微粒子4.95 g、及びイソプロピルアルコール34.97g、パーフルオロブチルエチルエーテル166.15gを仕込み、窒素バージし、70℃に加熱した。これにAIBN 0.62000 gを投入し、6時間反応した。重合後、固形分濃度を算出した。その他は、(溶液の調製)の項目のTC-750を0.031g、スミジュールN3300を0.589g、酢酸ブチルを9.789g、固形分4.89%の共重合体溶液を11.768g、パーフルオロブチルエチルエーテルを8.140gとした以外は実施例8と同様である。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して15.1wt%である。
(感光性溶液の調製)の項目のTAHFNHAの代わりにTMPTAを0.5537 g、アルキルフェノン系光重合開始剤を0.0409 g、IPAを1.1247 g、パーフルオロブチルエチルエーテルを13.5506 g、共重合体溶液を5.8534 gとした以外は実施例1と同じ方法で調製した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して11.4wt%である。
[Rf(C6)メタクリレート/微粒子]共重合体溶液をスクリュー管に7.47 g、IPAを9.92 g投入し超音波を照射し、[Rf(C6)メタクリレート/微粒子]共重合体を分散させた。その後、その溶液にシリコン基材を浸漬させ、被膜を作製した。作製した被膜のフッ素原子の含有量はすべての被膜構成成分に対して38.1wt%である。
(ポリマーの調製)
枝付試験管に、Rf(C6)メタクリレート25.0 g、パーフルオロブチルエチルエーテル75.0 gを仕込み、10分間窒素バージし、70℃に加熱した。これにAIBN 0.136 gを投入し、6時間反応した。重合後固形分濃度を算出した。
バイアルに、上記、重合溶液0.50 g、パーフルオロブチルエチルエーテル115 gを投入した。
実施例1~11および比較例1~3で得られた試験片について、水とn-HDに対する接触角測定を行った。接触角の測定および装置に関しては本文中に記載の方法に準じた。
実施例1~11および比較例1~3で得られた試験片について下記の情報を記載の方法を用いて求めた。
KEYENCE CORPORATION社製のVK-9710を用いて351.4μm×351.5 μm四方の真の平滑平面の表面積に対しての作製した表面積の比率(比表面積比)を算出した。
KEYENCE CORPORATION社製のVK-9710を用いて一辺702.801μmの算術平均粗さRaを算出した。526.929μm×702.801μmの観測範囲よりランダムで5回上記のRaを算出しその平均を求めた。
その結果を表2に示す。
ラビング試験
実施例1~11また比較例2で得られた各試験片について、対水接触角を測定して初期接触角を求めた後、ラビングテスター(井元製作所製ラビングテスター「耐摩耗試験機151E 3連仕様」)のホルダー(試料に接する面積:1 cm2)にPETフィルム(商標名:U-46、東レ製)を装着し、荷重100gにて所定回数、表面の拭き取りを行い、その後対水接触角を測定し、拭き取りに対する耐摩耗性を評価した。ここでの耐摩耗性能は超撥水状態(5回平均の静的接触角の値が150°以上、もしくは、平均140°以上でその標準偏差をあわせると150°以上)を維持できる摩耗回数と定義した。表3にラビング試験の結果を示す。
Claims (3)
- 被膜であって、
フッ素の含有量が、1~60wt%であり、
平均表面粗さRaが、0.5~20μmであり、
比表面積比が、1.7~5であり、
水の接触角が、150°以上であり、
n-ヘキサデカンの接触角が、80°以上であり、かつ
PETフィルムを荷重100gで100回塗擦した後の水の接触角が、150°以上である表面を有する、被膜。 - フッ素化合物を含む、硬化性被膜形成用組成物であって、
硬化後の被膜が、
平均表面粗さRaが、0.5~20μmであり、
比表面積比が、1.7~5であり、
水の接触角が150°以上、
n-ヘキサデカンの接触角が80°以上、かつ
PETフィルムを荷重100gで100回塗擦した際、水の接触角が150°以上である表面を有する、
硬化性被膜形成用組成物。 - さらに、フッ素系溶剤を含む、請求項2に記載の硬化性被膜形成用組成物。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020246607A1 (ja) * | 2019-06-05 | 2020-12-10 | ダイキン工業株式会社 | 組成物 |
WO2021090812A1 (ja) | 2019-11-05 | 2021-05-14 | ダイキン工業株式会社 | アンテナカバー用基材 |
WO2021090814A1 (ja) | 2019-11-05 | 2021-05-14 | ダイキン工業株式会社 | 膜及びこれで表面が被覆された基材 |
JP2021080452A (ja) * | 2019-11-18 | 2021-05-27 | ダイキン工業株式会社 | 着雪防止被膜形成用組成物及び着雪防止被膜 |
EP3737587A4 (en) * | 2018-01-08 | 2022-02-23 | 3M Innovative Properties Company | PROTECTIVE FILM AND METHOD OF USE |
KR20220097944A (ko) | 2019-11-05 | 2022-07-08 | 다이킨 고교 가부시키가이샤 | 피막 형성용 조성물 및 피막 그리고 약액 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08211202A (ja) * | 1995-02-07 | 1996-08-20 | Hitachi Ltd | 撥水撥油性超微粒子を有する光透過板およびその製造方法 |
JP2005281370A (ja) * | 2004-03-29 | 2005-10-13 | Toyo Ink Mfg Co Ltd | 防汚性活性エネルギー線硬化型組成物及び被覆物 |
WO2014057712A1 (ja) * | 2012-10-13 | 2014-04-17 | 東洋アルミニウム株式会社 | 撥水・撥油性塗膜及びその塗膜を含む物品 |
JP2014213591A (ja) * | 2013-04-30 | 2014-11-17 | 日揮触媒化成株式会社 | 撥水性透明被膜付基材およびその製造方法 |
WO2016056663A1 (ja) * | 2014-10-10 | 2016-04-14 | ダイキン工業株式会社 | 被膜、それによるコーティング方法及びそれによりコーティングされてなる物品 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3619724B2 (ja) | 1999-11-09 | 2005-02-16 | 三菱レイヨン株式会社 | 透明な超撥水性表面を有する成形物およびその製造方法 |
JP4384898B2 (ja) * | 2003-11-28 | 2009-12-16 | 日油株式会社 | 撥水撥油性被膜の製造方法 |
CN1942545B (zh) * | 2004-04-12 | 2010-12-01 | 大金工业株式会社 | 防污涂料组合物 |
US20090018249A1 (en) * | 2006-01-30 | 2009-01-15 | Subbareddy Kanagasabapathy | Hydrophobic self-cleaning coating compositions |
JP5433926B2 (ja) | 2006-04-18 | 2014-03-05 | Jsr株式会社 | 硬化性樹脂組成物及び反射防止膜 |
JP5114355B2 (ja) | 2008-10-08 | 2013-01-09 | 株式会社Snt | 撥水・撥油性コーティング物品およびその製造 |
CN102216361B (zh) * | 2008-11-14 | 2014-01-29 | 纳幕尔杜邦公司 | 含氟聚合物组合物和处理的基底 |
US20100167965A1 (en) * | 2008-12-26 | 2010-07-01 | Bp Corporation North America Inc. | Amphiphobic Proppant |
CN101824273B (zh) * | 2010-03-31 | 2013-01-09 | 中科院广州化学有限公司 | 一种含氟聚合物/无机纳米杂化粒子改性的紫外光固化涂料及其制备方法 |
DE102012004278B4 (de) * | 2011-03-31 | 2022-07-07 | Few Chemicals Gmbh | Beschichtungszusammensetzung für abriebbeständige und antiadhäsive Oberflächenbeschichtungen, deren Verwendung sowie beschichtete Oberfläche |
CA2925495A1 (en) * | 2013-09-26 | 2015-04-02 | Ross Technology Corporation | Flexible superhydrophobic and/or oleophobic polyurethane coatings |
US10338276B2 (en) | 2014-09-12 | 2019-07-02 | Fujifilm Corporation | Antireflective film, polarizing plate, cover glass, image display device, and method of manufacturing antireflective film |
JP6343540B2 (ja) | 2014-09-30 | 2018-06-13 | 富士フイルム株式会社 | 反射防止フィルム、偏光板、カバーガラス、及び画像表示装置、並びに反射防止フィルムの製造方法 |
CN104449357B (zh) * | 2014-11-26 | 2017-01-04 | 浙江大学 | 一种透明超疏水涂层材料及其制备透明超疏水涂层的方法 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08211202A (ja) * | 1995-02-07 | 1996-08-20 | Hitachi Ltd | 撥水撥油性超微粒子を有する光透過板およびその製造方法 |
JP2005281370A (ja) * | 2004-03-29 | 2005-10-13 | Toyo Ink Mfg Co Ltd | 防汚性活性エネルギー線硬化型組成物及び被覆物 |
WO2014057712A1 (ja) * | 2012-10-13 | 2014-04-17 | 東洋アルミニウム株式会社 | 撥水・撥油性塗膜及びその塗膜を含む物品 |
JP2014213591A (ja) * | 2013-04-30 | 2014-11-17 | 日揮触媒化成株式会社 | 撥水性透明被膜付基材およびその製造方法 |
WO2016056663A1 (ja) * | 2014-10-10 | 2016-04-14 | ダイキン工業株式会社 | 被膜、それによるコーティング方法及びそれによりコーティングされてなる物品 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3737587A4 (en) * | 2018-01-08 | 2022-02-23 | 3M Innovative Properties Company | PROTECTIVE FILM AND METHOD OF USE |
WO2020246607A1 (ja) * | 2019-06-05 | 2020-12-10 | ダイキン工業株式会社 | 組成物 |
WO2021090812A1 (ja) | 2019-11-05 | 2021-05-14 | ダイキン工業株式会社 | アンテナカバー用基材 |
WO2021090814A1 (ja) | 2019-11-05 | 2021-05-14 | ダイキン工業株式会社 | 膜及びこれで表面が被覆された基材 |
KR20220097944A (ko) | 2019-11-05 | 2022-07-08 | 다이킨 고교 가부시키가이샤 | 피막 형성용 조성물 및 피막 그리고 약액 |
JP2021080452A (ja) * | 2019-11-18 | 2021-05-27 | ダイキン工業株式会社 | 着雪防止被膜形成用組成物及び着雪防止被膜 |
JP7235988B2 (ja) | 2019-11-18 | 2023-03-09 | ダイキン工業株式会社 | 着雪防止被膜形成用組成物及び着雪防止被膜 |
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US11578232B2 (en) | 2023-02-14 |
CN109072008B (zh) | 2021-07-23 |
JP7360051B2 (ja) | 2023-10-12 |
EP3444308A1 (en) | 2019-02-20 |
JPWO2017179678A1 (ja) | 2019-02-21 |
EP3444308A4 (en) | 2019-12-25 |
CN109072008A (zh) | 2018-12-21 |
CN113337171A (zh) | 2021-09-03 |
JP6717373B2 (ja) | 2020-07-01 |
US20200347258A1 (en) | 2020-11-05 |
JP2023011062A (ja) | 2023-01-23 |
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