WO2023058621A1 - Coating-forming composition, coating, and chemical liquid - Google Patents

Coating-forming composition, coating, and chemical liquid Download PDF

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Publication number
WO2023058621A1
WO2023058621A1 PCT/JP2022/037026 JP2022037026W WO2023058621A1 WO 2023058621 A1 WO2023058621 A1 WO 2023058621A1 JP 2022037026 W JP2022037026 W JP 2022037026W WO 2023058621 A1 WO2023058621 A1 WO 2023058621A1
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fine particles
inorganic fine
mass
group
parts
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PCT/JP2022/037026
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French (fr)
Japanese (ja)
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僚 井上
みちる 賀川
央基 山口
浩治 久保田
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ダイキン工業株式会社
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Publication of WO2023058621A1 publication Critical patent/WO2023058621A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D201/00Coating compositions based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular

Definitions

  • the present disclosure relates to a film-forming composition, a film, and a chemical solution.
  • Patent Document 1 discloses that a super water-repellent film having both super water repellency and abrasion resistance can be formed by using fine particles having a polymerizable group and a compound having two or more polymerizable groups in the molecule.
  • Patent Document 2 discloses a technique for forming a super water-repellent film that is a film containing fluorine atoms and has both super water repellency and abrasion resistance by appropriately controlling various properties of the film. .
  • Patent Document 3 discloses a film-forming composition containing a fluorine-based copolymer containing a fluoroolefin, a perfluoroalkyl group-containing monomer, and a hydroxyl group-containing unsaturated monomer, and silica fine powder. It is said to be capable of forming a film having excellent water and oil repellency, releasability, releasability, and storage stability.
  • An object of the present disclosure is to provide a film-forming composition, a film, and a chemical solution capable of forming a film having excellent water repellency and excellent abrasion resistance.
  • Item 1 including inorganic fine particles, a polymerizable component, and a water-repellent component
  • the inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 ⁇ m or less,
  • the content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component
  • the content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
  • X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, 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 (with the proviso that , R 1 is an alkyl group having 1 to 4 carbon atoms,
  • Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.).
  • a film-forming composition which is a polymer.
  • the content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
  • R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 Item 2.
  • Item 3 The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component.
  • Item 3. The film-forming composition according to Item 1 or 2.
  • Item 4 4. The film-forming composition according to any one of Items 1 to 3, wherein the polymerizable component is a polymer having a crosslinkable functional group and a curing agent.
  • Item 5 A film comprising a cured product of the film-forming composition according to any one of Items 1 to 4.
  • Item 6 including inorganic fine particles, a binder component, and a water-repellent component
  • the inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 ⁇ m or less,
  • the content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component
  • the content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component
  • the total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder
  • X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, 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 (with the proviso that , R 1 is an alkyl group having 1 to 4 carbon atoms,
  • Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.).
  • the content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
  • R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000
  • the content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component.
  • the inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 ⁇ m or less,
  • the contact angle of water is 150° or more
  • Item 10 The coating according to any one of claims 5 to 9, wherein the snow accretion start time measured by the following snow accretion test is 5 minutes or longer.
  • ⁇ Snow accretion test> A coating is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the coating is subjected to a wind speed of 10 m / sec and a collision amount of 110 kg /. Pre-made artificial snow is blown under the condition of m 2 /h. This blowing causes the artificial snow to impinge on the covering surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. Measured as the start time (no snow accretion time).
  • Item 11 A chemical solution comprising the film-forming composition according to any one of Items 1 to 4.
  • a film having excellent water repellency and excellent abrasion resistance can be formed.
  • the present inventors have conducted extensive research with the aim of forming a film that has excellent water repellency and excellent abrasion resistance.
  • abrasion resistance can be improved while maintaining high water repellency. It has been found that an improved coating can be formed, and the above objects can be achieved. In addition, we have found that such a coating can also have excellent anti-snow accretion performance.
  • the numerical range indicated using “-" indicates the range including the numerical values before and after "-" as the minimum and maximum values, respectively.
  • the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step.
  • the upper and lower limits of the numerical ranges may be replaced with values shown in Examples or values that can be uniquely derived from Examples.
  • the film-forming composition of the present disclosure contains at least inorganic fine particles, a polymerizable component, and a water-repellent component. First, each of these components will be described in detail.
  • the inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less and second inorganic fine particles having an average particle size of 500 nm or more and 5 ⁇ m or less.
  • first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less
  • second inorganic fine particles having an average particle size of 500 nm or more and 5 ⁇ m or less.
  • the film-forming composition of the present disclosure contains inorganic fine particles, the strength of the film is improved, and the second inorganic fine particles prevent the first inorganic fine particles from sliding down during abrasion, so the abrasion resistance of the film is improved. improves.
  • the average particle size of the first inorganic fine particles can be measured by the following method. First, the volatile components of the film-forming composition are removed by heat treatment (300° C., 3 hours). The microparticles thus obtained are directly observed with a scanning electron microscope, and 200 microparticles in the photographed image are selected. However, in this selection, fine particles having an equivalent circle diameter of 450 nm or more should not be selected. The average value of the equivalent circle diameters of the selected 200 fine particles is calculated, and this value is taken as the average particle size of the first inorganic fine particles in the film-forming composition.
  • the average particle size of the second inorganic fine particles can be measured by the following method. First, the volatile components of the film-forming composition are removed by heat treatment (300° C., 3 hours). The microparticles thus obtained are directly observed with a scanning electron microscope, and 200 microparticles in the photographed image are selected. However, in this selection, fine particles having an equivalent circle diameter of 450 nm or more are selected. The average value of the equivalent circle diameters of the selected 200 fine particles is calculated, and this value is taken as the average particle size of the first inorganic fine particles in the film-forming composition.
  • the average particle diameter of the first inorganic fine particles When the average particle diameter of the first inorganic fine particles is less than 1 nm, aggregation tends to occur, and the water repellency and abrasion resistance of the coating of the coating composition tend to decrease. In addition, when the average particle diameter of the first inorganic fine particles exceeds 100 nm, the difference between the average particle diameter of the second inorganic fine particles and the average particle diameter of the second inorganic fine particles becomes small, and the effect of using different average particle diameters together cannot be sufficiently obtained. As a result, it becomes difficult to improve the abrasion resistance of the film of the film-forming composition.
  • the average particle size of the first inorganic fine particles is preferably 2 nm or more, more preferably 3 nm or more, even more preferably 4 nm or more, and particularly preferably 5 nm or more.
  • the average particle size of the first inorganic fine particles is preferably 80 nm or less, more preferably 60 nm or less, even more preferably 50 nm or less, and particularly preferably 30 nm or less.
  • the average particle diameter of the second inorganic fine particles is less than 500 nm, the difference from the average particle diameter of the first inorganic fine particles becomes small, and the effect of using different average particle diameters together cannot be sufficiently obtained. As a result, it becomes difficult to improve the abrasion resistance of the film of the film-forming composition, and the anti-snow accretion performance is also deteriorated. If the average particle diameter of the second inorganic fine particles exceeds 5 ⁇ m, high water repellency cannot be obtained, and the particles tend to fall off the coating, resulting in poor abrasion resistance of the coating of the coating composition. difficult to improve.
  • the average particle diameter of the second inorganic fine particles is preferably 800 nm or more, more preferably 1 ⁇ m or more, even more preferably 1.5 ⁇ m or more, and particularly preferably 2 ⁇ m or more.
  • the average particle size of the second inorganic fine particles is preferably 4.5 ⁇ m or less, more preferably 4 ⁇ m or less, still more preferably 3.5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the types of the first inorganic fine particles and the second inorganic fine particles are not particularly limited as long as they satisfy the aforementioned average particle diameter, and for example, a wide range of known metal oxide fine particles can be exemplified.
  • Specific examples of metal oxides include silica, alumina, titanium oxide, zirconia, and the like, and the first inorganic fine particles and the second inorganic fine particles are silica in that the hardness and water resistance of the coating are likely to increase.
  • first inorganic fine particles and the second inorganic fine particles may be the same or different, preferably the first inorganic fine particles and the second inorganic fine particles are the same, more preferably , both the first inorganic fine particles and the second inorganic fine particles are silica.
  • the specific surface areas of the first inorganic fine particles and the second inorganic fine particles are not particularly limited.
  • the specific surface area is preferably 30 to 700 m 2 /g, more preferably 80 to 330 m 2 in terms of easily improving the hardness of the obtained coating. /g is more preferred.
  • the specific surface area of the fine particles means a value measured by the BET method (so-called BET specific surface area).
  • the surfaces of the first inorganic fine particles and the second inorganic fine particles may be hydrophilic or hydrophobic.
  • the first inorganic fine particles and the second inorganic fine particles may be a mixture of hydrophilic and hydrophobic properties.
  • the first inorganic fine particles and the second inorganic fine particles may be treated with a surface treatment agent to control wettability.
  • the first inorganic fine particles and the second inorganic fine particles preferably do not have a radically polymerizable reactive group (for example, a polymerizable double bond such as an acryloyl group) on the surface, that is, the first inorganic fine particles And it is preferable that the polymer is not covalently bonded to the surface of the second inorganic fine particles.
  • the wear resistance of the coating is improved, and particularly the snow accretion prevention performance is likely to be enhanced.
  • the shape of the first inorganic fine particles and the second inorganic fine particles is also not particularly limited, and examples thereof include spherical, ellipsoidal and the like, and may be amorphous particles such as irregular shaped particles.
  • the first inorganic fine particles and the second inorganic fine particles can also form aggregates. Aggregates may be spherical or non-spherical, and may be chain-like.
  • the inorganic fine particles contained in the film-forming composition of the present disclosure can contain 80% by mass or more of the first inorganic fine particles and the second inorganic fine particles, preferably 90% by mass or more, and more preferably 95% by mass or more. , more preferably 99% by mass or more.
  • the inorganic fine particles contained in the film-forming composition of the present disclosure may be only the first inorganic fine particles and the second inorganic fine particles, and particularly the first inorganic fine particles and the second inorganic fine particles. preferable.
  • the content ratio of both the first inorganic fine particles and the second inorganic fine particles is not particularly limited.
  • the film-forming composition of the present disclosure has excellent water repellency and easily forms a film having excellent abrasion resistance and snow accretion prevention performance.
  • the first inorganic fine particles are preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more of the total mass. Further, the first inorganic fine particles are preferably 90% by mass or less, more preferably 80% by mass or less, and 60% by mass or less with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. More preferably, the content is particularly preferably 50% by mass or less.
  • the water-repellent component is a component capable of imparting water repellency to the film when the film is formed, and is based on a compound represented by the following general formula (1). It is a polymer having structural units.
  • X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different, a hydrogen atom, a fluorine atom, or chlorine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a 1 to 20 carbon atoms represents a linear or branched alkyl group.
  • X is an alkyl group having 3 or more carbon atoms or a fluoroalkyl group, these may be either cyclic or acyclic.
  • X is an alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 2 carbon atoms.
  • the fluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 2 carbon atoms.
  • Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms optionally having an oxygen atom, a —CH 2 CH 2 N(R 1 )SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R a and the left end is bonded to O.), —CH 2 CH(OY 1 )CH 2 — group (with the proviso that Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R a and the left end is bonded to O.), or a —(CH 2 ) n SO 2 — group (where n is 1 to 10, and the formula The right end of is bound to Ra , and the left end is bound to O.).
  • Direct bond means that R a and O at both ends of Y are directly bonded in the above formula (1), that is, Y does not contain an element.
  • Y is a hydrocarbon group having 1 to 10 carbon atoms, it is specifically an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms. is an alkylene group of
  • R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, a polysiloxane having a molecular weight of 300 to 50,000, or It represents a polyether group with a molecular weight of 400-5000 or a fluoropolyether group with a molecular weight of 400-5000.
  • the fluoroalkyl group is preferably, for example, a perfluoroalkyl group.
  • the polysiloxane is preferably polydimethylsiloxane, more preferably R 2 —(Si(CH 3 ) 2 O) n —.
  • R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and 1 to 6 carbon atoms. is more preferred.
  • n is 3-680, preferably 10-500, more preferably 100-400.
  • the fluoropolyether group is preferably, for example, a perolopolyether group.
  • Specific examples of the compound represented by Formula (1) include a wide range of acrylic acid esters disclosed in Patent Document 1 described above.
  • the compound represented by the formula (1) has a hydrogen atom, a chlorine atom, a fluorine atom, or a methyl Y is a direct bond or an alkylene group having 1 to 10 carbon atoms (preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms), and R a is 1 carbon atom -20 linear or branched alkyl groups, C1-6 linear or branched fluoroalkyl groups, polysiloxanes with molecular weights of 300 to 50,000, or polyether groups with molecular weights of 400 to 5,000, or molecular weights of 400 Combinations of ⁇ 5000 fluoropolyether groups can be mentioned.
  • a more preferred compound represented by formula (1) has X being a hydrogen atom or a methyl group, Y being an alkylene group having 1 to 2 carbon atoms, and R a being a linear or branched fluoroalkyl having 1 to 6 carbon atoms. It is a polysiloxane with a group or molecular weight of 300-50,000.
  • X is a hydrogen atom or a methyl group
  • Y is a direct bond
  • R a is a linear or branched alkyl group having 1 to 20 carbon atoms or polysiloxane having a molecular weight of 300 to 50,000 is also preferred.
  • Specific compounds of the compound represented by formula (1) include fluoroalkyl (meth)acrylates having a fluoroalkyl group having 1 to 6 carbon atoms and alkyl groups having 1 to 20 carbon atoms (preferably 1 to 18). of alkyl (meth)acrylates.
  • the compound represented by Formula (1) can also be obtained from a commercial item.
  • examples of compounds in which Ra is a polysiloxane having a molecular weight of 300 to 50000 include JNC's product names "Silaplane (registered trademark) FM-0711” and “Silaplane (registered trademark) FM-0721”, “Silaplane (registered trademark) FM-0725”, and “Silaplane (registered trademark) FM-0701T”.
  • the water-repellent component is a structural unit based on a (meth)acrylate having an epoxy site, or a (meth)acrylate having an amide bond (for example, Y in the formula (1) is compound replaced with a functional group having an amide bond).
  • the (meth)acrylate having an epoxy moiety can be glycidyl (meth)acrylate
  • the (meth)acrylate having an amide bond can be stearamidoethyl (meth)acrylate.
  • the polymer having at least a structural unit based on the compound represented by formula (1) can contain a structural unit based on a compound other than the compound represented by formula (1).
  • structural units include structural units based on hydroxyalkyl (meth)acrylates, structural units based on (meth)acrylates having an epoxy site, and (meth)acrylates having an amide bond (for example, Y in the formula (1) is amide a compound substituted with a functional group having a bond), a structural unit based on a chlorine-containing vinyl monomer, a structural unit based on a chlorine-containing vinylidene monomer, a structural unit based on an acrylamide monomer, etc. can be done.
  • structural units based on hydroxyalkyl (meth)acrylates include 2-hydroxyethyl methacrylate and the like, and (meth)acrylates having an epoxy moiety include glycidyl (meth)acrylate and the like.
  • (meth)acrylates having an amide bond include stearamidoethyl (meth)acrylate.
  • chlorine-containing vinyl monomers include vinyl chloride.
  • chlorine-containing vinylidene monomers include vinylidene chloride.
  • the acrylamide monomer can include N-methylolacrylamide.
  • the polymer having at least structural units based on the compound represented by formula (1) may further contain other structural units.
  • Monomers for forming other structural units may include one or more of various monofunctional monomers and/or polyfunctional monomers. Such monomers have ethylenically unsaturated double bonds and include acid group-containing monomers, hydroxyl group-containing monomers, chlorine-containing monomers, nitrogen-containing monomers, alkylene glycol group-containing Examples include monomers, alkoxyalkyl group-containing monomers, carbonyl group-containing monomers, silane group-containing monomers, ring structure-containing monomers, etc., but the present invention is not limited thereto. .
  • Acid group-containing monomers include (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, Itaconic acid monobutyl ester, vinyl benzoic acid and the like can be mentioned.
  • hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) acrylates and the like.
  • Chlorine-containing monomers include vinyl chloride and vinylidene chloride.
  • Nitrogen-containing monomers include (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N - isopropyl (meth)acrylamide, methylenebis (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropylacrylamide, diacetoneacrylamide , dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, stearamidoethyl (meth)acrylate, N-vinylpyrrolidone, (meth)acrylonitrile and the like.
  • alkylene glycol group-containing monomers examples include ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate.
  • alkoxyalkyl group-containing monomers include methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, and trimethylolpropane tripropoxy (meth)acrylate.
  • Carbonyl group-containing monomers include acrolein, bomylstyrene, vinyl ethyl ketone, (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, 2-hydroxypropyl (meth)acrylate acetylacetate. , butanediol-1,4-acrylate acetylacetate, 2-(acetoacetoxy)ethyl (meth)acrylate and the like.
  • Silane group-containing monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, ⁇ -(meth)acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, ⁇ -(meth)acryloyloxypropylhydroxysilane, ⁇ -(meth)acryloyloxypropylmethylhydroxysilane and the like.
  • Ring structure-containing monomers include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, glycidyl allyl ether, benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, naphthylmethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, styrene, ⁇ -methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, (meth)acryloylaziridine, (meth)acrylic acid 2- aziridinylethyl, vinyltoluene, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-
  • polyfunctional monomers examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, Di(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as tripropylene glycol di(meth)acrylate; Alkyl di(meth)acrylates having 2 to 50 moles of alkylene oxide groups having 2 to 4 carbon atoms, such as polypropylene glycol di(meth)acrylate having 2 to 50 and tripropylene glycol di(meth)
  • the polymer having at least a structural unit based on the compound represented by formula (1) contains 40% by mass or more of the structural unit based on the compound represented by formula (1) with respect to the total mass of the water-repellent component. is preferable, more preferably 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more.
  • a polymer having at least structural units based on the compound represented by formula (1) can also be formed only with structural units based on the compound represented by formula (1).
  • the water-repellent component can contain one or more structural units based on the compound represented by formula (1).
  • the water repellent component can also be obtained from commercial products, for example, the product name "Unidyne (registered trademark) TG series” manufactured by Daikin Industries, Ltd., the product name “Scotchguard (registered trademark)” manufactured by 3M, Toagosei trade names "Symac (registered trademark) US-270", “Symac (registered trademark) US-350", “Symac (registered trademark) US-352", “Symac (registered trademark) US-380” manufactured by Japan A trade name “SG-204” manufactured by Catalyst Co., Ltd. can be mentioned.
  • the polymerizable component is a component that becomes a binder component when the film is formed, and can be called a binder component precursor.
  • the polymerizable component is a component that can be cured (eg, a polymerization reaction or a curing reaction) and that, after curing, forms the binder component of the coating.
  • the polymerizable component excludes the polymer of the compound represented by the formula (1).
  • the type of the polymerizable component is not particularly limited as long as it can form a binder component, and a wide range of known materials can be used.
  • the polymerizable component contained in the film-forming composition is a component that can give a cured product by the progress of a curing reaction by applying heat, or can give a cured product by irradiation with light such as UV. is an ingredient.
  • a component that can give a cured product as a result of the curing reaction progressing by applying heat is called a “thermosetting resin component”, and a component that can give a cured product by light irradiation is called a “photocurable resin component”. do.
  • the polymerizable component is preferably at least one of a thermosetting resin component and a photocurable resin component.
  • thermosetting resin component is not particularly limited, and for example, it can be a mixture of a known polymer and a curing agent that is included as necessary.
  • a polymer preferably has, for example, a crosslinkable functional group, and in this case, for example, thermal curing facilitates the progress of the crosslinking reaction.
  • the polymerizable component is preferably a polymer having a crosslinkable functional group and a curing agent.
  • crosslinkable polymer a polymer having a crosslinkable functional group.
  • the crosslinkable polymer may or may not have a fluorine atom (fluoroalkyl group). However, from the viewpoint that the water repellency of the film is likely to be improved, the crosslinkable polymer preferably has a fluoroalkyl group.
  • the crosslinkable polymer having no fluorine atom can be obtained from commercial products.
  • UWS-2740 “Halshybrid Udable (registered trademark) UWS-2841”, “Halshybrid Udable (registered trademark) UWS-2818”, “Halshybrid Udable (registered trademark) UWS-2816”
  • Hals Hybrid Udable (registered trademark) UWH-4818 "Hals Hybrid UV-G (registered trademark) UV-G12", “Hals Hybrid UV-G (registered trademark) UV-G13", “Hals Hybrid UV- G (registered trademark) UV-G101”, “Hals Hybrid UV-G (registered trademark) UV-G301”, “Hals Hybrid UV-G (registered trademark) UV-G137”, “Acryset (registered trademark) ATH-2060 ”, “Acryset (registered trademark) ATH-2070”, “
  • the crosslinkable functional group is preferably, for example, a hydroxyl group, a carboxyl group, an amino group, a thiol group, an isocyanate group, or the like. In this case, such compounds preferably further have a fluoroalkyl group.
  • the crosslinkable functional groups are preferably covalently bonded, for example, to the side chains of the crosslinkable polymer.
  • examples of the crosslinkable polymer include fluorine-containing polymers having various crosslinkable functional groups.
  • other monomer structural units provided that (d) does not contain aromatic group-containing monomer structural units that do not contain hydroxyl groups and carboxyl groups)
  • a polymer consisting of can be mentioned.
  • this polymer is referred to as "Polymer F".
  • the thermosetting resin is polymer F, the water resistance of the coating is particularly improved.
  • the content of the (a) tetrafluoroethylene structural unit and/or chlorotrifluoroethylene structural unit has a lower limit of 20 mol%, preferably 30 mol%, more preferably 40 mol%, particularly It is preferably 42 mol %, and the upper limit is 49 mol %, preferably 47 mol %.
  • Examples of the monomer that provides the non-aromatic vinyl ester monomer structural unit (b) include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, and lauric acid.
  • One or more of vinyl, vinyl stearate, vinyl cyclohexylcarboxylate and the like can be mentioned.
  • These monomers are non-aromatic monomers containing no hydroxyl group or carboxyl group.
  • Monomers that give a particularly preferred non-aromatic vinyl ester monomer structural unit (b) are selected from the group consisting of vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate and vinyl acetate from the viewpoint of excellent weather resistance. It is the one of choice.
  • non-aromatic carboxylic acid vinyl esters particularly carboxylic acid vinyl esters having 6 or more carbon atoms, more preferably vinyl carboxylates having 9 or more carbon atoms, are preferred from the viewpoint of chemical resistance. Esters are preferred.
  • the upper limit of the carbon number of the carboxylic acid in the carboxylic acid vinyl ester is preferably 20 or less, more preferably 15 or less.
  • vinyl versatate is most preferable.
  • the content of the non-aromatic vinyl ester monomer structural unit (b) has a lower limit of 25 mol%, preferably 30 mol%, and an upper limit of 69.9 mol%, preferably 69.9 mol%, based on the total amount of the polymer F. 60 mol %, more preferably 43 mol %, particularly preferably 40 mol %.
  • the monomer that gives the hydroxyl group-containing vinyl monomer structural unit (c) is a non-aromatic monomer containing no carboxyl group, and examples thereof include hydroxyalkyl vinyl ethers and hydroxyalkyl allyl ethers represented by formula (2).
  • CH2 CHR10 (2)
  • R 10 represents —OR 20 or —CH 2 OR 20 (where R 20 is an alkyl group having a hydroxyl group).
  • R 20 is, for example, a linear or branched alkyl group having 1 to 8 carbon atoms to which 1 to 3, preferably 1 hydroxyl group is bonded.
  • Examples of formula (2) include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methyl
  • One or more of butyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether and the like can be used.
  • 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are preferable as the monomer that provides the hydroxyl group-containing vinyl monomer structural unit (c).
  • this hydroxyl group-containing vinyl monomer structural unit (c) can improve the workability, impact resistance, and stain resistance of the film.
  • the content of the hydroxyl group-containing vinyl monomer structural unit (c) has a lower limit of 8 mol%, preferably 10 mol%, more preferably 15 mol%, and an upper limit of 30 mol%, preferably 30 mol%, based on the total amount of the polymer F. 20 mol %.
  • Polymer F can be basically composed of (a), (b) and (c) (however, two or more of each unit may be copolymerized), but up to 10 mol % Other copolymerizable monomeric units (f) may be included.
  • Other copolymerizable monomer structural units (f) are the above (a), (b) and (c), aromatic group-containing monomer structural units (d) and carboxyl group-containing monomer structural units other than (e). It is a monomer structural unit.
  • Examples of monomers that give other copolymerizable monomer structural units (f) include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; non-fluorine olefins such as ethylene, propylene, n-butene and isobutene. .
  • the content in polymer F is 10 mol % or less, preferably less than 5 mol %, more preferably 4 mol % or less.
  • Polymer F can further contain (d) aromatic group-containing monomer structural units that do not contain hydroxyl groups and carboxyl groups.
  • aromatic group-containing monomer structural unit that does not contain a hydroxyl group and a carboxyl group includes, for example, one or more vinyl benzoate monomers such as vinyl benzoate and vinyl para-t-butylbenzoate. para-t-butyl vinyl benzoate, and vinyl benzoate is particularly preferred.
  • the content of the aromatic group-containing monomer structural unit (d) in the polymer F has a lower limit of 2 mol%, preferably 4 mol%, and an upper limit of 15 mol%, preferably 10 mol%, more preferably 8. in mol %.
  • Polymer F can further contain (e) a carboxyl group-containing monomer structural unit that does not contain a hydroxyl group and an aromatic group.
  • carboxyl group-containing monomers include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, and maleic anhydride. , fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, and the like. Among them, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, and 3-allyloxypropionic acid, which have low homopolymerizability, are preferred.
  • the content of the carboxyl group-containing monomer structural unit (e) in the polymer F has a lower limit of 0.1 mol%, preferably 0.4 mol%, and an upper limit of 2.0 mol%, preferably 1.5. in mol %.
  • Polymer F has a number average molecular weight of, for example, 1,000 to 1,000,000, preferably 3,000 to 50,000 as measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.
  • the glass transition temperature (2nd run) of polymer F determined by a differential scanning calorimeter (DSC) is, for example, 10 to 60°C, preferably 20 to 40°C.
  • the method for producing the polymer F is also not particularly limited, and a wide range of known production methods can be employed.
  • the polymer F can be obtained from commercial products and the like.
  • polymer F examples include Zeffle (registered trademark) GK series manufactured by Daikin Industries, Ltd., Lumiflon (registered trademark) LF series manufactured by Asahi Glass Co., Ltd., Fluorate (registered trademark) series manufactured by DIC Corporation, and Kyner manufactured by Arkema.
  • examples include Aquatec (registered trademark) and KYNAR 500 Plus.
  • the thermosetting resin component contains a curing agent as described above in addition to the crosslinkable polymer.
  • the curing agent is not particularly limited, and for example, compounds used as curing agents for thermosetting resins can be widely applied.
  • the curing agent is preferably a compound having two or more polymerizable groups in the molecule described above.
  • a specific example of the curing agent is an isocyanate curing agent.
  • isocyanate-based curing agents include compounds having an isocyanate group (hereinafter simply referred to as isocyanate compounds).
  • isocyanate compounds include those represented by the following general formula (20).
  • Z 6 has at least one terminal isocyanate group, 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. It is preferably a linear or branched monovalent hydrocarbon group or carbonyl group which may have a carbon-carbon unsaturated bond.
  • R 3 at least one carbon atom may be substituted with a hetero atom, at least one hydrogen atom may be substituted with a halogen atom, or at least one carbon atom may be substituted with a hetero atom. It is preferably a branched or cyclic hydrocarbon group having a valence of 2 or more or a carbonyl group, which may have a carbon-carbon unsaturated bond.
  • o in the formula (20) is an integer of 2 or more.
  • 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 preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.
  • the isocyanate compound may be used singly or in combination.
  • isocyanate compounds include polyisocyanates.
  • polyisocyanate means a compound having two or more isocyanate groups in the molecule.
  • the isocyanate compound may be a polyisocyanate obtained by trimerizing a diisocyanate.
  • Polyisocyanates obtained by trimerizing such diisocyanates may be triisocyanates.
  • Polyisocyanate, which is a trimer of diisocyanate may exist as a polymer obtained by polymerizing these.
  • the diisocyanate is not particularly limited, but isocyanate groups such as trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate are bonded to aliphatic groups.
  • isocyanate groups such as trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate are bonded to aliphatic groups.
  • Diisocyanate diisocyanates in which an isocyanate group is bonded to an aromatic group, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, and naphthalene diisocyanate.
  • Specific polyisocyanates include, but are not limited to, compounds having the following structures.
  • polyisocyanates may exist as polymers.
  • polymers in the case of an isocyanurate-type polyisocyanate of hexamethylene diisocyanate, they may have a polymer having the following structure.
  • the isocyanate compound is an isocyanurate-type polyisocyanate.
  • the above 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 monocyclic compounds having only one isocyanurate ring can be used.
  • a mixture containing an isocyanate compound that is an isocyanurate-type polyisocyanate can be used.
  • the isocyanurate-type polyisocyanate may be, for example, a triisocyanate, specifically a triisocyanate obtained by trimerizing a diisocyanate.
  • isocyanate compounds include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene.
  • Diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts thereof, burettes and isocyanurates, polymers thereof having two or more isocyanate groups, further blocked Isocyanates and the like can be mentioned.
  • More detailed curing agents include Sumidule (registered trademark) N3300 (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) N3600 (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur T, L, IL, HL series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) 2460M (manufactured by Sumika Covestro Urethane Co., Ltd.), Sumidule (registered trademark) 44 series (Sumika Covestro Urethane Co., Ltd.) company), SBU isocyanate series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) E, M series (manufactured by Sumika Covestro Urethane Co., Ltd.), Sumidule HT (Sumika Covestro
  • the content of the curing agent can be 10 to 100% by mass, preferably 15 to 35% by mass, based on the total mass of the crosslinkable polymer and the curing agent.
  • the polymerizable component when the polymerizable component is a photocurable resin component, a monomer that undergoes a polymerization reaction upon irradiation with light such as UV can be used.
  • a wide range of known photopolymerizable monomers can be employed.
  • the polymerizable component is a photocurable resin component, for example, it is also preferable to use a known photopolymerization initiator.
  • the type of photopolymerization initiator is also not particularly limited, and for example, a wide range of known photopolymerization initiators used for forming water-repellent coating films can be employed.
  • the content ratios of the inorganic fine particles, the polymerizable component and the water-repellent component are not particularly limited as long as the effects of the present disclosure are not impaired.
  • the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component (hereinafter referred to as "total mass (S1)")
  • the content of the first inorganic fine particles per 100 parts by mass is 3 to 25 parts by mass.
  • the content of the first inorganic fine particles is less than 3 parts by mass per 100 parts by mass of the total mass (S1), the effect of the first inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved.
  • the content of the first inorganic fine particles is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 10 parts by mass or more per 100 parts by mass of the total mass (S1). is more preferred.
  • the content of the first inorganic fine particles is preferably 23 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less per 100 parts by mass of the total mass (S1). It is even more preferable to have
  • the content of the second inorganic fine particles per 100 parts by mass of the total mass (S1) is 12 to 27 parts by mass.
  • the content of the second inorganic fine particles is less than 12 parts by mass per 100 parts by mass of the total mass (S1), the effect of the second inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, the anti-snow accretion performance is lowered, and even if it exceeds 27 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating.
  • the content of the second inorganic fine particles is preferably 15 parts by mass or more, more preferably 16 parts by mass or more, and 18 parts by mass or more per 100 parts by mass of the total mass (S1). is more preferably 26 parts by mass or less, and more preferably 25 parts by mass or less.
  • the total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts by mass or more per 100 parts by mass of the total mass (S1). As a result, desired water repellency and abrasion resistance can be obtained, excellent film-forming property can be achieved, and snow accretion prevention performance can be easily improved.
  • the “total mass (S1) of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component” is calculated as solid content. It means mass and does not include volatile components such as solvents. Further, when the polymerizable component is the thermosetting resin component, the mass of the polymerizable component in the total mass (S1) is the total mass of the polymer having a crosslinkable functional group and the curing agent. When the polymerizable component is the photocurable resin component, it means the total mass of the photopolymerizable monomer and the photopolymerization initiator.
  • the mass of the polymerizable component in the total mass (S1) is a polymer having a crosslinkable functional group and a curing is the total weight of the agent and the photopolymerizable monomer and photoinitiator.
  • the content of the water-repellent component (polymer having a structural unit based on the compound represented by formula (1)) in the film-forming composition of the present disclosure has excellent water repellency and abrasion resistance. It is preferably 0.1 to 30 parts by mass per 100 parts by mass of the total mass (S1) in terms of easy formation of a coating excellent in the above.
  • the content of the water-repellent component is more preferably 1 part by mass or more, more preferably 15 parts by mass or less, and 10 parts by mass or less per 100 parts by mass of the total mass (S1). is more preferred.
  • the content of the polymerizable component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S1). In this case, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.
  • the content of the polymerizable component is more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass, per 100 parts by mass of the total mass (S1).
  • the content of the thermosetting resin component is 40 to 90 parts by mass per 100 parts by mass of the total mass (S1). , more preferably 50 to 90 parts by mass, even more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.
  • the content of the photocurable resin component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S1), and 50 to It is more preferably 90 parts by mass, and even more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.
  • At least one of the polymerizable component and the water-repellent component preferably has a fluorine atom (that is, a fluoroalkyl group) or polysiloxane, and more preferably has a fluorine atom, Among them, it is particularly preferable that the polymerizable component has a fluorine atom.
  • the film formed from the film-forming composition has excellent water repellency, high hardness, excellent water resistance, and improved abrasion resistance.
  • both the polymerizable component and the water-repellent component may have a fluorine atom (fluoroalkyl group), or both the polymerizable component and the water-repellent component may have no fluorine atom.
  • An example of the case where the polymerizable component has a fluoroalkyl group is the case where the crosslinkable polymer contained in the thermosetting resin component is the polymer F.
  • An example of the case where the water-repellent component has a fluoroalkyl group is a polymer that is a fluoroalkyl (meth)acrylate in which the fluoroalkyl group has 1 to 6 carbon atoms in the compound represented by formula (1). .
  • the abrasion resistance of the film is likely to be further improved.
  • the water-repellent component is a compound represented by the formula (1), and R a is a linear or branched alkyl group having 20 or less carbon atoms, the abrasion resistance of the coating is more likely to be improved. .
  • saturated fatty acids contained in known lubricating oils examples of which include caprylic acid, capric acid, Structures having straight-chain alkyl groups with the same number of carbon atoms as those of lauric acid, myristic acid, palmitic acid, stearic acid, or these saturated fatty acids can be mentioned.
  • the film-forming composition of the present disclosure may contain other components as long as it contains the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component.
  • the film-forming composition can contain a component capable of exhibiting water repellency in addition to the polymer having a structural unit based on the compound represented by formula (1).
  • a specific example of such a component is a polymer having a (meth)acrylate as a main skeleton and having a fluoroalkyl group or an alkyl group at its side chain site.
  • the film-forming composition can also contain a solvent, if necessary.
  • a solvent is not limited, and for example, a wide range of solvents that are used to form a film can be used. Examples include fluorine-based solvents such as hydrofluoroethers, ester compounds, alcohol compounds, and the like. can.
  • the content of the solvent contained in the film-forming composition is not particularly limited. It can be 200 to 2000 parts by mass.
  • the film-forming composition can also contain additives other than a component capable of exhibiting water repellency and a solvent.
  • the content ratio thereof is 5% by mass or less with respect to the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component. is desirable.
  • first inorganic fine particles, second inorganic fine particles, a polymerizable component for example, a thermosetting resin component containing the polymer F and a curing agent
  • a water-repellent component represented by formula (1) It can be prepared by mixing with a predetermined compounding amount.
  • the mixing method is also not particularly limited, and for example, a wide range of known mixers and the like can be used.
  • the method of forming a film using the film-forming composition of the present disclosure is not particularly limited.
  • a film can be formed by applying the film-forming composition to a substrate for forming a film to form a coating film, and curing the coating film.
  • Such a coating is a cured product of the coating-forming composition of the present disclosure.
  • the coating method of the film-forming composition is not particularly limited, and a wide range of known coating film-forming methods can be employed. For example, it can be applied by a method such as brush coating, spray coating, spin coating, or dispenser.
  • the type of base material for forming the coating film of the film-forming composition is not particularly limited. material can be mentioned.
  • the method of curing the film-forming composition is also not particularly limited, and for example, various methods such as heat curing and photo-curing can be employed, and heat-curing and photo-curing can be combined.
  • heat curing it is preferable to heat the coating film of the film-forming composition to 60 to 150 ° C.
  • the film of the film-forming composition is easily formed, has high hardness, and is also water resistant. Excellent.
  • the heating time is not particularly limited, and can be appropriately set according to the heating temperature.
  • a chemical solution can be prepared using the film-forming composition of the present disclosure. Since such a chemical solution contains the film-forming composition of the present disclosure, it is suitable for use in forming a film.
  • the chemical solution can be composed only of the film-forming composition, or other additives (for example, film-forming solvent known additives used as drugs).
  • Coating The coating of the present disclosure can be formed, for example, using the coating composition of the present disclosure described above, or the coating of the present disclosure can be formed using the chemical solution.
  • the film of the present disclosure is a cured product of the film-forming composition or chemical solution of the present disclosure.
  • the coating of the present disclosure includes first inorganic fine particles, second inorganic fine particles, a binder component, and a water-repellent component.
  • the binder component is a component formed by polymerizing the polymerizable component.
  • the first inorganic fine particles and the second inorganic fine particles are respectively the same as the first inorganic fine particles and the second inorganic fine particles contained in the film-forming composition of the present disclosure. Therefore, the average particle size of the first inorganic fine particles contained in the coating is 1 nm or more and 100 nm or less, and the average particle size of the second inorganic fine particles contained in the coating is 500 nm or more and 5 ⁇ m or less.
  • the average particle size of the first inorganic fine particles is preferably 2 nm or more, more preferably 3 nm or more, even more preferably 4 nm or more, and particularly preferably 5 nm or more.
  • the average particle size of the first inorganic fine particles is preferably 80 nm or less, more preferably 60 nm or less, even more preferably 50 nm or less, and particularly preferably 30 nm or less.
  • the average particle diameter of the second inorganic fine particles is preferably 800 nm or more, more preferably 1 ⁇ m or more, even more preferably 1.5 ⁇ m or more, and particularly preferably 2 ⁇ m or more.
  • the average particle size of the second inorganic fine particles is preferably 4.5 ⁇ m or less, more preferably 4 ⁇ m or less, still more preferably 3.5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the types of the first inorganic fine particles and the second inorganic fine particles are not particularly limited as long as they satisfy the aforementioned average particle diameter, and for example, a wide range of known metal oxide fine particles can be exemplified.
  • Specific examples of metal oxides include silica, alumina, titanium oxide, zirconia, and the like, and the first inorganic fine particles and the second inorganic fine particles are silica in that the hardness and water resistance of the coating are likely to increase.
  • first inorganic fine particles and the second inorganic fine particles may be the same or different, preferably the first inorganic fine particles and the second inorganic fine particles are the same, more preferably , both the first inorganic fine particles and the second inorganic fine particles are silica.
  • the specific surface areas of the first inorganic fine particles and the second inorganic fine particles are not particularly limited.
  • the specific surface area is preferably from 30 to 700 m 2 /g, more preferably from 800 to 330 m 2 , from the viewpoint of easily improving the hardness of the resulting coating. /g is more preferred.
  • the specific surface area of the fine particles means a value measured by the BET method (so-called BET specific surface area).
  • the surfaces of the first inorganic fine particles and the second inorganic fine particles may be hydrophilic or hydrophobic.
  • the first inorganic fine particles and the second inorganic fine particles may be a mixture of hydrophilic and hydrophobic properties.
  • the shapes of the first inorganic fine particles and the second inorganic fine particles are also not particularly limited, and examples thereof include spherical, ellipsoidal and the like, and may be amorphous particles such as irregular shaped particles.
  • the first inorganic fine particles and the second inorganic fine particles preferably do not have a radically polymerizable reactive group (for example, a polymerizable double bond such as an acryloyl group) on the surface, that is, the first inorganic fine particles And it is preferable that no polymer (for example, a binder component and a water-repellent component) is covalently bonded to the surface of the second inorganic fine particles.
  • a radically polymerizable reactive group for example, a polymerizable double bond such as an acryloyl group
  • no polymer for example, a binder component and a water-repellent component
  • the shape of the first inorganic fine particles and the second inorganic fine particles is also not particularly limited, and examples thereof include spherical, ellipsoidal and the like, and may be amorphous particles such as irregular shaped particles.
  • the first inorganic fine particles and the second inorganic fine particles can also form aggregates. Aggregates may be spherical or non-spherical, and may be chain-like.
  • the inorganic fine particles contained in the coating of the present disclosure can contain 80% by mass or more of the first inorganic fine particles and the second inorganic fine particles, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably It is 99% by mass or more.
  • the inorganic fine particles contained in the film of the present disclosure may be only the first inorganic fine particles and the second inorganic fine particles, and are particularly preferably only the first inorganic fine particles and the second inorganic fine particles.
  • the content ratio of both the first inorganic fine particles and the second inorganic fine particles is not particularly limited.
  • the first inorganic fine particles are 5 masses with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. % or more, more preferably 10 mass % or more, and even more preferably 20 mass % or more.
  • the first inorganic fine particles are preferably 90% by mass or less, more preferably 80% by mass or less, and 60% by mass or less with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. More preferably, the content is particularly preferably 50% by mass or less.
  • the binder component is a component formed by curing the polymerizable component described above.
  • the polymerizable component is the aforementioned thermosetting resin component
  • the polymer F is a polymer cured (crosslinked) with the curing agent.
  • the binder component may contain an uncured polymerizable component as long as the performance of the film of the present disclosure is not impaired.
  • the water-repellent component is the same as the water-repellent component contained in the above-described film-forming composition of the present disclosure. Therefore, the water-repellent component in the film is a polymer having a structural unit derived from the compound represented by formula (1).
  • the polymer having structural units derived from the compound represented by formula (1) can contain structural units other than the compound represented by formula (1).
  • structural units include structural units based on hydroxyalkyl (meth)acrylates, structural units based on (meth)acrylates having an epoxy site, and (meth)acrylates having an amide bond (for example, Y in the formula (1) is amide a compound substituted with a functional group having a bond), a structural unit based on a chlorine-containing vinyl monomer, a structural unit based on a chlorine-containing vinylidene monomer, a structural unit based on an acrylamide monomer, etc. can be done.
  • structural units based on hydroxyalkyl (meth)acrylates include 2-hydroxyethyl methacrylate and the like, and (meth)acrylates having an epoxy moiety include glycidyl (meth)acrylate and the like.
  • (meth)acrylates having an amide bond include stearamidoethyl (meth)acrylate.
  • chlorine-containing vinyl monomers include vinyl chloride.
  • chlorine-containing vinylidene monomers include vinylidene chloride.
  • the acrylamide monomer can include N-methylolacrylamide.
  • the polymer having at least structural units based on the compound represented by formula (1) may further contain other structural units.
  • Monomers for forming other structural units may include one or more of various monofunctional monomers and/or polyfunctional monomers. Such monomers include the aforementioned acid group-containing monomers, hydroxyl group-containing monomers, chlorine-containing monomers, nitrogen-containing monomers, alkylene glycol group-containing monomers, alkoxyalkyl group-containing monomers, A carbonyl group-containing monomer, a silane group-containing monomer, and a ring structure-containing monomer can be mentioned, and the respective types are the same as those described above.
  • the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component (hereinafter referred to as “total mass (S2)”) per 100 parts by mass
  • the content of the first inorganic fine particles is 3 to 25 parts by mass.
  • the content of the first inorganic fine particles is less than 3 parts by mass per 100 parts by mass of the total mass (S2), the effect of the first inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved.
  • the content of the first inorganic fine particles is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 10 parts by mass or more per 100 parts by mass of the total mass (S2). is more preferred.
  • the content of the first inorganic fine particles is preferably 23 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less per 100 parts by mass of the total mass (S2). It is even more preferable to have
  • the content of the second inorganic fine particles per 100 parts by mass of the total mass (S2) is 12 to 27 parts by mass.
  • the content of the second inorganic fine particles is less than 12 parts by mass per 100 parts by mass of the total mass (S2), the effect of the second inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, the anti-snow accretion performance is lowered, and even if it exceeds 27 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating.
  • the content of the second inorganic fine particles is preferably 15 parts by mass or more, more preferably 16 parts by mass or more, and 18 parts by mass or more per 100 parts by mass of the total mass (S2). is more preferably 26 parts by mass or less, and more preferably 25 parts by mass or less.
  • the total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts by mass or more per 100 parts by mass of the total mass (S2).
  • the total content of the first inorganic fine particles and the second inorganic fine particles is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, per 100 parts by mass of the total mass (S2). Also, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.
  • the binder component is a cured product of the thermosetting resin
  • the mass of the binder component in the total mass (S2) means the total mass of the cured product of the polymer having a crosslinkable functional group and the curing agent
  • the binder component is the photocurable In the case of a cured product of a flexible resin, it means the total mass of the photopolymerizable monomer and the photopolymerization initiator.
  • the mass of the polymerizable component in the total mass (S2) includes a polymer having a crosslinkable functional group and a cured product. It means the total mass of the cured product of the agent and the cured product of the photopolymerizable monomer and the photopolymerization initiator.
  • the content of the water-repellent component in the coating film of the present disclosure is 0.00% per 100 parts by mass of the total mass (S2), since a coating film having excellent water repellency and excellent wear resistance can be easily formed. 1 to 30 parts by mass.
  • the content of the water-repellent component is preferably 1 part by mass or more, more preferably 15 parts by mass or less, and 10 parts by mass or less per 100 parts by mass of the total mass (S2). is more preferred.
  • the content of the binder component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S2). In this case, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.
  • the content of the binder component is more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass, per 100 parts by mass of the total mass (S2).
  • the content of the cured product of the thermosetting resin is 40 to 90 mass parts per 100 parts by mass of the total mass (S2). parts, more preferably 50 to 90 parts by mass, and more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.
  • the content of the cured product of the photocurable resin is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S2). , more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.
  • At least one of the binder component and the water-repellent component preferably has a fluorine atom (that is, a fluoroalkyl group) or polysiloxane, and more preferably has a fluorine atom. It is more preferable to have a fluorine atom.
  • the coating has excellent water repellency, high hardness, excellent water resistance, and even improved abrasion resistance.
  • both the binder component and the water repellent component may have fluorine atoms (fluoroalkyl groups), or both the binder component and the water repellent component may not have fluorine atoms.
  • binder component having a fluoroalkyl group is polymer F or a crosslinked product thereof.
  • the polymer represented by the formula (1) is a fluoroalkyl (meth)acrylate in which the fluoroalkyl group has 1 to 6 carbon atoms.
  • the binder component and the water-repellent component can coat the first inorganic fine particles and the second inorganic fine particles, but are not covalently bonded, for example, preferably physically adsorbed. . This makes it possible to improve both the wear resistance and the anti-snow accretion performance, which have conventionally been in a trade-off relationship.
  • the abrasion resistance of the coating is likely to be further improved.
  • the water-repellent component is a compound represented by the formula (1), and R a is a linear or branched alkyl group having 20 or less carbon atoms, the abrasion resistance of the coating is more likely to be improved. .
  • saturated fatty acids contained in known lubricating oils examples of which include caprylic acid, capric acid, Structures having straight-chain alkyl groups with the same number of carbon atoms as those of lauric acid, myristic acid, palmitic acid, stearic acid, or these saturated fatty acids can be mentioned.
  • the coating of the present disclosure can contain a component other than the compound represented by formula (1), which is a component capable of imparting water repellency to the coating when the coating is formed.
  • a component is a polymer having a (meth)acrylate as a main skeleton and having a fluoroalkyl group or an alkyl group at its side chain site.
  • the coating of the present disclosure has, for example, a water contact angle of 150° or more. This allows the coating of the present disclosure to exhibit excellent water repellency.
  • the coating of the present disclosure has a surface with a water contact angle of 150° or more after rubbing at least 50 times with a paper waste cloth under a load of 100 g/cm 2 .
  • the coating of the present disclosure preferably has a snow accretion start time of, for example, 5 minutes or longer, more preferably 7 minutes or longer, and even more preferably 10 minutes or longer.
  • the coating of the present disclosure has, for example, an average thickness of 10 nm to 100 ⁇ m, a minimum local thickness of 5 nm to 50 ⁇ m, and a maximum local thickness of 15 nm to 150 ⁇ m, preferably an average thickness of 15 nm to 95 ⁇ m, and a minimum local thickness of The thickness is 10 nm to 45 ⁇ m, the maximum local thickness is 20 nm to 145 ⁇ m, more preferably the average thickness is 20 nm to 90 ⁇ m, the minimum local thickness is 15 nm to 40 ⁇ m, and the maximum local thickness is 25 nm to 140 ⁇ m.
  • the average film thickness can be calculated from, for example, the amount of applied coating film, the solid content concentration, and the dry film thickness calculated from the density of the composition.
  • the minimum local film thickness and the maximum local film thickness can be calculated using a device capable of measuring three-dimensional shapes.
  • An example of such a device is a shape analysis laser microscope VK-X1000 manufactured by KEYENCE.
  • the coating of the present disclosure can be formed on various substrates.
  • the substrate include known resin substrates such as acrylic resins and polycarbonate resins, metals such as aluminum, and various substrates such as inorganic substrates.
  • the film of the present disclosure has excellent water repellency and excellent abrasion resistance, so it is easy to maintain its performance over the long term.
  • the film formed from the film-forming composition of the present disclosure is excellent in anti-snow accretion performance, and even when exposed to snow, snow accretion is unlikely to occur for a long period of time. For example, even in areas with heavy snowfall, the coating of the present disclosure can exhibit snow accretion prevention performance for a long period of time.
  • the coating of the present disclosure is suitably used for imparting water repellency and/or oil repellency to the surface to be treated, and can be suitably used for various articles that require super liquid repellency.
  • Applications of the coating of the present disclosure are not particularly limited, and examples include water and oil repellent agents, frost retardation applications, anti-icing agents, snow-resistant agents, anti-fingerprint agents, anti-fingerprint agents, low-friction agents, and lubricants. , a protein adhesion control agent, a cell adhesion control agent, a microorganism adhesion control agent, a scale adhesion inhibitor, an antifungal agent, an antibacterial agent, and the like.
  • the film of the present disclosure can be suitably used for various articles and the like that require a function to prevent snow accretion.
  • the base material on which the film is formed can be suitably used as an antenna cover. can.
  • the method of forming other coatings of the present disclosure is not particularly limited. For example, even when the film-forming composition or chemical liquid of the present disclosure is used, the other forms of the film can be formed.
  • the inorganic fine particles contained in the other coating of the present disclosure are the same as the inorganic fine particles contained in the aforementioned coating of the present disclosure. Therefore, the inorganic fine particles contained in the other coating of the present disclosure include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less and second inorganic fine particles having an average particle size of 500 nm or more and 5 ⁇ m or less. . In addition, the content ratio of the first inorganic fine particles and the second inorganic fine particles contained in the other coating of the present disclosure is also the same as that of the coating of the present disclosure.
  • coatings of the present disclosure can contain a binder component and a water-repellent component in the same manner as the coating of the present disclosure, and their types and content ratios can also be the same as the coating of the present disclosure.
  • Other coatings of the present disclosure may have thicknesses in similar ranges as the coatings of the present disclosure.
  • coatings of the present disclosure can exhibit excellent water repellency by having a water contact angle of 150° or more.
  • the contact angle of water can be adjusted, for example, by appropriately selecting the types and contents of the inorganic fine particles, the binder component, and the water-repellent component.
  • Another coating of the present disclosure has a water contact angle of 150 ° or more after rubbing with a paper waste cloth at least 50 times (preferably 50 times) with a load of 100 g / cm 2 . can have
  • the contact angle of water is the static contact angle of water.
  • the contact angle of water is measured using a contact angle meter (Kyowa Interface Science Co., Ltd. “Drop Master 701”). is done. If the static contact angle is 150° or more, the liquid may not be able to stand on its own on the substrate surface. In such a case, the static contact angle is measured using the syringe needle as a support, and the value obtained at that time is defined as the static contact angle.
  • ⁇ Snow accretion test> A coating is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the coating is subjected to a wind speed of 10 m / sec and a collision amount of 110 kg /. Pre-made artificial snow is blown under the condition of m 2 /h. This blowing causes the artificial snow to impinge on the covering surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. Measured as the start time (no snow accretion time).
  • Example 1 3 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles. / g, and 27 parts by mass of silica fine particles (“Sylysia 310P” manufactured by Fuji Silysia Chemical) having an average particle diameter of 2.7 ⁇ m, and tetrafluoroethylene and a hydroxyl group-containing thermosetting resin corresponding to the polymer F.
  • silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles.
  • silica fine particles (“S
  • the fluorine-containing copolymer (water-repellent component) described in Preparation Example 2 of Japanese Patent No. 5831599 was prepared as follows. A 300 ml reactor equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen inlet and heating device was prepared, and 45 parts by mass of isopropyl alcohol (IPA) as a solvent was added.
  • IPA isopropyl alcohol
  • (CF 2 ) 6 CH 2 CH 2 OCOC(CH 3 ) CH 2 (C6FMA) 65 parts by mass, isobornyl methacrylate (IBMA) 20 parts by mass, and 2-hydroxyethyl methacrylate (HEMA) 15 parts by mass under stirring.
  • 5 parts by mass of lauryl mercaptan (L-SH) as a chain transfer agent was added to monomers (total of 100 parts by mass of monomers) consisting of parts by mass, and 1 part by mass of t-butyl perpivalate as an initiator was added in this order. , and this mixture was mixed and stirred for 12 hours under a nitrogen atmosphere at 60°C to carry out copolymerization.
  • this reaction mixture was cooled to room temperature to obtain a fluorine-containing copolymer solution.
  • the solid content concentration of this solution was 70% by mass.
  • the monomer composition of the fluorine-containing copolymer almost matched the charged monomer composition, and the weight average molecular weight was 9,000.
  • Example 2 A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 9 parts by mass and the second inorganic fine particles were 21 parts by mass.
  • Example 3 A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 15 parts by mass and the second inorganic fine particles were 15 parts by mass.
  • Example 4 20 parts by mass of the first inorganic fine particles, 20 parts by mass of the second inorganic fine particles, 46 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), 10 parts by mass of Sumidule N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 4 parts by mass (in terms of solid content).
  • Example 5 25 parts by mass of the first inorganic fine particles, 25 parts by mass of the second inorganic fine particles, 37 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), 8 parts by mass of Sumidur N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 5 parts by mass (in terms of solid content).
  • Example 6 19 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles. / g, and 11 parts by mass of silica fine particles having an average particle diameter of 2.7 ⁇ m (“Silysia 310P” manufactured by Fuji Silysia Chemical), and 44 parts of “Udable UWS-2816 (manufactured by Nippon Shokubai Co., Ltd.)” as a thermosetting resin.
  • silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles.
  • Example 7 16 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles. / g, and 14 parts by mass of silica fine particles having an average particle diameter of 2.7 ⁇ m (“Sylysia 310P” manufactured by Fuji Silysia Chemical), and 38 parts of “Udable UWS-2816 (manufactured by Nippon Shokubai Co., Ltd.)” as a thermosetting resin.
  • silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles
  • Parts by mass (in terms of solid content) and butyl acetate as a solvent were prepared and blended to prepare a film-forming composition in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.
  • Example 8 8 parts by mass of silica fine particles ("Aerosil 300" manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles. / g, and 20 parts by mass of silica fine particles having an average particle diameter of 2.7 ⁇ m (“Sylysia 310P” manufactured by Fuji Silysia Chemical), and 25 parts of "Udable UWS-2818 (manufactured by Nippon Shokubai Co., Ltd.)" as a thermosetting resin.
  • silica fine particles (“Aerosil 300" manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles
  • Parts by mass (in terms of solid content) and butyl acetate as a solvent were prepared and blended to prepare a film-forming composition in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.
  • SYMAC US-352 and SYMAC US-380 used in Examples 6 to 8 are silicone-grafted acrylic polymers, and structural units based on compounds in which R a in formula (1) is polysiloxane having a molecular weight of 300 to 50,000. is a polymer having
  • Example 1 A film was formed in the same manner as in Example 1, except that the first inorganic fine particles were not used and the second inorganic fine particles were 30 parts by mass.
  • Example 2 A coating was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 21 parts by mass and the second inorganic fine particles were 9 parts by mass.
  • Example 3 A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 27 parts by mass and the second inorganic fine particles were 3 parts by mass.
  • Example 4 A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 30 parts by mass and the second inorganic fine particles were 0 parts by mass.
  • ⁇ Water contact angle (static contact angle)> The contact angle of water was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. "Drop Master 701"). Specifically, using water (droplet of 2 ⁇ L), 5 points were measured for one sample. When the static contact angle reaches 150° C. or more, the liquid cannot stand on its own and exist on the substrate surface. The value was taken as the static contact angle.
  • Abrasion resistance was evaluated by a rubbing test described below.
  • the initial contact angle was obtained by measuring the contact angle with water of the test piece of each coating obtained in Examples or Comparative Examples.
  • Kimwipe (trade name: Kimwipe, manufactured by Nippon Paper Crecia Co., Ltd.) as a paper waste was placed on the holder (area in contact with the sample: 1 cm 2 ) of the rubbing tester (Imoto Seisakusho's rubbing tester "wear resistance tester 151E triple specification"). It was worn and rubbed a certain number of times with a load of 100 g/cm 2 . After that, the water contact angle was measured to evaluate the abrasion resistance against wiping.
  • Abrasion resistance here means the number of times of abrasion that can maintain a super water-repellent state (an average static contact angle value of 5 times is 150° or more, or an average of 140° or more and a standard deviation of 150° or more). Defined. In this test, the contact angle was measured in the same manner as ⁇ water contact angle (static contact angle)>.
  • ⁇ Snow accretion test> An evaluation sample (film) is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the sample is subjected to a wind speed of 10 m / sec, Artificial snow prepared in advance was blown under the condition of a collision amount of 110 kg/m 2 /h. This blowing caused the artificial snow to impinge on the sample (coating) surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. The start time (that is, the non-snow accretion time) was used.
  • Table 1 shows the results of the static contact angle of water (20 ⁇ L of water), wear resistance evaluation, and snow accretion start time. It was confirmed that all of the films obtained in Examples were excellent in both abrasion resistance and snow adhesion prevention performance. On the other hand, the coatings obtained in the comparative examples were formed from a composition in which the inorganic fine particles were not appropriately blended, so the wear resistance was remarkably deteriorated.

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Abstract

The present disclosure provides: a coating-forming composition from which a coating having excellent water repellency and excellent wear resistance can be formed; a coating; and a chemical liquid. The composition comprises inorganic fine particles, a polymerizable component, and a water-repellent component, wherein: the inorganic fine particles comprise first inorganic fine particles having an average particle diameter of 1-100 nm and second inorganic fine particles having an average particle diameter of 500 nm to 5 μm; the content of the first inorganic fine particles is 3-25 parts by mass with respect to 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component; the content of the second inorganic fine particles is 12-27 parts by mass with respect to 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component; and the water-repellent component is a polymer having at least a structural unit based on a specific compound.

Description

被膜形成用組成物及び被膜並びに薬液Film-forming composition, film, and chemical solution
 本開示は、被膜形成用組成物及び被膜並びに薬液に関する。 The present disclosure relates to a film-forming composition, a film, and a chemical solution.
 従来、超撥水性を対象物の表面に付与しうる被膜が種々提案されている。例えば、特許文献1には、重合性基を有する微粒子及び分子内に2つ以上の重合性基を有する化合物を用いることで、超撥水性及び耐摩耗性を両立した超撥水性被膜を形成できることが開示されている。特許文献2には、フッ素原子を含む被膜であって、被膜の諸性能を適切に制御することで、超撥水性及び耐摩耗性を両立した超撥水性被膜を形成できる技術が開示されている。 Conventionally, various coatings have been proposed that can impart super water repellency to the surface of objects. For example, Patent Document 1 discloses that a super water-repellent film having both super water repellency and abrasion resistance can be formed by using fine particles having a polymerizable group and a compound having two or more polymerizable groups in the molecule. is disclosed. Patent Document 2 discloses a technique for forming a super water-repellent film that is a film containing fluorine atoms and has both super water repellency and abrasion resistance by appropriately controlling various properties of the film. .
 また、特許文献3には、フルオロオレフィン、パーフルオロアルキル基含有単量体、水酸基含有不飽和単量体を含むフッ素系共重合体と、シリカ微粉末を含む、被膜形成用の組成物が開示されている。斯かる組成物によれば、撥水撥油性や離型性、剥離性、保存安定性に優れる被膜を形成できるとされている。 Further, Patent Document 3 discloses a film-forming composition containing a fluorine-based copolymer containing a fluoroolefin, a perfluoroalkyl group-containing monomer, and a hydroxyl group-containing unsaturated monomer, and silica fine powder. It is Such a composition is said to be capable of forming a film having excellent water and oil repellency, releasability, releasability, and storage stability.
国際公開第2016/056663号WO2016/056663 国際公開第2017/179678号WO2017/179678 特開2011-84745号公報JP 2011-84745 A
 本開示は、優れた撥水性を有し、耐摩耗性にも優れる被膜を形成することができる被膜形成用組成物及び被膜並びに薬液を提供することを目的とする。 An object of the present disclosure is to provide a film-forming composition, a film, and a chemical solution capable of forming a film having excellent water repellency and excellent abrasion resistance.
 すなわち、本開示は、例えば、以下の項に記載の主題を包含する。
項1
無機微粒子と、重合性成分と、撥水性成分とを含み、
前記無機微粒子は、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含み、
前記第1の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、3~25質量部であり、
前記第2の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、12~27質量部であり、
前記第1の無機微粒子及び前記第2の無機微粒子の総含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、20質量部以上であり、
前記撥水性成分は、下記一般式(1):
That is, the present disclosure encompasses subject matter described in, for example, the following sections.
Item 1
including inorganic fine particles, a polymerizable component, and a water-repellent component,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
The content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
The total content of the first inorganic fine particles and the second inorganic fine particles per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component, 20 parts by mass or more,
The water-repellent component has the following general formula (1):
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
(式中、Xは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX基(但し、XおよびXは、同一又は異なって、水素原子、フッ素原子又は塩素原子である。)、シアノ基、炭素数1~6の直鎖状又は分岐状のフルオロアルキル基、置換又は非置換のベンジル基、置換又は非置換のフェニル基、もしくは炭素数1~20の直鎖状または分岐状アルキル基であり、Yは、直接結合、酸素原子を有していてもよい炭素数1~10の炭化水素基、-CHCHN(R)SO-基(但し、Rは炭素数1~4のアルキル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、-CHCH(OY)CH-基(但し、Yは水素原子またはアセチル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、又は-(CHSO-基(nは1~10であり、式の右端がRに、左端がOにそれぞれ結合している。)であり、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、分子量300~50000のポリシロキサン、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である。)で表される化合物に基づく構造単位を少なくとも有する重合体である、被膜形成用組成物。
項2
前記第2の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、15~27質量部であり、
前記式(1)中、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である、項1に記載の被膜形成用組成物。
項3
前記撥水性成分の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、0.1~30質量部である、項1又は2に記載の被膜形成用組成物。
項4
前記重合性成分は、架橋性官能基を有する重合体及び硬化剤である、項1~3のいずれか1項に記載の被膜形成用組成物。
項5
項1~4のいずれか1項に記載の被膜形成用組成物の硬化物を含む、被膜。
項6
無機微粒子と、バインダー成分と、撥水性成分とを含み、
前記無機微粒子は、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含み、
前記第1の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、3~25質量部であり、
前記第2の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、12~27質量部であり、
前記第1の無機微粒子及び前記第2の無機微粒子の総含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、20質量部以上であり、
前記撥水性成分は、下記一般式(1):
(Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, 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 (with the proviso that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R a and the left end is bonded to O.), —CH 2 CH(OY 1 )CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R a and the left end is bonded to O.), or a —(CH 2 ) n SO 2 — group (where n is 1 to 10). , The right end of the formula is bonded to Ra , and the left end is bonded to O.), where Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.). A film-forming composition, which is a polymer.
Item 2
The content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
In the above formula (1), R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 Item 2. The film-forming composition according to Item 1, which is a fluoropolyether group having a molecular weight of 400 to 5,000.
Item 3
The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component. Item 3. The film-forming composition according to Item 1 or 2.
Item 4
4. The film-forming composition according to any one of Items 1 to 3, wherein the polymerizable component is a polymer having a crosslinkable functional group and a curing agent.
Item 5
A film comprising a cured product of the film-forming composition according to any one of Items 1 to 4.
Item 6
including inorganic fine particles, a binder component, and a water-repellent component,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
The content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
The total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component. Part by mass or more,
The water-repellent component has the following general formula (1):
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
(式中、Xは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX基(但し、XおよびXは、同一又は異なって、水素原子、フッ素原子又は塩素原子である。)、シアノ基、炭素数1~6の直鎖状又は分岐状のフルオロアルキル基、置換又は非置換のベンジル基、置換又は非置換のフェニル基、もしくは炭素数1~20の直鎖状または分岐状アルキル基であり、Yは、直接結合、酸素原子を有していてもよい炭素数1~10の炭化水素基、-CHCHN(R)SO-基(但し、Rは炭素数1~4のアルキル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、-CHCH(OY)CH-基(但し、Yは水素原子またはアセチル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、又は-(CHSO-基(nは1~10であり、式の右端がRに、左端がOにそれぞれ結合している。)であり、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、分子量300~50000のポリシロキサン、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である。)で表される化合物に基づく構造単位を少なくとも有する重合体である、被膜。
項7
前記第2の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、15~27質量部であり、
前記式(1)中、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である、項6に記載の被膜。
項8
前記撥水性成分の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、0.1~30質量部である、項6又は7に記載の被膜。
項9
無機微粒子を含む被膜において、
前記無機微粒子は、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含み、
水の接触角が、150°以上であり、
紙製ウエスを荷重100g/cmで少なくとも50回塗擦した後の水の接触角が、150°以上である、被膜。
項10
下記着雪試験により測定される着雪開始時間が5分以上である、請求項5~9のいずれか1項に記載の被膜。
<着雪試験>
1~2℃の範囲で恒温に保った試験室内の試験台に、着雪面が地面に対して鉛直になるように被膜を設置し、該被膜に対し、風速10m/sec、衝突量110kg/m/hの条件下で、予め作製した人工雪を吹きつける。この吹きつけは、被膜表面に人口雪が衝突するようにする。この吹きつけ開始時から、サンプルの吹き付け面全面を動画撮影して試験終了後に得られた映像から被膜表面の着雪の有無を目視で確認し、吹きつけ開始から着雪までの時間を着雪開始時間(無着雪時間)として計測する。
項11
項1~4のいずれか1項に記載の被膜形成用組成物を含む、薬液。
(Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, 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 (with the proviso that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R a and the left end is bonded to O.), —CH 2 CH(OY 1 )CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R a and the left end is bonded to O.), or a —(CH 2 ) n SO 2 — group (where n is 1 to 10). , The right end of the formula is bonded to Ra , and the left end is bonded to O.), where Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.). A coating that is a polymer.
Item 7
The content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
In the above formula (1), R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 Alternatively, the coating according to item 6, which is a fluoropolyether group having a molecular weight of 400 to 5,000.
Item 8
The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component. The coating according to 6 or 7.
Item 9
In a coating containing inorganic fine particles,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The contact angle of water is 150° or more,
A film having a water contact angle of 150° or more after being rubbed with a paper waste cloth at least 50 times with a load of 100 g/cm 2 .
Item 10
The coating according to any one of claims 5 to 9, wherein the snow accretion start time measured by the following snow accretion test is 5 minutes or longer.
<Snow accretion test>
A coating is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the coating is subjected to a wind speed of 10 m / sec and a collision amount of 110 kg /. Pre-made artificial snow is blown under the condition of m 2 /h. This blowing causes the artificial snow to impinge on the covering surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. Measured as the start time (no snow accretion time).
Item 11
A chemical solution comprising the film-forming composition according to any one of Items 1 to 4.
 本開示の被膜形成用組成物によれば、優れた撥水性を有し、耐摩耗性にも優れる被膜を形成することができる。 According to the film-forming composition of the present disclosure, a film having excellent water repellency and excellent abrasion resistance can be formed.
 従来の超撥水性被膜は、優れた撥水性を有しているものの、耐摩耗性が十分でないことが多く、結果として、長期的に使用し続けると、摩耗により被膜が劣化し、撥水性が低下する等の問題を抱えていた。この観点から、超撥水性被膜においては、高い撥水性を維持しつつ、耐摩耗性を向上させることも求められていた。 Although conventional super water-repellent coatings have excellent water repellency, they often lack sufficient abrasion resistance. I was having problems with the drop. From this point of view, the superhydrophobic coating has been required to improve abrasion resistance while maintaining high water repellency.
 本発明者らは、かかる事情に鑑み、優れた撥水性を有し、耐摩耗性にも優れる被膜を形成することを目的として鋭意研究を重ねた。その結果、特定の無機微粒子、重合性成分及び撥水性成分を組み合わせ、特に、無機微粒子として平均粒子径が異なる2種類の微粒子を併用することで、高い撥水性を維持しつつ、耐摩耗性が向上する被膜を形成できることがわかり、上記目的を達成できることを見出した。加えて、斯かる被膜は、優れた着雪防止性能をも有し得ることを見出した。以下、本開示の実施形態について詳細に説明する。 In view of these circumstances, the present inventors have conducted extensive research with the aim of forming a film that has excellent water repellency and excellent abrasion resistance. As a result, by combining specific inorganic fine particles, a polymerizable component and a water-repellent component, in particular, by using two types of fine particles having different average particle sizes as inorganic fine particles in combination, abrasion resistance can be improved while maintaining high water repellency. It has been found that an improved coating can be formed, and the above objects can be achieved. In addition, we have found that such a coating can also have excellent anti-snow accretion performance. Hereinafter, embodiments of the present disclosure will be described in detail.
 以下、本発明の実施形態について詳細に説明する。なお、本明細書中において、「含有」及び「含む」なる表現については、「含有」、「含む」、「実質的にからなる」及び「のみからなる」という概念を含む。 Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expressions "contain" and "include" include the concepts of "contain", "include", "substantially consist of" and "consist only of".
 本明細書において「~」を用いて示された数値範囲は、「~」の前後に記載される数値を夫々最小値及び最大値として含む範囲を示す。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値と任意に組み合わせることができる。本明細書に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値又は実施例から一義的に導き出せる値に置き換えてもよい。 In this specification, the numerical range indicated using "-" indicates the range including the numerical values before and after "-" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step. In the numerical ranges described herein, the upper and lower limits of the numerical ranges may be replaced with values shown in Examples or values that can be uniquely derived from Examples.
 1.被膜形成用組成物
 本開示の被膜形成用組成物は、少なくとも無機微粒子と、重合性成分と、撥水性成分とを含む。まず、これら各成分について詳述する。
1. Film-Forming Composition The film-forming composition of the present disclosure contains at least inorganic fine particles, a polymerizable component, and a water-repellent component. First, each of these components will be described in detail.
 (無機微粒子)
 無機微粒子は、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含む。本開示の被膜形成用組成物が大きさの異なる2種の無機微粒子を含むことによって、第1の無機微粒子が被膜に埋没することなく、表面に特有の微細な凹凸構造を形成することができ、これにより、撥水性、付着防止性が顕著に向上する。また、本開示の被膜形成用組成物が無機微粒子を含むことで被膜の強度が向上し、さらに摩耗時に第1の無機微粒子の滑落を第2の無機微粒子が防止するので、被膜の耐摩耗性が向上する。
(Inorganic fine particles)
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less. By including two types of inorganic fine particles having different sizes in the film-forming composition of the present disclosure, the first inorganic fine particles are not embedded in the coating, and a unique fine uneven structure can be formed on the surface. As a result, water repellency and anti-adhesion properties are remarkably improved. In addition, since the film-forming composition of the present disclosure contains inorganic fine particles, the strength of the film is improved, and the second inorganic fine particles prevent the first inorganic fine particles from sliding down during abrasion, so the abrasion resistance of the film is improved. improves.
 本開示の被膜形成用組成物において、第1の無機微粒子の平均粒子径は以下の方法で計測することができる。まず、被膜形成用組成物の揮発分成分を加熱処理(300℃、3時間)により除去する。これにより得られた微粒子を走査型電子顕微鏡によって直接観察し、撮影画像中の微粒子を200個選択する。ただし、この選択にあたって、微粒子の円相当径が450nm以上の微粒子は選択しないようにする。選択した200個の微粒子の円相当径の平均値を算出し、この値を被膜形成用組成物中の第1の無機微粒子の平均粒子径とする。 In the film-forming composition of the present disclosure, the average particle size of the first inorganic fine particles can be measured by the following method. First, the volatile components of the film-forming composition are removed by heat treatment (300° C., 3 hours). The microparticles thus obtained are directly observed with a scanning electron microscope, and 200 microparticles in the photographed image are selected. However, in this selection, fine particles having an equivalent circle diameter of 450 nm or more should not be selected. The average value of the equivalent circle diameters of the selected 200 fine particles is calculated, and this value is taken as the average particle size of the first inorganic fine particles in the film-forming composition.
 本開示の被膜形成用組成物において、第2の無機微粒子の平均粒子径は以下の方法で計測することができる。まず、被膜形成用組成物の揮発分成分を加熱処理(300℃、3時間)により除去する。これにより得られた微粒子を走査型電子顕微鏡によって直接観察し、撮影画像中の微粒子を200個選択する。ただし、この選択にあたって、微粒子の円相当径が450nm以上の微粒子を選択するようにする。選択した200個の微粒子の円相当径の平均値を算出し、この値を被膜形成用組成物中の第1の無機微粒子の平均粒子径とする。 In the film-forming composition of the present disclosure, the average particle size of the second inorganic fine particles can be measured by the following method. First, the volatile components of the film-forming composition are removed by heat treatment (300° C., 3 hours). The microparticles thus obtained are directly observed with a scanning electron microscope, and 200 microparticles in the photographed image are selected. However, in this selection, fine particles having an equivalent circle diameter of 450 nm or more are selected. The average value of the equivalent circle diameters of the selected 200 fine particles is calculated, and this value is taken as the average particle size of the first inorganic fine particles in the film-forming composition.
 第1の無機微粒子は、平均粒子径が1nm未満となると、凝集が起こりやすくなり、被膜形成用組成物の被膜の撥水性及び耐摩耗性が低下しやすい。また、第1の無機微粒子は、平均粒子径が100nmを超えると、第2の無機微粒子の平均粒子径との差が小さくなり、異なる平均粒子径を併用することの効果を十分に得られず、この結果、被膜形成用組成物の被膜の耐摩耗性が向上しにくくなる。 When the average particle diameter of the first inorganic fine particles is less than 1 nm, aggregation tends to occur, and the water repellency and abrasion resistance of the coating of the coating composition tend to decrease. In addition, when the average particle diameter of the first inorganic fine particles exceeds 100 nm, the difference between the average particle diameter of the second inorganic fine particles and the average particle diameter of the second inorganic fine particles becomes small, and the effect of using different average particle diameters together cannot be sufficiently obtained. As a result, it becomes difficult to improve the abrasion resistance of the film of the film-forming composition.
 第1の無機微粒子の平均粒子径は、好ましくは2nm以上、より好ましくは3nm以上、さらに好ましくは4nm以上、特に好ましくは5nm以上である。また、第1の無機微粒子の平均粒子径は、好ましくは80nm以下、より好ましくは60nm以下、さらに好ましくは50nm以下、特に好ましくは30nm以下である。 The average particle size of the first inorganic fine particles is preferably 2 nm or more, more preferably 3 nm or more, even more preferably 4 nm or more, and particularly preferably 5 nm or more. The average particle size of the first inorganic fine particles is preferably 80 nm or less, more preferably 60 nm or less, even more preferably 50 nm or less, and particularly preferably 30 nm or less.
 第2の無機微粒子は、平均粒子径が500nm未満となると、第1の無機微粒子の平均粒子径との差が小さくなり、異なる平均粒子径を併用することの効果を十分に得られず、この結果、被膜形成用組成物の被膜の耐摩耗性が向上しにくくなり、また、着雪防止性能も悪化する。また、第2の無機微粒子は、平均粒子径が5μmを超えると、高い撥水性が得られず、また、粒子が被膜から脱落しやすくなって、被膜形成用組成物の被膜の耐摩耗性が向上しにくくなる。 When the average particle diameter of the second inorganic fine particles is less than 500 nm, the difference from the average particle diameter of the first inorganic fine particles becomes small, and the effect of using different average particle diameters together cannot be sufficiently obtained. As a result, it becomes difficult to improve the abrasion resistance of the film of the film-forming composition, and the anti-snow accretion performance is also deteriorated. If the average particle diameter of the second inorganic fine particles exceeds 5 µm, high water repellency cannot be obtained, and the particles tend to fall off the coating, resulting in poor abrasion resistance of the coating of the coating composition. difficult to improve.
 第2の無機微粒子の平均粒子径は、好ましくは800nm以上、より好ましくは1μm以上、さらに好ましくは1.5μm以上、特に好ましくは2μm以上である。また、第2の無機微粒子の平均粒子径は、好ましくは4.5μm以下、より好ましくは4μm以下、さらに好ましくは3.5μm以下、特に好ましくは3μm以下である。 The average particle diameter of the second inorganic fine particles is preferably 800 nm or more, more preferably 1 µm or more, even more preferably 1.5 µm or more, and particularly preferably 2 µm or more. The average particle size of the second inorganic fine particles is preferably 4.5 μm or less, more preferably 4 μm or less, still more preferably 3.5 μm or less, and particularly preferably 3 μm or less.
 第1の無機微粒子及び第2の無機微粒子は、前述の平均粒子径を満たす限り、その種類は特に限定されず、例えば、公知の金属酸化物の微粒子を広く例示することができる。具体的に金属酸化物としては、シリカ、アルミナ、酸化チタン、ジルコニア等を挙げることができ、被膜の硬度及び耐水性が高まりやすいという点で、第1の無機微粒子及び第2の無機微粒子はシリカであることが好ましい。第1の無機微粒子及び第2の無機微粒子の種類は同一であってもよいし、異なっていてもよく、好ましくは、第1の無機微粒子及び第2の無機微粒子が同一であり、より好ましくは、第1の無機微粒子及び第2の無機微粒子がいずれもシリカである。 The types of the first inorganic fine particles and the second inorganic fine particles are not particularly limited as long as they satisfy the aforementioned average particle diameter, and for example, a wide range of known metal oxide fine particles can be exemplified. Specific examples of metal oxides include silica, alumina, titanium oxide, zirconia, and the like, and the first inorganic fine particles and the second inorganic fine particles are silica in that the hardness and water resistance of the coating are likely to increase. is preferably The types of the first inorganic fine particles and the second inorganic fine particles may be the same or different, preferably the first inorganic fine particles and the second inorganic fine particles are the same, more preferably , both the first inorganic fine particles and the second inorganic fine particles are silica.
 第1の無機微粒子及び第2の無機微粒子の比表面積は特に限定されず、例えば、得られる被膜の硬度が向上しやすい点で、30~700m/gであることが好ましく、80~330m/gであることがさらに好ましい。本開示の被膜形成用組成物において、前記微粒子の比表面積は、BET法によって計測された値(いわゆるBET比表面積)を意味する。 The specific surface areas of the first inorganic fine particles and the second inorganic fine particles are not particularly limited. For example, the specific surface area is preferably 30 to 700 m 2 /g, more preferably 80 to 330 m 2 in terms of easily improving the hardness of the obtained coating. /g is more preferred. In the film-forming composition of the present disclosure, the specific surface area of the fine particles means a value measured by the BET method (so-called BET specific surface area).
 第1の無機微粒子及び第2の無機微粒子は、表面が親水性であってもよいし、疎水性であってもよい。第1の無機微粒子及び第2の無機微粒子は、親水性及び疎水性の混合物であってもよい。第1の無機微粒子及び第2の無機微粒子は濡れ性を制御すべく、表面処理剤で処理されていてもよい。第1の無機微粒子及び第2の無機微粒子は、表面にラジカル重合性の反応基(例えば、アクリロイル基等の重合性二重結合)を有していないことが好ましく、即ち、第1の無機微粒子及び第2の無機微粒子の表面には重合体が共有結合的に結合しないことが好ましい。これにより、被膜の耐摩耗性が向上し、特には着雪防止性能も高まりやすい。 The surfaces of the first inorganic fine particles and the second inorganic fine particles may be hydrophilic or hydrophobic. The first inorganic fine particles and the second inorganic fine particles may be a mixture of hydrophilic and hydrophobic properties. The first inorganic fine particles and the second inorganic fine particles may be treated with a surface treatment agent to control wettability. The first inorganic fine particles and the second inorganic fine particles preferably do not have a radically polymerizable reactive group (for example, a polymerizable double bond such as an acryloyl group) on the surface, that is, the first inorganic fine particles And it is preferable that the polymer is not covalently bonded to the surface of the second inorganic fine particles. As a result, the wear resistance of the coating is improved, and particularly the snow accretion prevention performance is likely to be enhanced.
 第1の無機微粒子及び第2の無機微粒子の形状も特に限定されず、例えば、球状、楕円球状等を挙げることができ、また、異形状等の不定形粒子であってもよい。第1の無機微粒子及び第2の無機微粒子は、凝集体を形成することもできる。凝集体は球体及び非球体のいずれでもよいし、鎖状的に形成されていてもよい。 The shape of the first inorganic fine particles and the second inorganic fine particles is also not particularly limited, and examples thereof include spherical, ellipsoidal and the like, and may be amorphous particles such as irregular shaped particles. The first inorganic fine particles and the second inorganic fine particles can also form aggregates. Aggregates may be spherical or non-spherical, and may be chain-like.
 本開示の被膜形成用組成物に含まれる無機微粒子は、第1の無機微粒子及び第2の無機微粒子を80質量%以上含むことができ、好ましくは90質量%以上、より好ましくは95質量%以上、さらに好ましくは99質量%以上である。本開示の被膜形成用組成物に含まれる無機微粒子は、第1の無機微粒子及び第2の無機微粒子のみであってもよく、第1の無機微粒子及び第2の無機微粒子のみであることが特に好ましい。 The inorganic fine particles contained in the film-forming composition of the present disclosure can contain 80% by mass or more of the first inorganic fine particles and the second inorganic fine particles, preferably 90% by mass or more, and more preferably 95% by mass or more. , more preferably 99% by mass or more. The inorganic fine particles contained in the film-forming composition of the present disclosure may be only the first inorganic fine particles and the second inorganic fine particles, and particularly the first inorganic fine particles and the second inorganic fine particles. preferable.
 本開示の被膜形成用組成物において、第1の無機微粒子及び第2の無機微粒子の両者の含有比率は特に制限されない。本開示の被膜形成用組成物が、優れた撥水性を有し、かつ、耐摩耗性及び着雪防止性能に優れる被膜を形成しやすい点で、第1の無機微粒子及び第2の無機微粒子の総質量に対し、第1の無機微粒子が5質量%以上であることが好ましく、10質量%以上であることがより好ましく、20質量%以上であることがさらに好ましい。また、第1の無機微粒子及び第2の無機微粒子の総質量に対し、第1の無機微粒子が90質量%以下であることが好ましく、80質量%以下であることがより好ましく、60質量%以下であることがさらに好ましく、50質量%以下であることが特に好ましい。 In the film-forming composition of the present disclosure, the content ratio of both the first inorganic fine particles and the second inorganic fine particles is not particularly limited. The film-forming composition of the present disclosure has excellent water repellency and easily forms a film having excellent abrasion resistance and snow accretion prevention performance. The first inorganic fine particles are preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more of the total mass. Further, the first inorganic fine particles are preferably 90% by mass or less, more preferably 80% by mass or less, and 60% by mass or less with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. More preferably, the content is particularly preferably 50% by mass or less.
 (撥水性成分)
 本開示の被膜形成用組成物において、撥水性成分は、被膜が形成されたときに被膜に撥水性を付与することができる成分であって、下記一般式(1)で表される化合物に基づく構成単位を有する重合体である。
(Water repellent component)
In the film-forming composition of the present disclosure, the water-repellent component is a component capable of imparting water repellency to the film when the film is formed, and is based on a compound represented by the following general formula (1). It is a polymer having structural units.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
 前記式(1)中、Xは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX基(但し、XおよびXは、同一又は異なって、水素原子、フッ素原子又は塩素原子である。)、シアノ基、炭素数1~6の直鎖状又は分岐状のフルオロアルキル基、置換又は非置換のベンジル基、置換又は非置換のフェニル基、もしくは炭素数1~20の直鎖状または分岐状アルキル基を示す。Xが炭素数3以上のアルキル基又はフルオロアルキル基である場合、これらは環状又は非環状のいずれであってもよい。また、Xがアルキル基の場合、その炭素数は、好ましくは1~10、より好ましくは1~6、さらに好ましくは1~2である。また、フルオロアルキル基の場合、その炭素数は、好ましくは1~6、より好ましくは1~4、さらに好ましくは1~2である。 In the above formula (1), X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different, a hydrogen atom, a fluorine atom, or chlorine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a 1 to 20 carbon atoms represents a linear or branched alkyl group. When X is an alkyl group having 3 or more carbon atoms or a fluoroalkyl group, these may be either cyclic or acyclic. When X is an alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 2 carbon atoms. The fluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 2 carbon atoms.
 前記式(1)中、Yは、直接結合、酸素原子を有していてもよい炭素数1~10の炭化水素基、-CHCHN(R)SO-基(但し、Rは炭素数1~4のアルキル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、-CHCH(OY)CH-基(但し、Yは水素原子またはアセチル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、又は-(CHSO-基(nは1~10であり、式の右端がRに、左端がOにそれぞれ結合している。)を示す。「直接結合」とは、前記式(1)において、Yの両端のRとOとが直接結合していることを意味し、つまりは、Yは元素を含まないことを意味する。Yが炭素数1~10の炭化水素基である場合、具体的には、炭素数1~10のアルキレン基であり、好ましくは炭素数1~6のアルキレン基、さらに好ましくは炭素数1~2のアルキレン基である。 In the above formula (1), Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms optionally having an oxygen atom, a —CH 2 CH 2 N(R 1 )SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R a and the left end is bonded to O.), —CH 2 CH(OY 1 )CH 2 — group (with the proviso that Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R a and the left end is bonded to O.), or a —(CH 2 ) n SO 2 — group (where n is 1 to 10, and the formula The right end of is bound to Ra , and the left end is bound to O.). "Direct bond" means that R a and O at both ends of Y are directly bonded in the above formula (1), that is, Y does not contain an element. When Y is a hydrocarbon group having 1 to 10 carbon atoms, it is specifically an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms. is an alkylene group of
 前記式(1)中、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、分子量300~50000のポリシロキサン、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基を示す。フルオロアルキル基は、例えば、パーフルオロアルキル基であることが好ましい。ポリシロキサンは、ポリジメチルシロキサンであることが好ましく、R-(Si(CHO)-であることがより好ましい。R-(Si(CHO)-において、Rは炭素数1~20の直鎖状又は分岐状のアルキル基であり、炭素数1~12が好ましく、炭素数1~6がより好ましい。R-(Si(CHO)-において、nは3~680であり、nは10~500が好ましく、nは100~400がより好ましい。フルオロポリエーテル基は、例えば、パーオロポリエーテル基であることが好ましい。 In the above formula (1), R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, a polysiloxane having a molecular weight of 300 to 50,000, or It represents a polyether group with a molecular weight of 400-5000 or a fluoropolyether group with a molecular weight of 400-5000. The fluoroalkyl group is preferably, for example, a perfluoroalkyl group. The polysiloxane is preferably polydimethylsiloxane, more preferably R 2 —(Si(CH 3 ) 2 O) n —. In R 2 —(Si(CH 3 ) 2 O) n —, R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and 1 to 6 carbon atoms. is more preferred. In R 2 —(Si(CH 3 ) 2 O) n —, n is 3-680, preferably 10-500, more preferably 100-400. The fluoropolyether group is preferably, for example, a perolopolyether group.
 式(1)で表される化合物の具体例としては、例えば、前述の特許文献1に開示されているアクリル酸エステルを広く挙げることができる。 Specific examples of the compound represented by Formula (1) include a wide range of acrylic acid esters disclosed in Patent Document 1 described above.
 中でも、形成される被膜の撥水性及び撥油性に優れ、耐摩耗性も向上しやすいという観点から、式(1)で表される化合物は、Xが水素原子、塩素原子、フッ素原子、又はメチル基であり、Yが直接結合又は炭素数1~10のアルキレン基(好ましくは炭素数1~6のアルキレン基、さらに好ましくは炭素数1~2のアルキレン基)であり、Rが炭素数1~20の直鎖状又は分岐状のアルキル基、炭素数1~6の直鎖状又は分岐状のフルオロアルキル基、分子量300~50000のポリシロキサン、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である組み合わせを挙げることができる。より好ましい式(1)で表される化合物は、Xが水素原子又はメチル基、Yが炭素数1~2のアルキレン基、Rが炭素数1~6の直鎖状又は分岐状のフルオロアルキル基若しくは分子量300~50000のポリシロキサンである。また、Xが水素原子又はメチル基、Yが直接結合、Rが炭素数1~20の直鎖状又は分岐状のアルキル基若しくは分子量300~50000のポリシロキサンである組み合わせも好ましい。 Among them, the compound represented by the formula (1) has a hydrogen atom, a chlorine atom, a fluorine atom, or a methyl Y is a direct bond or an alkylene group having 1 to 10 carbon atoms (preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms), and R a is 1 carbon atom -20 linear or branched alkyl groups, C1-6 linear or branched fluoroalkyl groups, polysiloxanes with molecular weights of 300 to 50,000, or polyether groups with molecular weights of 400 to 5,000, or molecular weights of 400 Combinations of ˜5000 fluoropolyether groups can be mentioned. A more preferred compound represented by formula (1) has X being a hydrogen atom or a methyl group, Y being an alkylene group having 1 to 2 carbon atoms, and R a being a linear or branched fluoroalkyl having 1 to 6 carbon atoms. It is a polysiloxane with a group or molecular weight of 300-50,000. A combination in which X is a hydrogen atom or a methyl group, Y is a direct bond, and R a is a linear or branched alkyl group having 1 to 20 carbon atoms or polysiloxane having a molecular weight of 300 to 50,000 is also preferred.
 式(1)で表される化合物の具体的な化合物として、フルオロアルキル基の炭素数が1~6のフルオロアルキル(メタ)アクリレート及びアルキル基の炭素数が1~20(好ましくは1~18)のアルキル(メタ)アクリレートが挙げられる。また、式(1)で表される化合物は、市販品から入手することもできる。例えば、式(1)で表される化合物において、Rが分子量300~50000のポリシロキサンである化合物としては、JNC社製の商品名「サイラプレーン(登録商標)FM-0711」、「サイラプレーン(登録商標)FM-0721」、「サイラプレーン(登録商標)FM-0725」、「サイラプレーン(登録商標)FM-0701T」を挙げることができる。 Specific compounds of the compound represented by formula (1) include fluoroalkyl (meth)acrylates having a fluoroalkyl group having 1 to 6 carbon atoms and alkyl groups having 1 to 20 carbon atoms (preferably 1 to 18). of alkyl (meth)acrylates. Moreover, the compound represented by Formula (1) can also be obtained from a commercial item. For example, in the compound represented by the formula (1), examples of compounds in which Ra is a polysiloxane having a molecular weight of 300 to 50000 include JNC's product names "Silaplane (registered trademark) FM-0711" and "Silaplane (registered trademark) FM-0721”, “Silaplane (registered trademark) FM-0725”, and “Silaplane (registered trademark) FM-0701T”.
 撥水性成分は、式(1)で表される化合物の他、エポキシ部位を有する(メタ)アクリレートに基づく構成単位又は、アミド結合を有する(メタ)アクリレート(例えば、前記式(1)のYがアミド結合を有する官能基に置き換えられた化合物)に基づく構成単位を含むことができる。例えば、エポキシ部位を有する(メタ)アクリレートとしてはグリシジル(メタ)アクリレートを挙げることができ、アミド結合を有する(メタ)アクリレートとしてはステアリン酸アミドエチル(メタ)アクリレートを挙げることができる。 In addition to the compound represented by the formula (1), the water-repellent component is a structural unit based on a (meth)acrylate having an epoxy site, or a (meth)acrylate having an amide bond (for example, Y in the formula (1) is compound replaced with a functional group having an amide bond). For example, the (meth)acrylate having an epoxy moiety can be glycidyl (meth)acrylate, and the (meth)acrylate having an amide bond can be stearamidoethyl (meth)acrylate.
 また、式(1)で表される化合物に基づく構造単位を少なくとも有する重合体は、式(1)で表される化合物以外に基づく構成単位を含むことができる。斯かる構成単位として、ヒドロキシアルキル(メタ)アクリレートに基づく構成単位、エポキシ部位を有する(メタ)アクリレートに基づく構成単位、アミド結合を有する(メタ)アクリレート(例えば、前記式(1)のYがアミド結合を有する官能基に置き換えられた化合物)に基づく構成単位、塩素含有ビニルモノマーに基づく構成単位、塩素含有ビニリデンモノマーに基づく構成単位、アクリルアミドモノマーに基づく構成単位等のいずれか1種以上を挙げることができる。例えば、ヒドロキシアルキル(メタ)アクリレートに基づく構成単位としてはとしては、2-ヒドロキシエチルメタアクリレート等を挙げることができ、エポキシ部位を有する(メタ)アクリレートとしてはグリシジル(メタ)アクリレート等を挙げることができ、アミド結合を有する(メタ)アクリレートとしてはステアリン酸アミドエチル(メタ)アクリレート等を挙げることができ、塩素含有ビニルモノマーとしては塩化ビニル等を挙げることができ、塩素含有ビニリデンモノマーとしては塩化ビニリデン等を挙げることができ、アクリルアミドモノマーとしてはN-メチロールアクリルアミドを挙げることができる。 In addition, the polymer having at least a structural unit based on the compound represented by formula (1) can contain a structural unit based on a compound other than the compound represented by formula (1). Examples of such structural units include structural units based on hydroxyalkyl (meth)acrylates, structural units based on (meth)acrylates having an epoxy site, and (meth)acrylates having an amide bond (for example, Y in the formula (1) is amide a compound substituted with a functional group having a bond), a structural unit based on a chlorine-containing vinyl monomer, a structural unit based on a chlorine-containing vinylidene monomer, a structural unit based on an acrylamide monomer, etc. can be done. For example, structural units based on hydroxyalkyl (meth)acrylates include 2-hydroxyethyl methacrylate and the like, and (meth)acrylates having an epoxy moiety include glycidyl (meth)acrylate and the like. Examples of (meth)acrylates having an amide bond include stearamidoethyl (meth)acrylate. Examples of chlorine-containing vinyl monomers include vinyl chloride. Examples of chlorine-containing vinylidene monomers include vinylidene chloride. and the acrylamide monomer can include N-methylolacrylamide.
 式(1)で表される化合物に基づく構造単位を少なくとも有する重合体には、さらに他の構造単位が含まれていてもよい。他の構造単位を形成するための単量体としては、種々の単官能単量体及び/又は多官能単量体の1種以上を挙げることができる。斯かる単量体は、エチレン性不飽和二重結合を有するものであって、酸基含有単量体、水酸基含有単量体、塩素含有単量体、窒素含有単量体、アルキレングリコール基含有単量体、アルコキシアルキル基含有単量体、カルボニル基含有単量体、シラン基含有単量体、環構造含有単量体などが挙げられるが、本発明は、これらに限定されるものではない。 The polymer having at least structural units based on the compound represented by formula (1) may further contain other structural units. Monomers for forming other structural units may include one or more of various monofunctional monomers and/or polyfunctional monomers. Such monomers have ethylenically unsaturated double bonds and include acid group-containing monomers, hydroxyl group-containing monomers, chlorine-containing monomers, nitrogen-containing monomers, alkylene glycol group-containing Examples include monomers, alkoxyalkyl group-containing monomers, carbonyl group-containing monomers, silane group-containing monomers, ring structure-containing monomers, etc., but the present invention is not limited thereto. .
 酸基含有単量体としては、(メタ)アクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、無水マレイン酸、マレイン酸モノメチルエステル、マレイン酸モノブチルエステル、イタコン酸モノメチルエステル、イタコン酸モノブチルエステル、ビニル安息香酸などが挙げられる。 Acid group-containing monomers include (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, Itaconic acid monobutyl ester, vinyl benzoic acid and the like can be mentioned.
 水酸基含有単量体としては、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートなどが挙げられる。 Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) acrylates and the like.
 塩素含有単量体としては、塩化ビニル、塩化ビニリデンなどが挙げられる。  Chlorine-containing monomers include vinyl chloride and vinylidene chloride.
 窒素含有単量体としては、(メタ)アクリルアミド、N-モノメチル(メタ)アクリルアミド、N-モノエチル(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-n-プロピル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、メチレンビス(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、ジメチルアミノエチル(メタ)アクリルアミド、N,N-ジメチルアミノプロピルアクリルアミド、ジアセトンアクリルアミド、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ステアリン酸アミドエチル(メタ)アクリレート、N-ビニルピロリドン、(メタ)アクリロニトリルなどが挙げられる。 Nitrogen-containing monomers include (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N - isopropyl (meth)acrylamide, methylenebis (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropylacrylamide, diacetoneacrylamide , dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, stearamidoethyl (meth)acrylate, N-vinylpyrrolidone, (meth)acrylonitrile and the like.
 アルキレングリコール基含有単量体としては、エチレングリコール(メタ)アクリレート、エチレングリコールメトキシ(メタ)アクリレート、ジエチレングリコール(メタ)アクリレート、ジエチレングリコールメトキシ(メタ)アクリレートなどが挙げられる。
アルコキシアルキル基含有単量体としては、例えば、メトキシエチル(メタ)アクリレート、メトキシブチル(メタ)アクリレート、エトキシブチル(メタ)アクリレート、トリメチロールプロパントリプロポキシ(メタ)アクリレートなどが挙げられる。
  カルボニル基含有単量体としては、アクロレイン、ホウミルスチロール、ビニルエチルケトン、(メタ)アクリルオキシアルキルプロペナール、アセトニル(メタ)アクリレート、ジアセトン(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレートアセチルアセテート、ブタンジオール-1,4-アクリレートアセチルアセテート、2-(アセトアセトキシ)エチル(メタ)アクリレートなどが挙げられる。
Examples of alkylene glycol group-containing monomers include ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate.
Examples of alkoxyalkyl group-containing monomers include methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, and trimethylolpropane tripropoxy (meth)acrylate.
Carbonyl group-containing monomers include acrolein, bomylstyrene, vinyl ethyl ketone, (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, 2-hydroxypropyl (meth)acrylate acetylacetate. , butanediol-1,4-acrylate acetylacetate, 2-(acetoacetoxy)ethyl (meth)acrylate and the like.
 シラン基含有単量体としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ(メトキシエトキシ)シラン、γ-(メタ)アクリロイルオキシプロピルトリメトキシシラン、2-スチリルエチルトリメトキシシラン、ビニルトリクロロシラン、γ-(メタ)アクリロイルオキシプロピルヒドロキシシラン、γ-(メタ)アクリロイルオキシプロピルメチルヒドロキシシランなどが挙げられる。 Silane group-containing monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, γ-(meth)acryloyloxypropylhydroxysilane, γ-(meth)acryloyloxypropylmethylhydroxysilane and the like.
 環構造含有単量体としては、グリシジル(メタ)アクリレート、α-メチルグリシジル(メタ)アクリレート、グリシジルアリルエーテル、ベンジル(メタ)アクリレート、フェニルエチル(メタ)アクリレート、メチルベンジル(メタ)アクリレート、ナフチルメチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、スチレン、α-メチルスチレン、p-メチルスチレン、tert-メチルスチレン、クロロスチレン、(メタ)アクリロイルアジリジン、(メタ)アクリル酸2-アジリジニルエチル、ビニルトルエン、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルオキシ-1,2,2,6,6-ペンタメチルピペリジン、4-(メタ)アクリロイル-1-メトキシ-2,2,6,6-テトラメチルピペリジン、4-シアノ-4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルアミノ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルアミノ-1,2,2,6,6-ペンタメチルピペリジン、4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジンなどが挙げられる。 Ring structure-containing monomers include glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, glycidyl allyl ether, benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, naphthylmethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, (meth)acryloylaziridine, (meth)acrylic acid 2- aziridinylethyl, vinyltoluene, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (Meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-( meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino- 2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2, 6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6 ,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like.
 多官能単量体としては、例えば、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,3-ブタンジオールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、エチレンオキシド変性1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、プロピレンオキシド変性ネオペンチルグリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレートなどの炭素数1~10の多価アルコールのジ(メタ)アクリレート;エチレンオキシドの付加モル数が2~50のポリエチレングリコールジ(メタ)アクリレート、プロピレンオキシドの付加モル数が2~50のポリプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレートなどの炭素数2~4のアルキレンオキシド基の付加モル数が2~50であるアルキルジ(メタ)アクリレート;エトキシ化グリセリントリ(メタ)アクリレート、プロピレンオキシド変性グリセロールトリ(メタ)アクリレート、エチレンオキシド変性トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールモノヒドロキシトリ(メタ)アクリレート、トリメチロールプロパントリエトキシトリ(メタ)アクリレートなどの炭素数1~10の多価アルコールのトリ(メタ)アクリレート;ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレートなどの炭素数1~10の多価アルコールのテトラ(メタ)アクリレート;ペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトール(モノヒドロキシ)ペンタ(メタ)アクリレートなどの炭素数1~10の多価アルコールのペンタ(メタ)アクリレート;ペンタエリスリトールヘキサ(メタ)アクリレートなどの炭素数1~10の多価アルコールのヘキサ(メタ)アクリレート;ビスフェノールAジ(メタ)アクリレート、2-(2’-ビニルオキシエトキシエチル)(メタ)アクリレート、エポキシ(メタ)アクリレートなどのエポキシ基含有(メタ)アクリレート;ウレタン(メタ)アクリレートなどの多官能(メタ)アクリレートなどが挙げられる。 Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, Di(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as tripropylene glycol di(meth)acrylate; Alkyl di(meth)acrylates having 2 to 50 moles of alkylene oxide groups having 2 to 4 carbon atoms, such as polypropylene glycol di(meth)acrylate having 2 to 50 and tripropylene glycol di(meth)acrylate; ethoxylation Glycerin tri(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate, trimethylolpropane Tri(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as triethoxytri(meth)acrylate; pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate Tetra (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as; Penta(meth)acrylate; hexa(meth)acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa(meth)acrylate; bisphenol A di(meth)acrylate, 2-(2'-vinyloxyethoxyethyl) Epoxy group-containing (meth)acrylates such as (meth)acrylates and epoxy (meth)acrylates; polyfunctional (meth)acrylates such as urethane (meth)acrylates;
 式(1)で表される化合物に基づく構造単位を少なくとも有する重合体は、撥水性成分の全質量に対して、式(1)で表される化合物に基づく構造単位を40質量%以上含むことが好ましく、60質量%以上含むことがより好ましく、80質量%以上含むことがさらに好ましく、95質量%以上含むことが特に好ましい。式(1)で表される化合物に基づく構造単位を少なくとも有する重合体は、式(1)で表される化合物に基づく構造単位のみで形成することもできる。撥水性成分は式(1)で表される化合物に基づく構造単位を1種または2種以上を含むことができる。 The polymer having at least a structural unit based on the compound represented by formula (1) contains 40% by mass or more of the structural unit based on the compound represented by formula (1) with respect to the total mass of the water-repellent component. is preferable, more preferably 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more. A polymer having at least structural units based on the compound represented by formula (1) can also be formed only with structural units based on the compound represented by formula (1). The water-repellent component can contain one or more structural units based on the compound represented by formula (1).
 撥水性成分は、市販品から入手することもでき、例えば、ダイキン工業社製の商品名「ユニダイン(登録商標)TGシリーズ」、3M社製の商品名「スコッチガード(登録商標)」、東亞合成社製の商品名「サイマック(登録商標)US-270」、「サイマック(登録商標)US-350」、「サイマック(登録商標)US-352」、「サイマック(登録商標)US-380」、日本触媒社製の商品名「SG-204」を挙げることができる。 The water repellent component can also be obtained from commercial products, for example, the product name "Unidyne (registered trademark) TG series" manufactured by Daikin Industries, Ltd., the product name "Scotchguard (registered trademark)" manufactured by 3M, Toagosei trade names "Symac (registered trademark) US-270", "Symac (registered trademark) US-350", "Symac (registered trademark) US-352", "Symac (registered trademark) US-380" manufactured by Japan A trade name “SG-204” manufactured by Catalyst Co., Ltd. can be mentioned.
 (重合性成分)
 本開示の被膜形成用組成物において、重合性成分は、被膜が形成されたときの後記バインダー成分となる成分であり、バインダー成分前駆体と呼ぶことができる。つまり、重合性成分は硬化すること(例えば、重合反応又は硬化反応)ができる成分であって、硬化後は被膜のバインダー成分を形成する成分である。ただし、重合性成分は、前記式(1)で表される化合物の重合体を除くものである。
(Polymerizable component)
In the film-forming composition of the present disclosure, the polymerizable component is a component that becomes a binder component when the film is formed, and can be called a binder component precursor. In other words, the polymerizable component is a component that can be cured (eg, a polymerization reaction or a curing reaction) and that, after curing, forms the binder component of the coating. However, the polymerizable component excludes the polymer of the compound represented by the formula (1).
 重合性成分は、バインダー成分を形成することができる限り、その種類は特に限定されず、公知の材料を広く使用することができる。例えば、被膜形成用組成物に含まれる重合性成分は、熱を与えることで硬化反応が進行して硬化物を与えることができる成分、あるいは、UV等の光照射によって硬化物を与えることができる成分である。熱を与えることで硬化反応が進行して硬化物を与えることができる成分を「熱硬化性樹脂成分」と、光照射によって硬化物を与えることができる成分を「光硬化性樹脂成分」と表記する。重合性成分は、熱硬化性樹脂成分及び光硬化性樹脂成分の少なくとも一方であることが好ましい。 The type of the polymerizable component is not particularly limited as long as it can form a binder component, and a wide range of known materials can be used. For example, the polymerizable component contained in the film-forming composition is a component that can give a cured product by the progress of a curing reaction by applying heat, or can give a cured product by irradiation with light such as UV. is an ingredient. A component that can give a cured product as a result of the curing reaction progressing by applying heat is called a “thermosetting resin component”, and a component that can give a cured product by light irradiation is called a “photocurable resin component”. do. The polymerizable component is preferably at least one of a thermosetting resin component and a photocurable resin component.
 熱硬化性樹脂成分の種類は特に限定されず、例えば、公知の重合体と、必要に応じて含まれる硬化剤との混合物とすることができる。斯かる重合体は、例えば、架橋性官能基を有することが好ましく、この場合、例えば、熱硬化によって架橋反応が進行しやすい。この観点から、重合性成分(熱硬化性樹脂成分)は、架橋性官能基を有する重合体及び硬化剤であることが好ましい。以下、架橋性官能基を有する重合体を「架橋性重合体」と略記する。 The type of thermosetting resin component is not particularly limited, and for example, it can be a mixture of a known polymer and a curing agent that is included as necessary. Such a polymer preferably has, for example, a crosslinkable functional group, and in this case, for example, thermal curing facilitates the progress of the crosslinking reaction. From this point of view, the polymerizable component (thermosetting resin component) is preferably a polymer having a crosslinkable functional group and a curing agent. Hereinafter, a polymer having a crosslinkable functional group is abbreviated as "crosslinkable polymer".
 架橋性重合体は、フッ素原子(フルオロアルキル基)を有していてもよいし、フッ素原子(フルオロアルキル基)を有していなくてもよい。ただし、被膜の撥水性が向上しやすいという観点から、架橋性重合体は、フルオロアルキル基を有していることが好ましい。 The crosslinkable polymer may or may not have a fluorine atom (fluoroalkyl group). However, from the viewpoint that the water repellency of the film is likely to be improved, the crosslinkable polymer preferably has a fluoroalkyl group.
 フッ素原子を有していない架橋性重合体は、市販品から入手することができ、例えば、日本触媒社製の商品名「ハルスハイブリッド・ユーダブル(登録商標)UWS-2710」、「ハルスハイブリッド・ユーダブル(登録商標)UWS-2740」、「ハルスハイブリッド・ユーダブル(登録商標)UWS-2841」、「ハルスハイブリッド・ユーダブル(登録商標)UWS-2818」、「ハルスハイブリッド・ユーダブル(登録商標)UWS-2816」、「ハルスハイブリッド・ユーダブル(登録商標)UWH-4818」、「ハルスハイブリッドUV-G(登録商標)UV-G12」、「ハルスハイブリッドUV-G(登録商標)UV-G13」、「ハルスハイブリッドUV-G(登録商標)UV-G101」、「ハルスハイブリッドUV-G(登録商標)UV-G301」、「ハルスハイブリッドUV-G(登録商標)UV-G137」、「アクリセット(登録商標)ATH-2060」、「アクリセット(登録商標)ATH-2070」、「アクリセット(登録商標)ATH-2077CR」、「アクリセット(登録商標)ATH-2088CR」を挙げることができる。 The crosslinkable polymer having no fluorine atom can be obtained from commercial products. (registered trademark) UWS-2740”, “Halshybrid Udable (registered trademark) UWS-2841”, “Halshybrid Udable (registered trademark) UWS-2818”, “Halshybrid Udable (registered trademark) UWS-2816” , "Hals Hybrid Udable (registered trademark) UWH-4818", "Hals Hybrid UV-G (registered trademark) UV-G12", "Hals Hybrid UV-G (registered trademark) UV-G13", "Hals Hybrid UV- G (registered trademark) UV-G101”, “Hals Hybrid UV-G (registered trademark) UV-G301”, “Hals Hybrid UV-G (registered trademark) UV-G137”, “Acryset (registered trademark) ATH-2060 ”, “Acryset (registered trademark) ATH-2070”, “Acryset (registered trademark) ATH-2077CR”, and “Acryset (registered trademark) ATH-2088CR”.
 架橋性重合体において、架橋性官能基は、例えば、水酸基、カルボキシ基、アミノ基、チオール基、イソシアネート基等が好ましい。この場合において、斯かる化合物はさらに、フルオロアルキル基を有していることが好ましい。架橋性官能基は、例えば、架橋性重合体の側鎖に共有結合していることが好ましい。 In the crosslinkable polymer, the crosslinkable functional group is preferably, for example, a hydroxyl group, a carboxyl group, an amino group, a thiol group, an isocyanate group, or the like. In this case, such compounds preferably further have a fluoroalkyl group. The crosslinkable functional groups are preferably covalently bonded, for example, to the side chains of the crosslinkable polymer.
 架橋性重合体がフルオロアルキル基を有している場合、架橋性重合体としては、種々の架橋性官能基を有する含フッ素重合体を挙げることができ、その一例として、
(a)テトラフルオロエチレン構造単位及び/又はクロロトリフルオロエチレン構造単位、
(b)水酸基とカルボキシル基とを含まない非芳香族系のビニルエステルモノマー構造単位、
(c)芳香族基とカルボキシル基とを含まない水酸基含有ビニルモノマー構造単位、
(e)水酸基と芳香族基とを含まないカルボキシル基含有モノマー構造単位および
(f)その他モノマー構造単位(ただし、(d)水酸基とカルボキシル基とを含まない芳香族基含有モノマー構造単位を含まない)
からなる重合体を挙げることができる。以下、この重合体を「重合体F」と表記する。熱硬化性樹脂が重合体Fである場合、被膜の耐水性が特に向上する。
When the crosslinkable polymer has a fluoroalkyl group, examples of the crosslinkable polymer include fluorine-containing polymers having various crosslinkable functional groups.
(a) tetrafluoroethylene structural units and/or chlorotrifluoroethylene structural units,
(b) a non-aromatic vinyl ester monomer structural unit containing no hydroxyl group or carboxyl group;
(c) a hydroxyl group-containing vinyl monomer structural unit that does not contain an aromatic group and a carboxyl group;
(e) carboxyl group-containing monomer structural units that do not contain hydroxyl groups and aromatic groups and (f) other monomer structural units (provided that (d) does not contain aromatic group-containing monomer structural units that do not contain hydroxyl groups and carboxyl groups) )
A polymer consisting of can be mentioned. Hereinafter, this polymer is referred to as "Polymer F". When the thermosetting resin is polymer F, the water resistance of the coating is particularly improved.
 前記(a)テトラフルオロエチレン構造単位及び/又はクロロトリフルオロエチレン構造単位の含有割合は、重合体Fの全量中、下限が20モル%、好ましくは30モル%、より好ましくは40モル%、特に好ましくは42モル%であり、上限が49モル%、好ましくは47モル%である。 The content of the (a) tetrafluoroethylene structural unit and/or chlorotrifluoroethylene structural unit has a lower limit of 20 mol%, preferably 30 mol%, more preferably 40 mol%, particularly It is preferably 42 mol %, and the upper limit is 49 mol %, preferably 47 mol %.
 前記非芳香族系のビニルエステルモノマー構造単位(b)を与えるモノマーとしては、例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、シクロヘキシルカルボン酸ビニルなどの1種または2種以上があげられる。これらのモノマーは水酸基とカルボキシル基とを含まない非芳香族系モノマーである。特に好ましい非芳香族系のビニルエステルモノマー構造単位(b)を与えるモノマーは、耐候性等に優れる点からバーサチック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、シクロヘキシルカルボン酸ビニル及び酢酸ビニルからなる群より選ばれる1種である。これらのなかでも耐薬品性の点から、非芳香族系カルボン酸ビニルエステル、特にカルボン酸の炭素数が6以上のカルボン酸ビニルエステル、さらに好ましくはカルボン酸の炭素数が9以上のカルボン酸ビニルエステルが好ましい。カルボン酸ビニルエステルにおけるカルボン酸の炭素数の上限は20以下、さらには15以下が好ましい。具体例としてはバーサチック酸ビニルが最も好ましい。 Examples of the monomer that provides the non-aromatic vinyl ester monomer structural unit (b) include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, and lauric acid. One or more of vinyl, vinyl stearate, vinyl cyclohexylcarboxylate and the like can be mentioned. These monomers are non-aromatic monomers containing no hydroxyl group or carboxyl group. Monomers that give a particularly preferred non-aromatic vinyl ester monomer structural unit (b) are selected from the group consisting of vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate and vinyl acetate from the viewpoint of excellent weather resistance. It is the one of choice. Among these, non-aromatic carboxylic acid vinyl esters, particularly carboxylic acid vinyl esters having 6 or more carbon atoms, more preferably vinyl carboxylates having 9 or more carbon atoms, are preferred from the viewpoint of chemical resistance. Esters are preferred. The upper limit of the carbon number of the carboxylic acid in the carboxylic acid vinyl ester is preferably 20 or less, more preferably 15 or less. As a specific example, vinyl versatate is most preferable.
 前記非芳香族系のビニルエステルモノマー構造単位(b)の含有割合は、重合体Fの全量中、下限が25モル%、好ましくは30モル%であり、上限が69.9モル%、好ましくは60モル%、より好ましくは43モル%、特に好ましくは40モル%である。 The content of the non-aromatic vinyl ester monomer structural unit (b) has a lower limit of 25 mol%, preferably 30 mol%, and an upper limit of 69.9 mol%, preferably 69.9 mol%, based on the total amount of the polymer F. 60 mol %, more preferably 43 mol %, particularly preferably 40 mol %.
 前記水酸基含有ビニルモノマー構造単位(c)を与えるモノマーはカルボキシル基を含まない非芳香族系のモノマーであり、たとえば式(2)で表わされるヒドロキシアルキルビニルエーテル又はヒドロキシアルキルアリルエーテルが挙げられる。
CH=CHR10   (2)
The monomer that gives the hydroxyl group-containing vinyl monomer structural unit (c) is a non-aromatic monomer containing no carboxyl group, and examples thereof include hydroxyalkyl vinyl ethers and hydroxyalkyl allyl ethers represented by formula (2).
CH2 = CHR10 (2)
 ここで、式(2)中、R10は-OR20または-CHOR20(ただし、R20は水酸基を有するアルキル基である。)を表す。R20としては、たとえば炭素数1~8の直鎖状または分岐鎖状のアルキル基に1~3個、好ましくは1個の水酸基が結合したものである。式(2)の例としては、2-ヒドロキシエチルビニルエーテル、3-ヒドロキシプロピルビニルエーテル、2-ヒドロキシプロピルビニルエーテル、2-ヒドロキシ-2-メチルプロピルビニルエーテル、4-ヒドロキシブチルビニルエーテル、4-ヒドロキシ-2-メチルブチルビニルエーテル、5-ヒドロキシペンチルビニルエーテル、6-ヒドロキシヘキシルビニルエーテル、2-ヒドロキシエチルアリルエーテル、4-ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテルなどの1種または2種以上が挙げられる。中でも、前記水酸基含有ビニルモノマー構造単位(c)を与えるモノマーは、4-ヒドロキシブチルビニルエーテル、2-ヒドロキシエチルビニルエーテルが好ましい。 Here, in formula (2), R 10 represents —OR 20 or —CH 2 OR 20 (where R 20 is an alkyl group having a hydroxyl group). R 20 is, for example, a linear or branched alkyl group having 1 to 8 carbon atoms to which 1 to 3, preferably 1 hydroxyl group is bonded. Examples of formula (2) include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methyl One or more of butyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether and the like can be used. Among them, 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are preferable as the monomer that provides the hydroxyl group-containing vinyl monomer structural unit (c).
 この水酸基含有ビニルモノマー構造単位(c)の存在によって、被膜の加工性、耐衝撃性、耐汚染性を改善することができる。 The presence of this hydroxyl group-containing vinyl monomer structural unit (c) can improve the workability, impact resistance, and stain resistance of the film.
 水酸基含有ビニルモノマー構造単位(c)の含有割合は、重合体Fの全量中、下限が8モル%、好ましくは10モル%であり、さらに好ましくは15モル%、上限が30モル%、好ましくは20モル%である。 The content of the hydroxyl group-containing vinyl monomer structural unit (c) has a lower limit of 8 mol%, preferably 10 mol%, more preferably 15 mol%, and an upper limit of 30 mol%, preferably 30 mol%, based on the total amount of the polymer F. 20 mol %.
 重合体Fは基本的には(a)、(b)及び(c)(ただし、各単位の内では2種以上共重合してもよい)で構成することができるが、10モル%までは他の共重合可能なモノマー単位(f)を含むことができる。他の共重合可能なモノマー構造単位(f)は、前記(a)、(b)および(c)のほか芳香族基含有モノマー構造単位(d)およびカルボキシル基含有モノマー構造単位(e)以外のモノマー構造単位である。 Polymer F can be basically composed of (a), (b) and (c) (however, two or more of each unit may be copolymerized), but up to 10 mol % Other copolymerizable monomeric units (f) may be included. Other copolymerizable monomer structural units (f) are the above (a), (b) and (c), aromatic group-containing monomer structural units (d) and carboxyl group-containing monomer structural units other than (e). It is a monomer structural unit.
 他の共重合可能なモノマー構造単位(f)を与えるモノマーとしては、例えば、メチルビニルエーテル、エチルビニルエーテルなどのアルキルビニルエーテル;エチレン、プロピレン、n-ブテン、イソブテンなどの非フッ素系のオレフィン等が挙げられる。他の共重合可能なモノマー構造単位(f)が含まれる場合、その含有割合は、重合体F中、10モル%以下、好ましくは5モル%未満、さらに好ましくは4モル%以下である。 Examples of monomers that give other copolymerizable monomer structural units (f) include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; non-fluorine olefins such as ethylene, propylene, n-butene and isobutene. . When other copolymerizable monomer structural units (f) are included, the content in polymer F is 10 mol % or less, preferably less than 5 mol %, more preferably 4 mol % or less.
 重合体Fはさらに、(d)水酸基とカルボキシル基とを含まない芳香族基含有モノマー構造単位を含むこともできる。(d)水酸基とカルボキシル基とを含まない芳香族基含有モノマー構造単位としては、例えば、安息香酸ビニル、パラ-t-ブチル安息香酸ビニルなどの安息香酸ビニルモノマーなどの1種または2種以上が挙げられ、特にパラ-t-ブチル安息香酸ビニル、さらには安息香酸ビニルが好ましい。 Polymer F can further contain (d) aromatic group-containing monomer structural units that do not contain hydroxyl groups and carboxyl groups. (d) The aromatic group-containing monomer structural unit that does not contain a hydroxyl group and a carboxyl group includes, for example, one or more vinyl benzoate monomers such as vinyl benzoate and vinyl para-t-butylbenzoate. para-t-butyl vinyl benzoate, and vinyl benzoate is particularly preferred.
 芳香族基含有モノマー構造単位(d)の含有割合は、重合体F中、下限が2モル%、好ましくは4モル%であり、上限は15モル%、好ましくは10モル%、より好ましくは8モル%である。 The content of the aromatic group-containing monomer structural unit (d) in the polymer F has a lower limit of 2 mol%, preferably 4 mol%, and an upper limit of 15 mol%, preferably 10 mol%, more preferably 8. in mol %.
 重合体Fはさらに、(e)水酸基と芳香族基とを含まないカルボキシル基含有モノマー構造単位を含むこともできる。カルボキシル基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、桂皮酸、3-アリルオキシプロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸無水物、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニルなどの1種または2種以上が挙げられる。中でも、単独重合性の低いクロトン酸、イタコン酸、マレイン酸、マレイン酸モノエステル、フマル酸、フマル酸モノエステル、3-アリルオキシプロピオン酸が好ましい。 Polymer F can further contain (e) a carboxyl group-containing monomer structural unit that does not contain a hydroxyl group and an aromatic group. Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, and maleic anhydride. , fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, and the like. Among them, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, and 3-allyloxypropionic acid, which have low homopolymerizability, are preferred.
 カルボキシル基含有モノマー構造単位(e)の含有割合は、重合体F中、下限が0.1モル%、好ましくは0.4モル%であり、上限が2.0モル%、好ましくは1.5モル%である。 The content of the carboxyl group-containing monomer structural unit (e) in the polymer F has a lower limit of 0.1 mol%, preferably 0.4 mol%, and an upper limit of 2.0 mol%, preferably 1.5. in mol %.
 重合体Fは、テトラヒドロフランを溶離液として用いるゲルパーミエイションクロマトグラフィー(GPC)により測定する数平均分子量が、例えば、1000から1000000、好ましくは3000から50000である。示差走査熱量計(DSC)により求める重合体Fのガラス転移温度(2nd run)は、例えば、10~60℃、好ましくは20~40℃である。重合体Fの製造方法も特に限定されず、公知の製造方法を広く採用することができる。また、重合体Fは市販品等からの入手も可能である。 Polymer F has a number average molecular weight of, for example, 1,000 to 1,000,000, preferably 3,000 to 50,000 as measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent. The glass transition temperature (2nd run) of polymer F determined by a differential scanning calorimeter (DSC) is, for example, 10 to 60°C, preferably 20 to 40°C. The method for producing the polymer F is also not particularly limited, and a wide range of known production methods can be employed. In addition, the polymer F can be obtained from commercial products and the like.
 重合体Fの具体例としては、ダイキン工業社製のゼッフル(登録商標)GKシリーズ、旭硝子社製のルミフロン(登録商標)LFシリーズ、DIC社製のフルオネート(登録商標)シリーズ、Arkema社製のKyner Aquatec(登録商標)やKYNAR 500 Plus等が挙げられる。 Specific examples of the polymer F include Zeffle (registered trademark) GK series manufactured by Daikin Industries, Ltd., Lumiflon (registered trademark) LF series manufactured by Asahi Glass Co., Ltd., Fluorate (registered trademark) series manufactured by DIC Corporation, and Kyner manufactured by Arkema. Examples include Aquatec (registered trademark) and KYNAR 500 Plus.
 熱硬化性樹脂成分は、架橋性重合体の他、前述のように硬化剤を含む。硬化剤は特に限定されず、例えば、熱硬化性樹脂用の硬化剤として使用される化合物を広く適用することができる。特に、硬化剤は、前述の分子内に2つ以上の重合性基を有する化合物であることが好ましい。 The thermosetting resin component contains a curing agent as described above in addition to the crosslinkable polymer. The curing agent is not particularly limited, and for example, compounds used as curing agents for thermosetting resins can be widely applied. In particular, the curing agent is preferably a compound having two or more polymerizable groups in the molecule described above.
 硬化剤の具体例としては、イソシアネート系硬化剤が挙げられる。イソシアネート系硬化剤としては、例えば、イソシアネート基を有する化合物(以下、単にイソシアネート化合物と表記)が挙げられる。イソシアネート化合物は、たとえば、下記一般式(20)で表されるが挙げられる。 A specific example of the curing agent is an isocyanate curing agent. Examples of isocyanate-based curing agents include compounds having an isocyanate group (hereinafter simply referred to as isocyanate compounds). Examples of isocyanate compounds include those represented by the following general formula (20).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
 式(20)中、Zは、少なくとも一つの末端にイソシアネート基を有する、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る。R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る。式(20)中のoは2以上の整数である。 In formula (20), Z 6 has at least one terminal isocyanate group, 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. It is preferably a linear or branched monovalent hydrocarbon group or carbonyl group which may have a carbon-carbon unsaturated bond. In R 3 , at least one carbon atom may be substituted with a hetero atom, at least one hydrogen atom may be substituted with a halogen atom, or at least one carbon atom may be substituted with a hetero atom. It is preferably a branched or cyclic hydrocarbon group having a valence of 2 or more or a carbonyl group, which may have a carbon-carbon unsaturated bond. o in the formula (20) is an integer of 2 or more.
 R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。 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。 Z 6 preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.
 イソシアネート化合物は、1種で用いてもよく、又は複数を組み合わせて用いてもよい。 The isocyanate compound may be used singly or in combination.
 イソシアネート化合物としては、例えば、ポリイソシアネートを挙げることができる。本明細書において、ポリイソシアネートとは、分子内にイソシアネート基を2個以上有する化合物を意味する。イソシアネート化合物は、ジイソシアネートを三量体化することにより得られるポリイソシアネートであってもよい。かかるジイソシアネートを三量体化することにより得られるポリイソシアネートは、トリイソシアネートであり得る。ジイソシアネートの三量体であるポリイソシアネートは、これらが重合した重合体として存在してもよい。 Examples of isocyanate compounds include polyisocyanates. As used herein, polyisocyanate means a compound having two or more isocyanate groups in the molecule. The isocyanate compound may be a polyisocyanate obtained by trimerizing a diisocyanate. Polyisocyanates obtained by trimerizing such diisocyanates may be triisocyanates. Polyisocyanate, which is a trimer of diisocyanate, may exist as a polymer obtained by polymerizing these.
 ジイソシアネートとしては、特に限定されないが、トリメチレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、シクロヘキサンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ノルボルナンジイソシアネート等のイソシアネート基が脂肪族基に結合したジイソシアネート;トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、トリジンジイソシアネート、ナフタレンジイソシアネート等のイソシアネート基が芳香族基に結合したジイソシアネートが挙げられる。 The diisocyanate is not particularly limited, but isocyanate groups such as trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate are bonded to aliphatic groups. Diisocyanate; diisocyanates in which an isocyanate group is bonded to an aromatic group, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, and naphthalene diisocyanate.
 具体的なポリイソシアネートとしては、特に限定するものではないが、下記の構造を有する化合物が挙げられる。 Specific polyisocyanates include, but are not limited to, compounds having the following structures.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
 これらのポリイソシアネートは重合体として存在してもよく、例えば、ヘキサメチレンジイソシアネートのイソシアヌレート型ポリイソシアネートである場合、下記構造を有する重合体を有していてもよい。 These polyisocyanates may exist as polymers. For example, in the case of an isocyanurate-type polyisocyanate of hexamethylene diisocyanate, they may have a polymer having the following structure.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
 好ましい実施形態において、イソシアネート化合物は、イソシアヌレート型ポリイソシアネートである。 In a preferred embodiment, the isocyanate compound is an isocyanurate-type polyisocyanate.
 上記イソシアヌレート型ポリイソシアネートは、これらが重合した重合体であってもよい。イソシアヌレート型ポリイソシアネートは、イソシアヌレート環を1つのみ有する単環式化合物であってもよく、又はこの単環式化合物が重合して得られる多環式化合物であってもよい。 The above 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.
 二種以上のイソシアネート化合物を用いる一の態様において、イソシアヌレート環を1つのみ有する単環式化合物を含む混合物を用いることができる。 In one embodiment using two or more isocyanate compounds, a mixture containing monocyclic compounds having only one isocyanurate ring can be used.
 二種以上のイソシアネート化合物を用いる別の態様において、イソシアヌレート型ポリイソシアネートであるイソシアネート化合物を含む混合物を用いることができる。イソシアヌレート型ポリイソシアネートは、例えば、トリイソシアネートであってもよく、具体的には、ジイソシアネートを三量体化することにより得られるトリイソシアネートであってもよい。 In another embodiment using two or more isocyanate compounds, a mixture containing an isocyanate compound that is an isocyanurate-type polyisocyanate can be used. The isocyanurate-type polyisocyanate may be, for example, a triisocyanate, specifically a triisocyanate obtained by trimerizing a diisocyanate.
 イソシアネート化合物の具体例としては、例えば、2,4-トリレンジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、リジンメチルエステルジイソシアネート、メチルシクロヘキシルジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ヘキサメチレンジイソシアネート、n-ペンタン-1,4-ジイソシアネート、これらの三量体、これらのアダクト体、ビュウレット体やイソシアヌレート体、これらの重合体で2個以上のイソシアネート基を有するもの、更にブロック化されたイソシアネート類等が挙げられる。より詳しい硬化剤の具体例としては、スミジュール(登録商標)N3300(住化コベストロウレタン株式会社製)、デスモジュール(登録商標)N3600(住化コベストロウレタン株式会社製)、デスモジュールT、L、IL、HLシリーズ(住化コベストロウレタン株式会社製)、デスモジュール(登録商標)2460M(住化コベストロウレタン株式会社製)、スミジュール(登録商標)44シリーズ(住化コベストロウレタン株式会社製)、SBUイソシアネートシリーズ(住化コベストロウレタン株式会社製)、デスモジュール(登録商標)E、Mシリーズ(住化コベストロウレタン株式会社製)、スミジュールHT(住化コベストロウレタン株式会社製)、デスモジュールNシリーズ(住化コベストロウレタン株式会社製)、デスモジュールZ4470シリーズ(住化コベストロウレタン株式会社製)、デュラネートTPA-100(旭化成株式会社製)、デュラネートTKA-100(旭化成株式会社製)、デュラネート24A-100(旭化成株式会社製)、デュラネート22A-75P(旭化成株式会社製)及びデュラネートP301-75E(旭化成株式会社製)、デュラネートMF-K60B(旭化成株式会社製)、デュラネートSBB-70P(旭化成株式会社製)、デュラネートSBN-70D(旭化成株式会社製)、デュラネートMF-B60B(旭化成株式会社製)、デュラネート17B-60P(旭化成株式会社製)、デュラネートTPA-B80E(旭化成株式会社製)、デュラネートE402-B80B(旭化成株式会社製)、デュラネートWM44-L70G(旭化成株式会社製)として市販されているもの等を用いることができる。 Specific examples of isocyanate compounds include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene. Diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts thereof, burettes and isocyanurates, polymers thereof having two or more isocyanate groups, further blocked Isocyanates and the like can be mentioned. Specific examples of more detailed curing agents include Sumidule (registered trademark) N3300 (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) N3600 (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur T, L, IL, HL series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) 2460M (manufactured by Sumika Covestro Urethane Co., Ltd.), Sumidule (registered trademark) 44 series (Sumika Covestro Urethane Co., Ltd.) company), SBU isocyanate series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) E, M series (manufactured by Sumika Covestro Urethane Co., Ltd.), Sumidule HT (Sumika Covestro Urethane Co., Ltd.) ), Desmodur N series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur Z4470 series (manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate TPA-100 (manufactured by Asahi Kasei Corporation), Duranate TKA-100 (Asahi Kasei Corporation), Duranate 24A-100 (manufactured by Asahi Kasei Corporation), Duranate 22A-75P (manufactured by Asahi Kasei Corporation) and Duranate P301-75E (manufactured by Asahi Kasei Corporation), Duranate MF-K60B (manufactured by Asahi Kasei Corporation), Duranate SBB-70P (manufactured by Asahi Kasei Corp.), Duranate SBN-70D (manufactured by Asahi Kasei Corp.), Duranate MF-B60B (manufactured by Asahi Kasei Corp.), Duranate 17B-60P (manufactured by Asahi Kasei Corp.), Duranate TPA-B80E (manufactured by Asahi Kasei Corp.) (manufactured by Asahi Kasei Corp.), Duranate E402-B80B (manufactured by Asahi Kasei Corp.), and Duranate WM44-L70G (manufactured by Asahi Kasei Corp.).
 熱硬化性樹脂成分において、硬化剤の含有割合は、架橋性重合体及び硬化剤の全質量に対して10~100質量%とすることができ、15~35質量%であることが好ましい。 In the thermosetting resin component, the content of the curing agent can be 10 to 100% by mass, preferably 15 to 35% by mass, based on the total mass of the crosslinkable polymer and the curing agent.
 一方、重合性成分が光硬化性樹脂成分である場合、UV等の光照射によって重合反応が進行する単量体を挙げることができ、例えば、撥水性塗膜を形成するために使用されている公知の光重合性モノマーを広く採用することができる。重合性成分が光硬化性樹脂成分である場合、例えば、公知の光重合開始剤を使用することも好ましい。光重合開始剤の種類も特に限定されず、例えば、撥水性塗膜を形成するために使用されている公知の光重合開始剤を広く採用することができる。 On the other hand, when the polymerizable component is a photocurable resin component, a monomer that undergoes a polymerization reaction upon irradiation with light such as UV can be used. A wide range of known photopolymerizable monomers can be employed. When the polymerizable component is a photocurable resin component, for example, it is also preferable to use a known photopolymerization initiator. The type of photopolymerization initiator is also not particularly limited, and for example, a wide range of known photopolymerization initiators used for forming water-repellent coating films can be employed.
 (被膜形成用組成物)
 本開示の被膜形成用組成物において、無機微粒子、重合性成分及び撥水性成分の含有割合は、本開示の効果が阻害されない限り、特に限定されない。
(Coating film-forming composition)
In the film-forming composition of the present disclosure, the content ratios of the inorganic fine particles, the polymerizable component and the water-repellent component are not particularly limited as long as the effects of the present disclosure are not impaired.
 本開示の被膜形成用組成物において、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量(以下、「総質量(S1)」と表記する)100質量部あたりの前記第1の無機微粒子の含有量は、3~25質量部である。前記第1の無機微粒子の含有量が、前記総質量(S1)100質量部あたり3質量部を下回ると、第1の無機微粒子の効果を十分に発揮できず、所望の撥水性及び耐摩耗性が得られず、着雪防止性能も低下し、また、25質量部を超えても所望の撥水性及び耐摩耗性が得られず、そればかりか被膜の形成も難しくなる。前記第1の無機微粒子の含有量は、前記総質量(S1)100質量部あたり、5質量部以上であることが好ましく、8質量部以上であることがより好ましく、10質量部以上であることがさらに好ましい。また、前記第1の無機微粒子の含有量は、前記総質量(S1)100質量部あたり、23質量部以下であることが好ましく、22質量部以下であることがより好ましく、20質量部以下であることがさらに好ましい。 In the film-forming composition of the present disclosure, the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component (hereinafter referred to as "total mass (S1)") The content of the first inorganic fine particles per 100 parts by mass is 3 to 25 parts by mass. When the content of the first inorganic fine particles is less than 3 parts by mass per 100 parts by mass of the total mass (S1), the effect of the first inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, and the anti-snow accretion performance is lowered, and even if the amount exceeds 25 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating. The content of the first inorganic fine particles is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 10 parts by mass or more per 100 parts by mass of the total mass (S1). is more preferred. In addition, the content of the first inorganic fine particles is preferably 23 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less per 100 parts by mass of the total mass (S1). It is even more preferable to have
 また、本開示の被膜形成用組成物において、前記総質量(S1)100質量部あたりの前記第2の無機微粒子の含有量は、12~27質量部である。前記第2の無機微粒子の含有量が、前記総質量(S1)100質量部あたり12質量部を下回ると、第2の無機微粒子の効果を十分に発揮できず、所望の撥水性及び耐摩耗性が得られず、着雪防止性能も低下し、また、27質量部を超えても所望の撥水性及び耐摩耗性が得られず、そればかりか被膜の形成も難しくなる。前記第2の無機微粒子の含有量は、前記総質量(S1)100質量部あたり、15質量部以上であることが好ましく、16質量部以上であることがより好ましく、18質量部以上であることがさらに好ましく、また、26質量部以下であることが好ましく、25質量部以下であることがより好ましい。 In addition, in the film-forming composition of the present disclosure, the content of the second inorganic fine particles per 100 parts by mass of the total mass (S1) is 12 to 27 parts by mass. When the content of the second inorganic fine particles is less than 12 parts by mass per 100 parts by mass of the total mass (S1), the effect of the second inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, the anti-snow accretion performance is lowered, and even if it exceeds 27 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating. The content of the second inorganic fine particles is preferably 15 parts by mass or more, more preferably 16 parts by mass or more, and 18 parts by mass or more per 100 parts by mass of the total mass (S1). is more preferably 26 parts by mass or less, and more preferably 25 parts by mass or less.
 前記第1の無機微粒子及び前記第2の無機微粒子の総含有量は、前記総質量(S1)100質量部あたり、20質量部以上である。これにより、所望の撥水性及び耐摩耗性が得られ、製膜製にも優れ、着雪防止性能も向上しやすい。前記第1の無機微粒子及び前記第2の無機微粒子の総含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、25質量部以上であることが好ましく、30質量部以上であることがより好ましく、また、50質量部以下であることが好ましく、45質量部以下であることがより好ましく、40質量部以下であることがさらに好ましい。 The total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts by mass or more per 100 parts by mass of the total mass (S1). As a result, desired water repellency and abrasion resistance can be obtained, excellent film-forming property can be achieved, and snow accretion prevention performance can be easily improved. The total content of the first inorganic fine particles and the second inorganic fine particles per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component, It is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and 40 parts by mass or less. is more preferred.
 なお、本開示の被膜形成用組成物において、「前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量(S1)」とは、固形分換算の質量を意味し、溶媒等の揮発成分は含まない。また、重合性成分が前記熱硬化性樹脂成分である場合は、当該総質量(S1)における前記重合性成分の質量とは、架橋性官能基を有する重合体及び硬化剤の全質量であることを意味し、重合性成分が前記光硬化性樹脂成分である場合は、光重合性モノマー及び光重合開始剤の全質量であることを意味する。重合性成分が前記熱硬化性樹脂成分及び前記光硬化性樹脂成分の両方である場合は、当該総質量(S1)における前記重合性成分の質量とは、架橋性官能基を有する重合体及び硬化剤並びに光重合性モノマー及び光重合開始剤の全質量であることを意味する。 In the film-forming composition of the present disclosure, the “total mass (S1) of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component” is calculated as solid content. It means mass and does not include volatile components such as solvents. Further, when the polymerizable component is the thermosetting resin component, the mass of the polymerizable component in the total mass (S1) is the total mass of the polymer having a crosslinkable functional group and the curing agent. When the polymerizable component is the photocurable resin component, it means the total mass of the photopolymerizable monomer and the photopolymerization initiator. When the polymerizable component is both the thermosetting resin component and the photocurable resin component, the mass of the polymerizable component in the total mass (S1) is a polymer having a crosslinkable functional group and a curing is the total weight of the agent and the photopolymerizable monomer and photoinitiator.
 本開示の被膜形成用組成物における前記撥水性成分(式(1)で表される化合物に基づく構造単位を有する重合体)の含有量は、優れた撥水性を有し、かつ、耐摩耗性に優れる被膜を形成しやすい点で、前記総質量(S1)100質量部あたり、0.1~30質量部であることが好ましい。前記撥水性成分の含有量は、前記総質量(S1)100質量部あたり、1質量部以上であることがより好ましく、また、15質量部以下であることがより好ましく、10質量部以下であることがさらに好ましい。 The content of the water-repellent component (polymer having a structural unit based on the compound represented by formula (1)) in the film-forming composition of the present disclosure has excellent water repellency and abrasion resistance. It is preferably 0.1 to 30 parts by mass per 100 parts by mass of the total mass (S1) in terms of easy formation of a coating excellent in the above. The content of the water-repellent component is more preferably 1 part by mass or more, more preferably 15 parts by mass or less, and 10 parts by mass or less per 100 parts by mass of the total mass (S1). is more preferred.
 本開示の被膜形成用組成物において、重合性成分の含有量は、前記総質量(S1)100質量部あたり、40~90質量部であることが好ましい。この場合、被膜の硬度が低下しにくく、撥水性及び耐水性が向上しやすい。重合性成分の含有量は、前記総質量(S1)100質量部あたり、50~90質量部であることがより好ましく、60~80質量部であることがさらに好ましい。 In the film-forming composition of the present disclosure, the content of the polymerizable component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S1). In this case, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved. The content of the polymerizable component is more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass, per 100 parts by mass of the total mass (S1).
 より具体的には、重合性成分が前記熱硬化性樹脂成分である場合は、前記熱硬化性樹脂成分の含有量は、前記総質量(S1)100質量部あたり、40~90質量部であることが好ましく、50~90質量部であることがより好ましく、60~80質量部であることがさらに好ましい。これにより、被膜の硬度が低下しにくく、撥水性及び耐水性が向上しやすい。重合性成分が前記光硬化性樹脂成分である場合は、前記光硬化性樹脂成分の含有量は、前記総質量(S1)100質量部あたり、40~90質量部であることが好ましく、50~90質量部であることがより好ましく、60~80質量部であることがさらに好ましい。これにより、被膜の硬度が低下しにくく、撥水性及び耐水性が向上しやすい。 More specifically, when the polymerizable component is the thermosetting resin component, the content of the thermosetting resin component is 40 to 90 parts by mass per 100 parts by mass of the total mass (S1). , more preferably 50 to 90 parts by mass, even more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved. When the polymerizable component is the photocurable resin component, the content of the photocurable resin component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S1), and 50 to It is more preferably 90 parts by mass, and even more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.
 本開示の被膜形成用組成物では、前記重合性成分及び前記撥水性成分の少なくとも一方はフッ素原子(つまり、フルオロアルキル基)又はポリシロキサンを有することが好ましく、フッ素原子を有することがさらに好ましく、中でも前記重合性成分がフッ素原子を有することが特に好ましい。これにより、被膜形成用組成物から形成される被膜は、優れた撥水性を有し、硬度も高く、しかも、耐水性にも優れ、さらには耐摩耗性が向上することもある。もちろん、前記重合性成分及び前記撥水性成分の両方がフッ素原子(フルオロアルキル基)を有することもでき、あるいは、前記重合性成分及び前記撥水性成分の両方がフッ素原子を有していなくてもよい。前記重合性成分がフルオロアルキル基を有する場合の一例として、前記熱硬化性樹脂成分に含まれる架橋性重合体が重合体Fである場合が挙げられる。前記撥水性成分がフルオロアルキル基を有する場合の一例としては、式(1)で表される化合物においてフルオロアルキル基の炭素数が1~6のフルオロアルキル(メタ)アクリレートである重合体が挙げられる。 In the film-forming composition of the present disclosure, at least one of the polymerizable component and the water-repellent component preferably has a fluorine atom (that is, a fluoroalkyl group) or polysiloxane, and more preferably has a fluorine atom, Among them, it is particularly preferable that the polymerizable component has a fluorine atom. As a result, the film formed from the film-forming composition has excellent water repellency, high hardness, excellent water resistance, and improved abrasion resistance. Of course, both the polymerizable component and the water-repellent component may have a fluorine atom (fluoroalkyl group), or both the polymerizable component and the water-repellent component may have no fluorine atom. good. An example of the case where the polymerizable component has a fluoroalkyl group is the case where the crosslinkable polymer contained in the thermosetting resin component is the polymer F. An example of the case where the water-repellent component has a fluoroalkyl group is a polymer that is a fluoroalkyl (meth)acrylate in which the fluoroalkyl group has 1 to 6 carbon atoms in the compound represented by formula (1). .
 本開示の被膜形成用組成物に含まれる撥水性成分がフッ素原子(特にフルオロアルキル基)を有さない場合は、被膜の耐摩耗性がさらに向上しやすい。中でも、撥水性成分が、前記式(1)で表される化合物において、Rが炭素数20以下の直鎖又は分岐状のアルキル基である場合は、被膜の耐摩耗性がより向上しやすい。斯かる化合物としては、例えば、公知の潤滑油に含まれている飽和脂肪酸等を挙げることができ、その例として、ヤシ油、パーム油、菜種油、ヒマシ油等に含まれるカプリル酸、カプリン酸、ラウリン酸、ミスチリン酸、パルチミン酸、ステアリン酸またはこれらの飽和脂肪酸と同様の炭素数の直鎖アルキル基を有する構造体が挙げられる。 When the water-repellent component contained in the film-forming composition of the present disclosure does not have a fluorine atom (especially a fluoroalkyl group), the abrasion resistance of the film is likely to be further improved. Among them, when the water-repellent component is a compound represented by the formula (1), and R a is a linear or branched alkyl group having 20 or less carbon atoms, the abrasion resistance of the coating is more likely to be improved. . Examples of such compounds include saturated fatty acids contained in known lubricating oils, examples of which include caprylic acid, capric acid, Structures having straight-chain alkyl groups with the same number of carbon atoms as those of lauric acid, myristic acid, palmitic acid, stearic acid, or these saturated fatty acids can be mentioned.
 本開示の被膜形成用組成物は、第1の無機微粒子及び第2の無機微粒子と、重合性成分と、撥水性成分とを含む限り、他の成分が含まれていてもよい。例えば、被膜形成用組成物は、前記式(1)で表される化合物に基づく構造単位を有する重合体以外に、撥水性を示し得る成分を含むことができる。斯かる成分の具体例としては、主幹骨格が(メタ)アクリレートであって、その側鎖部位にフルオロアルキル基又はアルキル基を有するポリマーが挙げられる。 The film-forming composition of the present disclosure may contain other components as long as it contains the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component. For example, the film-forming composition can contain a component capable of exhibiting water repellency in addition to the polymer having a structural unit based on the compound represented by formula (1). A specific example of such a component is a polymer having a (meth)acrylate as a main skeleton and having a fluoroalkyl group or an alkyl group at its side chain site.
 また、被膜形成用組成物は、必要に応じて、溶媒を含むこともできる。溶媒の種類は限定されず、例えば、被膜を形成するために使用されている溶媒を広く使用することができ、例えば、ハイドロフルオロエーテル等のフッ素系溶剤、エステル化合物、アルコール化合物等を挙げることができる。 The film-forming composition can also contain a solvent, if necessary. The type of solvent is not limited, and for example, a wide range of solvents that are used to form a film can be used. Examples include fluorine-based solvents such as hydrofluoroethers, ester compounds, alcohol compounds, and the like. can.
 被膜形成用組成物に含まれる溶媒の含有量は特に限定されず、例えば、第1の無機微粒子、第2の無機微粒子、重合性成分及び撥水性成分の総質量(S1)100質量部あたり、200~2000質量部とすることができる。 The content of the solvent contained in the film-forming composition is not particularly limited. It can be 200 to 2000 parts by mass.
 被膜形成用組成物は、撥水性を示し得る成分及び溶媒以外の他の添加剤を含むこともできる。被膜形成用組成物が他の添加剤を含む場合、その含有割合は、第1の無機微粒子、第2の無機微粒子、重合性成分及び撥水性成分の全質量に対して5質量%以下とすることが望ましい。 The film-forming composition can also contain additives other than a component capable of exhibiting water repellency and a solvent. When the film-forming composition contains other additives, the content ratio thereof is 5% by mass or less with respect to the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component. is desirable.
 本開示の被膜形成用組成物の調製方法は特に限定されない。例えば、第1の無機微粒子と、第2の無機微粒子と、重合性成分(例えば、前記重合体Fと硬化剤を含む熱硬化性樹脂成分)と、撥水性成分(式(1)で表される化合物)とを所定の配合量で混合することで調製することができる。混合方法も特に限定されず、例えば、公知の混合機等を広く使用することができる。 The method for preparing the film-forming composition of the present disclosure is not particularly limited. For example, first inorganic fine particles, second inorganic fine particles, a polymerizable component (for example, a thermosetting resin component containing the polymer F and a curing agent), and a water-repellent component (represented by formula (1) It can be prepared by mixing with a predetermined compounding amount. The mixing method is also not particularly limited, and for example, a wide range of known mixers and the like can be used.
 本開示の被膜形成用組成物を用いて被膜を形成する方法は特に限定されない。例えば、被膜形成用組成物を、被膜を形成するための基材に塗布して塗膜を形成し、該塗膜を硬化することで、被膜を形成することができる。斯かる被膜は本開示の被膜形成用組成物の硬化物である。 The method of forming a film using the film-forming composition of the present disclosure is not particularly limited. For example, a film can be formed by applying the film-forming composition to a substrate for forming a film to form a coating film, and curing the coating film. Such a coating is a cured product of the coating-forming composition of the present disclosure.
 被膜形成用組成物の塗布方法は特に制限されず、公知の塗膜形成方法を広く採用することができる。例えば、刷毛塗り、スプレー、スピンコート、ディスペンサー等の方法で塗布できる。被膜形成用組成物の塗膜を形成するための基材の種類は特に限定されず、例えば、アクリル樹脂、ポリカーボネート樹脂等の公知の樹脂基材、その他、金属、無機基材等の各種の基材を挙げることができる。 The coating method of the film-forming composition is not particularly limited, and a wide range of known coating film-forming methods can be employed. For example, it can be applied by a method such as brush coating, spray coating, spin coating, or dispenser. The type of base material for forming the coating film of the film-forming composition is not particularly limited. material can be mentioned.
 被膜形成用組成物の硬化方法も特に限定されず、例えば、熱硬化、光硬化等の種々の方法を採用することができ、熱硬化と光硬化とを組み合わせることもできる。熱硬化を採用する場合、被膜形成用組成物の塗膜を60~150℃に加熱することが好ましく、この場合、被膜形成用組成物の被膜が形成されやすく、硬度も高く、耐水性にも優れる。加熱時間は特に制限されず、加熱温度に応じて適宜設定することができる。 The method of curing the film-forming composition is also not particularly limited, and for example, various methods such as heat curing and photo-curing can be employed, and heat-curing and photo-curing can be combined. When heat curing is employed, it is preferable to heat the coating film of the film-forming composition to 60 to 150 ° C. In this case, the film of the film-forming composition is easily formed, has high hardness, and is also water resistant. Excellent. The heating time is not particularly limited, and can be appropriately set according to the heating temperature.
 本開示の被膜形成用組成物を用いて薬液を調製することができる。斯かる薬液は、本開示の被膜形成用組成物を含むので、被膜を形成するための使用に好適である。薬液は、被膜形成用組成物のみで構成することができ、あるいは、本開示の被膜形成用組成物の目的とする諸性能が阻害されない程度である限り、他の添加剤(例えば、被膜形成溶薬剤として使用される公知の添加剤)を含むことができる。 A chemical solution can be prepared using the film-forming composition of the present disclosure. Since such a chemical solution contains the film-forming composition of the present disclosure, it is suitable for use in forming a film. The chemical solution can be composed only of the film-forming composition, or other additives (for example, film-forming solvent known additives used as drugs).
 2.被膜
 本開示の被膜は、例えば、前述の本開示の被膜形成用組成物を用いて形成することができ、あるいは、本開示の被膜は、前記薬液を用いて形成することができる。この場合、本開示の被膜は、本開示の被膜形成用組成物又は薬液の硬化物である。
2. Coating The coating of the present disclosure can be formed, for example, using the coating composition of the present disclosure described above, or the coating of the present disclosure can be formed using the chemical solution. In this case, the film of the present disclosure is a cured product of the film-forming composition or chemical solution of the present disclosure.
 従って、本開示の被膜は、第1の無機微粒子と、第2の無機微粒子と、バインダー成分と、撥水性成分とを含む。ここで、バインダー成分とは、前記重合性成分が重合して形成される成分である。 Therefore, the coating of the present disclosure includes first inorganic fine particles, second inorganic fine particles, a binder component, and a water-repellent component. Here, the binder component is a component formed by polymerizing the polymerizable component.
 本開示の被膜において、第1の無機微粒子及び第2の無機微粒子はそれぞれ、本開示の被膜形成用組成物に含まれる第1の無機微粒子及び第2の無機微粒子と同じである。従って、被膜に含まれる第1の無機微粒子は平均粒子径が1nm以上100nm以下、被膜に含まれる第2の無機微粒子は平均粒子径が500nm以上5μm以下である。 In the film of the present disclosure, the first inorganic fine particles and the second inorganic fine particles are respectively the same as the first inorganic fine particles and the second inorganic fine particles contained in the film-forming composition of the present disclosure. Therefore, the average particle size of the first inorganic fine particles contained in the coating is 1 nm or more and 100 nm or less, and the average particle size of the second inorganic fine particles contained in the coating is 500 nm or more and 5 μm or less.
 第1の無機微粒子の平均粒子径は、好ましくは2nm以上、より好ましくは3nm以上、さらに好ましくは4nm以上、特に好ましくは5nm以上である。また、第1の無機微粒子の平均粒子径は、好ましくは80nm以下、より好ましくは60nm以下、さらに好ましくは50nm以下、特に好ましくは30nm以下である。 The average particle size of the first inorganic fine particles is preferably 2 nm or more, more preferably 3 nm or more, even more preferably 4 nm or more, and particularly preferably 5 nm or more. The average particle size of the first inorganic fine particles is preferably 80 nm or less, more preferably 60 nm or less, even more preferably 50 nm or less, and particularly preferably 30 nm or less.
 第2の無機微粒子の平均粒子径は、好ましくは800nm以上、より好ましくは1μm以上、さらに好ましくは1.5μm以上、特に好ましくは2μm以上である。また、第2の無機微粒子の平均粒子径は、好ましくは4.5μm以下、より好ましくは4μm以下、さらに好ましくは3.5μm以下、特に好ましくは3μm以下である。 The average particle diameter of the second inorganic fine particles is preferably 800 nm or more, more preferably 1 µm or more, even more preferably 1.5 µm or more, and particularly preferably 2 µm or more. The average particle size of the second inorganic fine particles is preferably 4.5 μm or less, more preferably 4 μm or less, still more preferably 3.5 μm or less, and particularly preferably 3 μm or less.
 第1の無機微粒子及び第2の無機微粒子は、前述の平均粒子径を満たす限り、その種類は特に限定されず、例えば、公知の金属酸化物の微粒子を広く例示することができる。具体的に金属酸化物としては、シリカ、アルミナ、酸化チタン、ジルコニア等を挙げることができ、被膜の硬度及び耐水性が高まりやすいという点で、第1の無機微粒子及び第2の無機微粒子はシリカであることが好ましい。第1の無機微粒子及び第2の無機微粒子の種類は同一であってもよいし、異なっていてもよく、好ましくは、第1の無機微粒子及び第2の無機微粒子が同一であり、より好ましくは、第1の無機微粒子及び第2の無機微粒子がいずれもシリカである。 The types of the first inorganic fine particles and the second inorganic fine particles are not particularly limited as long as they satisfy the aforementioned average particle diameter, and for example, a wide range of known metal oxide fine particles can be exemplified. Specific examples of metal oxides include silica, alumina, titanium oxide, zirconia, and the like, and the first inorganic fine particles and the second inorganic fine particles are silica in that the hardness and water resistance of the coating are likely to increase. is preferably The types of the first inorganic fine particles and the second inorganic fine particles may be the same or different, preferably the first inorganic fine particles and the second inorganic fine particles are the same, more preferably , both the first inorganic fine particles and the second inorganic fine particles are silica.
 第1の無機微粒子及び第2の無機微粒子の比表面積は特に限定されず、例えば、得られる被膜の硬度が向上しやすい点で、30~700m/gであることが好ましく、800~330m/gであることがさらに好ましい。本開示の被膜形成用組成物において、前記微粒子の比表面積は、BET法によって計測された値(いわゆるBET比表面積)を意味する。 The specific surface areas of the first inorganic fine particles and the second inorganic fine particles are not particularly limited. For example, the specific surface area is preferably from 30 to 700 m 2 /g, more preferably from 800 to 330 m 2 , from the viewpoint of easily improving the hardness of the resulting coating. /g is more preferred. In the film-forming composition of the present disclosure, the specific surface area of the fine particles means a value measured by the BET method (so-called BET specific surface area).
 第1の無機微粒子及び第2の無機微粒子は、表面が親水性であってもよいし、疎水性であってもよい。第1の無機微粒子及び第2の無機微粒子は、親水性及び疎水性の混合物であってもよい。第1の無機微粒子及び第2の無機微粒子の形状も特に限定されず、例えば、球状、楕円球状等を挙げることができ、また、異形状等の不定形粒子であってもよい。第1の無機微粒子及び第2の無機微粒子は、表面にラジカル重合性の反応基(例えば、アクリロイル基等の重合性二重結合)を有していないことが好ましく、即ち、第1の無機微粒子及び第2の無機微粒子の表面には重合体(例えば、バインダー成分及び撥水性成分)が共有結合的に結合しないことが好ましい。これにより、被膜の耐摩耗性が向上し、特には着雪防止性能も高まりやすい。 The surfaces of the first inorganic fine particles and the second inorganic fine particles may be hydrophilic or hydrophobic. The first inorganic fine particles and the second inorganic fine particles may be a mixture of hydrophilic and hydrophobic properties. The shapes of the first inorganic fine particles and the second inorganic fine particles are also not particularly limited, and examples thereof include spherical, ellipsoidal and the like, and may be amorphous particles such as irregular shaped particles. The first inorganic fine particles and the second inorganic fine particles preferably do not have a radically polymerizable reactive group (for example, a polymerizable double bond such as an acryloyl group) on the surface, that is, the first inorganic fine particles And it is preferable that no polymer (for example, a binder component and a water-repellent component) is covalently bonded to the surface of the second inorganic fine particles. As a result, the wear resistance of the coating is improved, and particularly the snow accretion prevention performance is likely to be enhanced.
 第1の無機微粒子及び第2の無機微粒子の形状も特に限定されず、例えば、球状、楕円球状等を挙げることができ、また、異形状等の不定形粒子であってもよい。第1の無機微粒子及び第2の無機微粒子は、凝集体を形成することもできる。凝集体は球体及び非球体のいずれでもよいし、鎖状的に形成されていてもよい。 The shape of the first inorganic fine particles and the second inorganic fine particles is also not particularly limited, and examples thereof include spherical, ellipsoidal and the like, and may be amorphous particles such as irregular shaped particles. The first inorganic fine particles and the second inorganic fine particles can also form aggregates. Aggregates may be spherical or non-spherical, and may be chain-like.
 本開示の被膜に含まれる無機微粒子は、第1の無機微粒子及び第2の無機微粒子を80質量%以上含むことができ、好ましくは90質量%以上、より好ましくは95質量%以上、さらに好ましくは99質量%以上である。本開示の被膜に含まれる無機微粒子は、第1の無機微粒子及び第2の無機微粒子のみであってもよく、第1の無機微粒子及び第2の無機微粒子のみであることが特に好ましい。 The inorganic fine particles contained in the coating of the present disclosure can contain 80% by mass or more of the first inorganic fine particles and the second inorganic fine particles, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably It is 99% by mass or more. The inorganic fine particles contained in the film of the present disclosure may be only the first inorganic fine particles and the second inorganic fine particles, and are particularly preferably only the first inorganic fine particles and the second inorganic fine particles.
 本開示の被膜において、第1の無機微粒子及び第2の無機微粒子の両者の含有比率は特に制限されない。本開示の被膜が、優れた撥水性を有し、かつ、耐摩耗性に優れるという点で、第1の無機微粒子及び第2の無機微粒子の総質量に対し、第1の無機微粒子が5質量%以上であることが好ましく、10質量%以上であることがより好ましく、20質量%以上であることがさらに好ましい。また、第1の無機微粒子及び第2の無機微粒子の総質量に対し、第1の無機微粒子が90質量%以下であることが好ましく、80質量%以下であることがより好ましく、60質量%以下であることがさらに好ましく、50質量%以下であることが特に好ましい。 In the coating of the present disclosure, the content ratio of both the first inorganic fine particles and the second inorganic fine particles is not particularly limited. In that the film of the present disclosure has excellent water repellency and excellent abrasion resistance, the first inorganic fine particles are 5 masses with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. % or more, more preferably 10 mass % or more, and even more preferably 20 mass % or more. Further, the first inorganic fine particles are preferably 90% by mass or less, more preferably 80% by mass or less, and 60% by mass or less with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. More preferably, the content is particularly preferably 50% by mass or less.
 本開示の被膜において、バインダー成分は、前述の重合性成分が硬化して形成される成分である。例えば、重合性成分が前述の熱硬化性樹脂成分である場合は、前記重合体Fが前記硬化剤で硬化された(架橋された)重合体である。バインダー成分には、本開示の被膜の性能が損なわれない範囲で、未硬化の重合性成分が混在していても良い。 In the film of the present disclosure, the binder component is a component formed by curing the polymerizable component described above. For example, when the polymerizable component is the aforementioned thermosetting resin component, the polymer F is a polymer cured (crosslinked) with the curing agent. The binder component may contain an uncured polymerizable component as long as the performance of the film of the present disclosure is not impaired.
 本開示の被膜において、撥水性成分は、前述の本開示の被膜形成用組成物に含まれる撥水性成分と同じである。従って、被膜中の撥水性成分は、前記式(1)で表される化合物に由来する構造単位を有する重合体である。 In the film of the present disclosure, the water-repellent component is the same as the water-repellent component contained in the above-described film-forming composition of the present disclosure. Therefore, the water-repellent component in the film is a polymer having a structural unit derived from the compound represented by formula (1).
 本開示の被膜において、式(1)で表される化合物に由来する構造単位を有する重合体は、式(1)で表される化合物以外に基づく構成単位を含むことができる。斯かる構成単位として、ヒドロキシアルキル(メタ)アクリレートに基づく構成単位、エポキシ部位を有する(メタ)アクリレートに基づく構成単位、アミド結合を有する(メタ)アクリレート(例えば、前記式(1)のYがアミド結合を有する官能基に置き換えられた化合物)に基づく構成単位、塩素含有ビニルモノマーに基づく構成単位、塩素含有ビニリデンモノマーに基づく構成単位、アクリルアミドモノマーに基づく構成単位等のいずれか1種以上を挙げることができる。例えば、ヒドロキシアルキル(メタ)アクリレートに基づく構成単位としてはとしては、2-ヒドロキシエチルメタアクリレート等を挙げることができ、エポキシ部位を有する(メタ)アクリレートとしてはグリシジル(メタ)アクリレート等を挙げることができ、アミド結合を有する(メタ)アクリレートとしてはステアリン酸アミドエチル(メタ)アクリレート等を挙げることができ、塩素含有ビニルモノマーとしては塩化ビニル等を挙げることができ、塩素含有ビニリデンモノマーとしては塩化ビニリデン等を挙げることができ、アクリルアミドモノマーとしてはN-メチロールアクリルアミドを挙げることができる。 In the coating of the present disclosure, the polymer having structural units derived from the compound represented by formula (1) can contain structural units other than the compound represented by formula (1). Examples of such structural units include structural units based on hydroxyalkyl (meth)acrylates, structural units based on (meth)acrylates having an epoxy site, and (meth)acrylates having an amide bond (for example, Y in the formula (1) is amide a compound substituted with a functional group having a bond), a structural unit based on a chlorine-containing vinyl monomer, a structural unit based on a chlorine-containing vinylidene monomer, a structural unit based on an acrylamide monomer, etc. can be done. For example, structural units based on hydroxyalkyl (meth)acrylates include 2-hydroxyethyl methacrylate and the like, and (meth)acrylates having an epoxy moiety include glycidyl (meth)acrylate and the like. Examples of (meth)acrylates having an amide bond include stearamidoethyl (meth)acrylate. Examples of chlorine-containing vinyl monomers include vinyl chloride. Examples of chlorine-containing vinylidene monomers include vinylidene chloride. and the acrylamide monomer can include N-methylolacrylamide.
 本開示の被膜において、式(1)で表される化合物に基づく構造単位を少なくとも有する重合体には、さらに他の構造単位が含まれていてもよい。他の構造単位を形成するための単量体としては、種々の単官能単量体及び/又は多官能単量体の1種以上を挙げることができる。斯かる単量体は、前述した酸基含有単量体、水酸基含有単量体、塩素含有単量体、窒素含有単量体、アルキレングリコール基含有単量体、アルコキシアルキル基含有単量体、カルボニル基含有単量体、シラン基含有単量体、環構造含有単量体を挙げることができ、それぞれの種類も前述同様である。 In the coating of the present disclosure, the polymer having at least structural units based on the compound represented by formula (1) may further contain other structural units. Monomers for forming other structural units may include one or more of various monofunctional monomers and/or polyfunctional monomers. Such monomers include the aforementioned acid group-containing monomers, hydroxyl group-containing monomers, chlorine-containing monomers, nitrogen-containing monomers, alkylene glycol group-containing monomers, alkoxyalkyl group-containing monomers, A carbonyl group-containing monomer, a silane group-containing monomer, and a ring structure-containing monomer can be mentioned, and the respective types are the same as those described above.
 本開示の被膜において、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量(以下、「総質量(S2)」と表記する)100質量部あたりの前記第1の無機微粒子の含有量は、3~25質量部である。前記第1の無機微粒子の含有量が、前記総質量(S2)100質量部あたり3質量部を下回ると、第1の無機微粒子の効果を十分に発揮できず、所望の撥水性及び耐摩耗性が得られず、着雪防止性能も低下し、また、25質量部を超えても所望の撥水性及び耐摩耗性が得られず、そればかりか被膜の形成も難しくなる。前記第1の無機微粒子の含有量は、前記総質量(S2)100質量部あたり、5質量部以上であることが好ましく、8質量部以上であることがより好ましく、10質量部以上であることがさらに好ましい。また、前記第1の無機微粒子の含有量は、前記総質量(S2)100質量部あたり、23質量部以下であることが好ましく、22質量部以下であることがより好ましく、20質量部以下であることがさらに好ましい。 In the coating film of the present disclosure, the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component (hereinafter referred to as “total mass (S2)”) per 100 parts by mass The content of the first inorganic fine particles is 3 to 25 parts by mass. When the content of the first inorganic fine particles is less than 3 parts by mass per 100 parts by mass of the total mass (S2), the effect of the first inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, and the anti-snow accretion performance is lowered, and even if the amount exceeds 25 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating. The content of the first inorganic fine particles is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 10 parts by mass or more per 100 parts by mass of the total mass (S2). is more preferred. In addition, the content of the first inorganic fine particles is preferably 23 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less per 100 parts by mass of the total mass (S2). It is even more preferable to have
 また、本開示の被膜において、総質量(S2)100質量部あたりの前記第2の無機微粒子の含有量は、12~27質量部である。前記第2の無機微粒子の含有量が、前記総質量(S2)100質量部あたり12質量部を下回ると、第2の無機微粒子の効果を十分に発揮できず、所望の撥水性及び耐摩耗性が得られず、着雪防止性能も低下し、また、27質量部を超えても所望の撥水性及び耐摩耗性が得られず、そればかりか被膜の形成も難しくなる。前記第2の無機微粒子の含有量は、前記総質量(S2)100質量部あたり、15質量部以上であることが好ましく、16質量部以上であることがより好ましく、18質量部以上であることがさらに好ましく、また、26質量部以下であることが好ましく、25質量部以下であることがより好ましい。 Further, in the coating of the present disclosure, the content of the second inorganic fine particles per 100 parts by mass of the total mass (S2) is 12 to 27 parts by mass. When the content of the second inorganic fine particles is less than 12 parts by mass per 100 parts by mass of the total mass (S2), the effect of the second inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, the anti-snow accretion performance is lowered, and even if it exceeds 27 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating. The content of the second inorganic fine particles is preferably 15 parts by mass or more, more preferably 16 parts by mass or more, and 18 parts by mass or more per 100 parts by mass of the total mass (S2). is more preferably 26 parts by mass or less, and more preferably 25 parts by mass or less.
 前記第1の無機微粒子及び前記第2の無機微粒子の総含有量は、前記総質量(S2)100質量部あたり、20質量部以上である。これにより、所望の撥水性及び耐摩耗性が得られ、製膜製にも優れ、着雪防止性能も向上しやすい。前記第1の無機微粒子及び前記第2の無機微粒子の総含有量は、前記総質量(S2)100質量部あたり、25質量部以上であることが好ましく、30質量部以上であることがより好ましく、また、50質量部以下であることが好ましく、45質量部以下であることがより好ましく、40質量部以下であることがさらに好ましい。 The total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts by mass or more per 100 parts by mass of the total mass (S2). As a result, desired water repellency and abrasion resistance can be obtained, excellent film-forming property can be achieved, and snow accretion prevention performance can be easily improved. The total content of the first inorganic fine particles and the second inorganic fine particles is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, per 100 parts by mass of the total mass (S2). Also, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.
 なお、本開示の被膜の「前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量(S2)」において、バインダー成分が前記熱硬化性樹脂の硬化物である場合は、当該総質量(S2)における前記バインダー成分の質量とは、架橋性官能基を有する重合体及び硬化剤の硬化物の全質量であることを意味し、バインダー成分が前記光硬化性樹脂の硬化物である場合は、光重合性モノマー及び光重合開始剤の全質量であることを意味する。バインダー成分が前記熱硬化性樹及び前記光硬化性樹脂の硬化物の両方である場合は、当該総質量(S2)における前記重合性成分の質量とは、架橋性官能基を有する重合体及び硬化剤の硬化物並びに光重合性モノマー及び光重合開始剤の硬化物の全質量であることを意味する。 In the "total mass (S2) of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component" of the coating of the present disclosure, the binder component is a cured product of the thermosetting resin , the mass of the binder component in the total mass (S2) means the total mass of the cured product of the polymer having a crosslinkable functional group and the curing agent, and the binder component is the photocurable In the case of a cured product of a flexible resin, it means the total mass of the photopolymerizable monomer and the photopolymerization initiator. When the binder component is both the thermosetting resin and the cured product of the photocurable resin, the mass of the polymerizable component in the total mass (S2) includes a polymer having a crosslinkable functional group and a cured product. It means the total mass of the cured product of the agent and the cured product of the photopolymerizable monomer and the photopolymerization initiator.
 本開示の被膜における前記撥水性成分の含有量は、優れた撥水性を有し、かつ、耐摩耗性に優れる被膜を形成しやすい点で、前記総質量(S2)100質量部あたり、0.1~30質量部である。前記撥水性成分の含有量は、前記総質量(S2)100質量部あたり、1質量部以上であることが好ましく、また、15質量部以下であることがより好ましく、10質量部以下であることがさらに好ましい。 The content of the water-repellent component in the coating film of the present disclosure is 0.00% per 100 parts by mass of the total mass (S2), since a coating film having excellent water repellency and excellent wear resistance can be easily formed. 1 to 30 parts by mass. The content of the water-repellent component is preferably 1 part by mass or more, more preferably 15 parts by mass or less, and 10 parts by mass or less per 100 parts by mass of the total mass (S2). is more preferred.
 本開示の被膜において、バインダー成分の含有量は、前記総質量(S2)100質量部あたり、40~90質量部であることが好ましい。この場合、被膜の硬度が低下しにくく、撥水性及び耐水性が向上しやすい。バインダー成分の含有量は、前記総質量(S2)100質量部あたり、50~90質量部であることがより好ましく、60~80質量部であることがさらに好ましい。 In the coating of the present disclosure, the content of the binder component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S2). In this case, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved. The content of the binder component is more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass, per 100 parts by mass of the total mass (S2).
 より具体的には、バインダー成分が前記熱硬化性樹脂の硬化物である場合は、前記熱硬化性樹脂の硬化物の含有量は、前記総質量(S2)100質量部あたり、40~90質量部であることが好ましく、50~90質量部であることがより好ましく、60~80質量部であることがより好ましい。これにより、被膜の硬度が低下しにくく、撥水性及び耐水性が向上しやすい。バインダー成分が前記光硬化性樹脂の硬化物である場合は、前記光硬化性樹脂の硬化物の含有量は、前記総質量(S2)100質量部あたり、40~90質量部であることが好ましく、50~90質量部であることがより好ましく、60~80質量部であることがより好ましい。これにより、被膜の硬度が低下しにくく、撥水性及び耐水性が向上しやすい。 More specifically, when the binder component is a cured product of the thermosetting resin, the content of the cured product of the thermosetting resin is 40 to 90 mass parts per 100 parts by mass of the total mass (S2). parts, more preferably 50 to 90 parts by mass, and more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved. When the binder component is a cured product of the photocurable resin, the content of the cured product of the photocurable resin is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S2). , more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.
 本開示の被膜では、前記バインダー成分及び前記撥水性成分の少なくとも一方はフッ素原子(つまり、フルオロアルキル基)又はポリシロキサンを有することが好ましく、フッ素原子を有することがさらに好ましく、中でも前記バインダー成分がフッ素原子を有することがさらに好ましい。これにより、被膜は、優れた撥水性を有し、硬度も高く、しかも、耐水性にも優れ、さらには耐摩耗性が向上することもある。もちろん、前記バインダー成分及び前記撥水性成分の両方がフッ素原子(フルオロアルキル基)を有することもでき、あるいは、前記バインダー成分及び前記撥水性成分の両方がフッ素原子を有していなくてもよい。前記バインダー成分がフルオロアルキル基を有する場合の一例としては重合体F又はその架橋体が挙げられる。前記撥水性成分がフルオロアルキル基を有する場合、式(1)で表される化合物においてフルオロアルキル基の炭素数が1~6のフルオロアルキル(メタ)アクリレートである重合体が挙げられる。 In the film of the present disclosure, at least one of the binder component and the water-repellent component preferably has a fluorine atom (that is, a fluoroalkyl group) or polysiloxane, and more preferably has a fluorine atom. It is more preferable to have a fluorine atom. As a result, the coating has excellent water repellency, high hardness, excellent water resistance, and even improved abrasion resistance. Of course, both the binder component and the water repellent component may have fluorine atoms (fluoroalkyl groups), or both the binder component and the water repellent component may not have fluorine atoms. An example of the binder component having a fluoroalkyl group is polymer F or a crosslinked product thereof. When the water-repellent component has a fluoroalkyl group, the polymer represented by the formula (1) is a fluoroalkyl (meth)acrylate in which the fluoroalkyl group has 1 to 6 carbon atoms.
 本開示の被膜は、バインダー成分及び撥水性成分は、第1の無機微粒子及び第2の無機微粒子を被覆し得るが、共有結合的には結合せず、例えば、物理的に吸着することが好ましい。これにより、従来トレードオフの関係にあった耐摩耗性及び着雪防止性能の両方を向上させることが可能となる。 In the film of the present disclosure, the binder component and the water-repellent component can coat the first inorganic fine particles and the second inorganic fine particles, but are not covalently bonded, for example, preferably physically adsorbed. . This makes it possible to improve both the wear resistance and the anti-snow accretion performance, which have conventionally been in a trade-off relationship.
 本開示の被膜に含まれる撥水性成分がフッ素原子(特にフルオロアルキル基)を有さない場合は、被膜の耐摩耗性がさらに向上しやすい。中でも、撥水性成分が、前記式(1)で表される化合物において、Rが炭素数20以下の直鎖又は分岐状のアルキル基である場合は、被膜の耐摩耗性がより向上しやすい。斯かる化合物としては、例えば、公知の潤滑油に含まれている飽和脂肪酸等を挙げることができ、その例として、ヤシ油、パーム油、菜種油、ヒマシ油等に含まれるカプリル酸、カプリン酸、ラウリン酸、ミスチリン酸、パルチミン酸、ステアリン酸またはこれらの飽和脂肪酸と同様の炭素数の直鎖アルキル基を有する構造体が挙げられる。 When the water-repellent component contained in the coating of the present disclosure does not have a fluorine atom (especially a fluoroalkyl group), the abrasion resistance of the coating is likely to be further improved. Among them, when the water-repellent component is a compound represented by the formula (1), and R a is a linear or branched alkyl group having 20 or less carbon atoms, the abrasion resistance of the coating is more likely to be improved. . Examples of such compounds include saturated fatty acids contained in known lubricating oils, examples of which include caprylic acid, capric acid, Structures having straight-chain alkyl groups with the same number of carbon atoms as those of lauric acid, myristic acid, palmitic acid, stearic acid, or these saturated fatty acids can be mentioned.
 また、本開示の被膜は、被膜が形成されたときに被膜に撥水性を付与することができる成分であって、式(1)で表される化合物以外の成分を含むことができる。斯かる成分の具体例としては、主幹骨格が(メタ)アクリレートであって、その側鎖部位にフルオロアルキル基又はアルキル基を有するポリマーが挙げられる。 In addition, the coating of the present disclosure can contain a component other than the compound represented by formula (1), which is a component capable of imparting water repellency to the coating when the coating is formed. A specific example of such a component is a polymer having a (meth)acrylate as a main skeleton and having a fluoroalkyl group or an alkyl group at its side chain site.
 本開示の被膜は、例えば、水の接触角は150°以上である。これにより、本開示の被膜は優れた撥水性が発揮され得る。 The coating of the present disclosure has, for example, a water contact angle of 150° or more. This allows the coating of the present disclosure to exhibit excellent water repellency.
 本開示の被膜は、例えば、紙製ウエスを荷重100g/cmで少なくとも50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。 The coating of the present disclosure has a surface with a water contact angle of 150° or more after rubbing at least 50 times with a paper waste cloth under a load of 100 g/cm 2 .
 本開示の被膜は、後記する被膜の着雪試験において、着雪開始時間が例えば5分以上であることが好ましく、7分以上であることがより好ましく、10分以上であることがさらに好ましい。 In the snow accretion test of the coating described later, the coating of the present disclosure preferably has a snow accretion start time of, for example, 5 minutes or longer, more preferably 7 minutes or longer, and even more preferably 10 minutes or longer.
 本開示の被膜は、例えば、平均膜厚が10nm~100μm、最低局部膜厚が5nm~50μm、最大局部膜厚が15nm~150μmであり、好ましくは、平均膜厚が15nm~95μm、最低局部膜厚が10nm~45μm、最大局部膜厚が20nm~145μm、より好ましくは、平均膜厚が20nm~90μm、最低局部膜厚が15nm~40μm、最大局部膜厚が25nm~140μm、である。平均膜厚は、例えば、塗布した塗膜量、固形分濃度、組成物の密度より算出した乾燥膜厚により算出可能である。最低局部膜厚、最大局部膜厚は、3次元の形状を測定できる装置を用いることで、算出可能である。その装置の一例として、KEYENCE製の形状解析レーザー顕微鏡VK-X1000が挙げられる。 The coating of the present disclosure has, for example, an average thickness of 10 nm to 100 μm, a minimum local thickness of 5 nm to 50 μm, and a maximum local thickness of 15 nm to 150 μm, preferably an average thickness of 15 nm to 95 μm, and a minimum local thickness of The thickness is 10 nm to 45 μm, the maximum local thickness is 20 nm to 145 μm, more preferably the average thickness is 20 nm to 90 μm, the minimum local thickness is 15 nm to 40 μm, and the maximum local thickness is 25 nm to 140 μm. The average film thickness can be calculated from, for example, the amount of applied coating film, the solid content concentration, and the dry film thickness calculated from the density of the composition. The minimum local film thickness and the maximum local film thickness can be calculated using a device capable of measuring three-dimensional shapes. An example of such a device is a shape analysis laser microscope VK-X1000 manufactured by KEYENCE.
 本開示の被膜は、各種基材上に形成され得る。基材としては、例えば、アクリル樹脂、ポリカーボネート樹脂等の公知の樹脂基材、その他、アルミニウム等の金属、無機基材等の各種の基材を挙げることができる。 The coating of the present disclosure can be formed on various substrates. Examples of the substrate include known resin substrates such as acrylic resins and polycarbonate resins, metals such as aluminum, and various substrates such as inorganic substrates.
 本開示の被膜は、優れた撥水性を有し、耐摩耗性にも優れるので、長期的に性能が維持されやすい。また、本開示の被膜形成用組成物から形成される被膜は、着雪防止性能に優れ、雪に晒されたとしても長時間にわたり着雪が生じにくい。例えば、豪雪地帯であっても、本開示の被膜は長時間にわたって着雪防止性能を発揮することができる。 The film of the present disclosure has excellent water repellency and excellent abrasion resistance, so it is easy to maintain its performance over the long term. In addition, the film formed from the film-forming composition of the present disclosure is excellent in anti-snow accretion performance, and even when exposed to snow, snow accretion is unlikely to occur for a long period of time. For example, even in areas with heavy snowfall, the coating of the present disclosure can exhibit snow accretion prevention performance for a long period of time.
 従って、本開示の被膜は、撥水性及び/又は撥油性を被処理面に付与するために好適に用いられ、超撥液性が要求される種々の物品等に好適に使用することができる。本開示の被膜の用途は特に限定されず、例えば、撥水撥油剤、着霜遅延用途、防氷効果剤、防雪効果剤、指紋付着防止剤、指紋不認化剤、低摩擦剤、潤滑剤、タンパク質付着制御剤、細胞付着制御剤、微生物付着制御剤、スケール付着抑制剤、防カビ剤、防菌剤等に好適に使用することができる。また、本開示の被膜は、着雪防止機能が要求される種々の物品等に好適に使用することができ、例えば、被膜が形成された基材は、アンテナカバー用として好適に使用することができる。 Therefore, the coating of the present disclosure is suitably used for imparting water repellency and/or oil repellency to the surface to be treated, and can be suitably used for various articles that require super liquid repellency. Applications of the coating of the present disclosure are not particularly limited, and examples include water and oil repellent agents, frost retardation applications, anti-icing agents, snow-resistant agents, anti-fingerprint agents, anti-fingerprint agents, low-friction agents, and lubricants. , a protein adhesion control agent, a cell adhesion control agent, a microorganism adhesion control agent, a scale adhesion inhibitor, an antifungal agent, an antibacterial agent, and the like. In addition, the film of the present disclosure can be suitably used for various articles and the like that require a function to prevent snow accretion. For example, the base material on which the film is formed can be suitably used as an antenna cover. can.
 3.被膜の他の態様
 本開示の被膜の他の態様(以下、本開示の他の被膜という)として、無機微粒子を含み、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含み、水の接触角が、150°以上であり、紙製ウエスを荷重100g/cmで少なくとも50回塗擦した後の水の接触角が、150°以上である被膜を挙げることができる。本開示の他の被膜を形成する方法は特に制限されない。例えば、前述の本開示の被膜形成用組成物又は薬液を用いて形成した場合であっても、前記他の形態の被膜を形成することができる。
3. Other Aspects of the Coating As another aspect of the coating of the present disclosure (hereinafter referred to as another coating of the present disclosure), first inorganic fine particles containing inorganic fine particles and having an average particle diameter of 1 nm or more and 100 nm or less, and an average It contains second inorganic fine particles having a particle diameter of 500 nm or more and 5 μm or less, and has a water contact angle of 150° or more, and the water contact angle after rubbing at least 50 times with a paper waste cloth with a load of 100 g/cm 2 . is 150° or more. The method of forming other coatings of the present disclosure is not particularly limited. For example, even when the film-forming composition or chemical liquid of the present disclosure is used, the other forms of the film can be formed.
 本開示の他の被膜に含まれる無機微粒子は、前述の本開示の被膜に含まれる無機微粒子と同一である。従って、本開示の他の被膜に含まれる無機微粒子は、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含む。また、本開示の他の被膜に含まれる第1の無機微粒子、及び、第2の無機微粒子の含有割合も前述の本開示の被膜と同一である。 The inorganic fine particles contained in the other coating of the present disclosure are the same as the inorganic fine particles contained in the aforementioned coating of the present disclosure. Therefore, the inorganic fine particles contained in the other coating of the present disclosure include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less. . In addition, the content ratio of the first inorganic fine particles and the second inorganic fine particles contained in the other coating of the present disclosure is also the same as that of the coating of the present disclosure.
 本開示の他の被膜は、本開示の被膜と同様、バインダー成分及び撥水性成分を含むことができ、それらの種類及び含有割合も本開示の被膜と同様とすることができる。本開示の他の被膜の厚みも本開示の被膜と同様の範囲とすることができる。 Other coatings of the present disclosure can contain a binder component and a water-repellent component in the same manner as the coating of the present disclosure, and their types and content ratios can also be the same as the coating of the present disclosure. Other coatings of the present disclosure may have thicknesses in similar ranges as the coatings of the present disclosure.
 本開示の他の被膜は、水の接触角が150°以上であることで、優れた撥水性が発揮され得る。水の接触角は、例えば、無機微粒子、バインダー成分、撥水性成分の種類及び含有量を適宜選択することで調節することができる。本開示の他の被膜は、紙製ウエスを荷重100g/cmで少なくとも50回(好ましくは50回)塗擦した後の水の接触角が、150°以上であることにより、優れた耐摩耗性を有することができる。 Other coatings of the present disclosure can exhibit excellent water repellency by having a water contact angle of 150° or more. The contact angle of water can be adjusted, for example, by appropriately selecting the types and contents of the inorganic fine particles, the binder component, and the water-repellent component. Another coating of the present disclosure has a water contact angle of 150 ° or more after rubbing with a paper waste cloth at least 50 times (preferably 50 times) with a load of 100 g / cm 2 . can have
 本開示の他の被膜の用途は特に限定されず、例えば、本開示の被膜が適用できる用途と同様の用途を挙げることができる。 Applications of other coatings of the present disclosure are not particularly limited, and examples thereof include uses similar to those to which the coating of the present disclosure can be applied.
 (本開示の被膜の各種物性の測定方法)
 本開示の被膜(前述の他の形態の被膜も含む)の各種物性の測定方法を説明する。
(Method for measuring various physical properties of the coating of the present disclosure)
A method for measuring various physical properties of the coating of the present disclosure (including coatings of the other forms described above) will be described.
 <水の接触角(静的接触角)>
 水の接触角は、すなわち水の静的接触角である。水の接触角は、接触角計(協和界面科学社「Drop Master 701」)用いて測定され、具体的には、水(2μLの液滴)を用いて、1サンプルに対して5点の測定が行われる。静的接触角が150°以上になると、その液体は自立して基材表面に存在することができなくなる場合がある。このような場合はシリンジのニードルを支持体として静的接触角を測定し、その時の得られた値を静的接触角とする。
<Water contact angle (static contact angle)>
The contact angle of water is the static contact angle of water. The contact angle of water is measured using a contact angle meter (Kyowa Interface Science Co., Ltd. “Drop Master 701”). is done. If the static contact angle is 150° or more, the liquid may not be able to stand on its own on the substrate surface. In such a case, the static contact angle is measured using the syringe needle as a support, and the value obtained at that time is defined as the static contact angle.
 <着雪試験>
 1~2℃の範囲で恒温に保った試験室内の試験台に、着雪面が地面に対して鉛直になるように被膜を設置し、該被膜に対し、風速10m/sec、衝突量110kg/m/hの条件下で、予め作製した人工雪を吹きつける。この吹きつけは、被膜表面に人口雪が衝突するようにする。この吹きつけ開始時から、サンプルの吹き付け面全面を動画撮影して試験終了後に得られた映像から被膜表面の着雪の有無を目視で確認し、吹きつけ開始から着雪までの時間を着雪開始時間(無着雪時間)として計測する。
<Snow accretion test>
A coating is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the coating is subjected to a wind speed of 10 m / sec and a collision amount of 110 kg /. Pre-made artificial snow is blown under the condition of m 2 /h. This blowing causes the artificial snow to impinge on the covering surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. Measured as the start time (no snow accretion time).
 以下、実施例により本発明をより具体的に説明するが、本発明はこれら実施例の態様に限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the embodiments of these examples.
 (実施例1)
 第1の無機微粒子として比表面積が300m/g、かつ、平均粒子径が7nmであるシリカ微粒子(日本アエロジル製「アエロジル300」)を3質量部、第2の無機微粒子として比表面積が300m/g、かつ、平均粒子径が2.7μmであるシリカ微粒子(富士シリシア化学製「サイリシア310P」)を27質量部、熱硬化性樹脂として前記重合体Fに該当する、テトラフルオロエチレンと水酸基含有ビニルモノマーの共重合体を55質量部(固形分換算)、硬化剤として「スミジュール N-3300」(住友コベストロウレタン製)を12質量部、撥水性成分(式(1)で表される化合物に基づく構成単位を含む重合体)として特許第5831599の調製例2に記載の含フッ素共重合体を3質量部(固形分換算)、溶媒として酢酸ブチルを準備し、これらを配合することで被膜形成用組成物をバイアルに調製した。当該被膜形成用組成物をスプレー法によってポリカーボネート基材に塗布した後、このポリカーボネート基材を130℃で10分間処理することで、被膜を形成した。
 なお、特許第5831599の調製例2に記載の含フッ素共重合体(撥水性成分)は以下のように調製した。撹拌装置、温度計、還流冷却器、滴下漏斗、窒素流入口および加熱装置を備えた容積300mlの反応器を準備し、溶媒のイソプロピルアルコール(IPA)を45質量部添加した。続いて、撹拌下(CFCHCHOCOC(CH)=CH(C6FMA)65質量部、イソボルニルメタクリレート(IBMA)20質量部、2-ヒドロキシエチルメタアクリレート(HEMA)15質量部からなるモノマー(モノマー合計100質量部)に、連鎖移動剤のラウリルメルカプタン(L-SH)を5質量部追加し、開始剤の過ピバリン酸-t-ブチル1質量部をこの順に添加し、この混合物を60℃の窒素雰囲気下で12時間混合撹拌して共重合を行なった。次にこの反応混合物を室温まで冷却し、含フッ素共重合体溶液を得た。この溶液の固形分濃度は70質量%であった。含フッ素共重合体の単量体組成は、仕込み単量体組成にほぼ一致し、質量平均分子量は9000であった。
(Example 1)
3 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles. / g, and 27 parts by mass of silica fine particles (“Sylysia 310P” manufactured by Fuji Silysia Chemical) having an average particle diameter of 2.7 μm, and tetrafluoroethylene and a hydroxyl group-containing thermosetting resin corresponding to the polymer F. 55 parts by mass of a vinyl monomer copolymer (in terms of solid content), 12 parts by mass of "Sumidule N-3300" (manufactured by Sumitomo Covestro Urethane) as a curing agent, and a water-repellent component (represented by formula (1) 3 parts by mass (in terms of solid content) of the fluorine-containing copolymer described in Preparation Example 2 of Patent No. 5831599 as a polymer containing a structural unit based on a compound) and butyl acetate as a solvent are prepared and blended. A film-forming composition was prepared in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.
The fluorine-containing copolymer (water-repellent component) described in Preparation Example 2 of Japanese Patent No. 5831599 was prepared as follows. A 300 ml reactor equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen inlet and heating device was prepared, and 45 parts by mass of isopropyl alcohol (IPA) as a solvent was added. Subsequently, (CF 2 ) 6 CH 2 CH 2 OCOC(CH 3 )=CH 2 (C6FMA) 65 parts by mass, isobornyl methacrylate (IBMA) 20 parts by mass, and 2-hydroxyethyl methacrylate (HEMA) 15 parts by mass under stirring. 5 parts by mass of lauryl mercaptan (L-SH) as a chain transfer agent was added to monomers (total of 100 parts by mass of monomers) consisting of parts by mass, and 1 part by mass of t-butyl perpivalate as an initiator was added in this order. , and this mixture was mixed and stirred for 12 hours under a nitrogen atmosphere at 60°C to carry out copolymerization. Next, this reaction mixture was cooled to room temperature to obtain a fluorine-containing copolymer solution. The solid content concentration of this solution was 70% by mass. The monomer composition of the fluorine-containing copolymer almost matched the charged monomer composition, and the weight average molecular weight was 9,000.
 (実施例2)
 第1の無機微粒子を9質量部、第2の無機微粒子を21質量部としたこと以外は、実施例1と同様の処方にて被膜を形成した。
(Example 2)
A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 9 parts by mass and the second inorganic fine particles were 21 parts by mass.
 (実施例3)
 第1の無機微粒子を15質量部、第2の無機微粒子を15質量部としたこと以外は、実施例1と同様の処方にて被膜を形成した。
(Example 3)
A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 15 parts by mass and the second inorganic fine particles were 15 parts by mass.
 (実施例4)
 第1の無機微粒子を20質量部、第2の無機微粒子を20質量部、テトラフルオロエチレンと水酸基含有ビニルモノマーの共重合体を46質量部(固形分換算)、スミジュールN-3300 10質量部、特許第5831599の調製例2に記載の含フッ素共重合体を4質量部(固形分換算)とした以外は、実施例1と同様の処方にて被膜を形成した。
(Example 4)
20 parts by mass of the first inorganic fine particles, 20 parts by mass of the second inorganic fine particles, 46 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), 10 parts by mass of Sumidule N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 4 parts by mass (in terms of solid content).
 (実施例5)
 第1の無機微粒子を25質量部、第2の無機微粒子を25質量部、テトラフルオロエチレンと水酸基含有ビニルモノマーの共重合体を37質量部(固形分換算)、スミジュール N-3300 8質量部、特許第5831599の調製例2に記載の含フッ素共重合体を5質量部(固形分換算)とした以外は、実施例1と同様の処方にて被膜を形成した。
(Example 5)
25 parts by mass of the first inorganic fine particles, 25 parts by mass of the second inorganic fine particles, 37 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), 8 parts by mass of Sumidur N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 5 parts by mass (in terms of solid content).
 (実施例6)
 第1の無機微粒子として比表面積が300m/g、かつ、平均粒子径が7nmであるシリカ微粒子(日本アエロジル製「アエロジル300」)を19質量部、第2の無機微粒子として比表面積が300m/g、かつ、平均粒子径が2.7μmであるシリカ微粒子(富士シリシア化学製「サイリシア310P」)を11質量部、熱硬化性樹脂として「ユーダブルUWS-2816(日本触媒社製)」を44質量部(固形分換算)、硬化剤として「スミジュール N-3300」(住友コベストロウレタン製)を20質量部、撥水性成分として「サイマックUS-352」(東亞合成社製)を6質量部(固形分換算)、溶媒として酢酸ブチルを準備し、これらを配合することで被膜形成用組成物をバイアルに調製した。当該被膜形成用組成物をスプレー法によってポリカーボネート基材に塗布した後、このポリカーボネート基材を130℃で10分間処理することで、被膜を形成した。
(Example 6)
19 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles. / g, and 11 parts by mass of silica fine particles having an average particle diameter of 2.7 μm (“Silysia 310P” manufactured by Fuji Silysia Chemical), and 44 parts of “Udable UWS-2816 (manufactured by Nippon Shokubai Co., Ltd.)” as a thermosetting resin. Parts by mass (in terms of solid content), 20 parts by mass of "Sumidule N-3300" (manufactured by Sumitomo Covestro Urethane) as a curing agent, and 6 parts by mass of "Symac US-352" (manufactured by Toagosei Co., Ltd.) as a water-repellent component. (Converted to solid content), butyl acetate was prepared as a solvent, and these were blended to prepare a film-forming composition in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.
 (実施例7)
 第1の無機微粒子として比表面積が300m/g、かつ、平均粒子径が7nmであるシリカ微粒子(日本アエロジル製「アエロジル300」)を16質量部、第2の無機微粒子として比表面積が300m/g、かつ、平均粒子径が2.7μmであるシリカ微粒子(富士シリシア化学製「サイリシア310P」)を14質量部、熱硬化性樹脂として「ユーダブルUWS-2816(日本触媒社製)」を38質量部(固形分換算)、硬化剤として「デュラネートE402-B80B」(旭化成社製)を20質量部(固形分換算)、撥水性成分として「サイマックUS-380」(東亞合成社製)を12質量部(固形分換算)、溶媒として酢酸ブチルを準備し、これらを配合することで被膜形成用組成物をバイアルに調製した。当該被膜形成用組成物をスプレー法によってポリカーボネート基材に塗布した後、このポリカーボネート基材を130℃で10分間処理することで、被膜を形成した。
(Example 7)
16 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles. / g, and 14 parts by mass of silica fine particles having an average particle diameter of 2.7 μm (“Sylysia 310P” manufactured by Fuji Silysia Chemical), and 38 parts of “Udable UWS-2816 (manufactured by Nippon Shokubai Co., Ltd.)” as a thermosetting resin. Parts by mass (in terms of solid content), 20 parts by mass (in terms of solid content) of “Duranate E402-B80B” (manufactured by Asahi Kasei Co., Ltd.) as a curing agent, and 12 parts of “Cymac US-380” (manufactured by Toagosei Co., Ltd.) as a water-repellent component. Parts by mass (in terms of solid content) and butyl acetate as a solvent were prepared and blended to prepare a film-forming composition in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.
 (実施例8)
 第1の無機微粒子として比表面積が300m/g、かつ、平均粒子径が7nmであるシリカ微粒子(日本アエロジル製「アエロジル300」)を8質量部、第2の無機微粒子として比表面積が300m/g、かつ、平均粒子径が2.7μmであるシリカ微粒子(富士シリシア化学製「サイリシア310P」)を20質量部、熱硬化性樹脂として「ユーダブルUWS-2818(日本触媒社製)」を25質量部(固形分換算)、硬化剤として「デュラネートE402-B80B」(旭化成社製)を15質量部(固形分換算)、撥水性成分として「サイマックUS-352」(東亞合成社製)を32質量部(固形分換算)、溶媒として酢酸ブチルを準備し、これらを配合することで被膜形成用組成物をバイアルに調製した。当該被膜形成用組成物をスプレー法によってポリカーボネート基材に塗布した後、このポリカーボネート基材を130℃で10分間処理することで、被膜を形成した。
(Example 8)
8 parts by mass of silica fine particles ("Aerosil 300" manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m 2 /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m 2 as the second inorganic fine particles. / g, and 20 parts by mass of silica fine particles having an average particle diameter of 2.7 μm ("Sylysia 310P" manufactured by Fuji Silysia Chemical), and 25 parts of "Udable UWS-2818 (manufactured by Nippon Shokubai Co., Ltd.)" as a thermosetting resin. Parts by mass (in terms of solid content), 15 parts by mass (in terms of solid content) of “Duranate E402-B80B” (manufactured by Asahi Kasei Co., Ltd.) as a curing agent, and “Cymac US-352” (manufactured by Toagosei Co., Ltd.) as a water-repellent component 32. Parts by mass (in terms of solid content) and butyl acetate as a solvent were prepared and blended to prepare a film-forming composition in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.
 なお、実施例6~8で使用したサイマックUS-352及びサイマックUS-380はシリコーングラフトアクリルポリマーであって、(1)式におけるRが分子量300~50000のポリシロキサンである化合物にもとづく構造単位を有する重合体である。 SYMAC US-352 and SYMAC US-380 used in Examples 6 to 8 are silicone-grafted acrylic polymers, and structural units based on compounds in which R a in formula (1) is polysiloxane having a molecular weight of 300 to 50,000. is a polymer having
 (比較例1)
 第1の無機微粒子を使用せず、第2の無機微粒子を30質量部としたこと以外は、実施例1と同様の方法で被膜を形成した。
(Comparative example 1)
A film was formed in the same manner as in Example 1, except that the first inorganic fine particles were not used and the second inorganic fine particles were 30 parts by mass.
 (比較例2)
 第1の無機微粒子を21質量部、第2の無機微粒子を9質量部としたこと以外は、実施例1と同様の処方にて被膜を形成した。
(Comparative example 2)
A coating was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 21 parts by mass and the second inorganic fine particles were 9 parts by mass.
 (比較例3)
第1の無機微粒子を27質量部、第2の無機微粒子を3質量部としたこと以外は、実施例1と同様の処方にて被膜を形成した。
(Comparative Example 3)
A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 27 parts by mass and the second inorganic fine particles were 3 parts by mass.
 (比較例4)
 第1の無機微粒子を30量部、第2の無機微粒子を0質量部としたこと以外は、実施例1と同様の処方にて被膜を形成した。
(Comparative Example 4)
A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 30 parts by mass and the second inorganic fine particles were 0 parts by mass.
 (比較例5)
 第1の無機微粒子を30質量部、第2の無機微粒子を30質量部、テトラフルオロエチレンと水酸基含有ビニルモノマーの共重合体を28質量部(固形分換算)、「スミジュール N-3300」 6質量部、特許第5831599の調製例2に記載の含フッ素共重合体を6質量部(固形分換算)とした以外は、実施例1と同様の処方にて被膜を形成した。
(Comparative Example 5)
30 parts by mass of the first inorganic fine particles, 30 parts by mass of the second inorganic fine particles, 28 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), "Sumidule N-3300" 6 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 6 parts by mass (in terms of solid content).
 (比較例6)
 第1の無機微粒子を10質量部、第2の無機微粒子を10質量部、テトラフルオロエチレンと水酸基含有ビニルモノマーの共重合体を64質量部(固形分換算)、スミジュール N-3300 14質量部、特許第5831599の調製例2に記載の含フッ素共重合体を2質量部(固形分換算)とした以外は、実施例1と同様の処方にて被膜を形成した。
(Comparative Example 6)
10 parts by mass of the first inorganic fine particles, 10 parts by mass of the second inorganic fine particles, 64 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), 14 parts by mass of Sumidule N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 2 parts by mass (on a solid content basis).
 (比較例7)
 第1の無機微粒子を5質量部、第2の無機微粒子を5質量部、テトラフルオロエチレンと水酸基含有ビニルモノマーの共重合体を73質量部(固形分換算)、スミジュール N-3300 16質量部、特許第5831599の調製例2に記載の含フッ素共重合体を1質量部(固形分換算)とした以外は、実施例1と同様の処方にて被膜を形成した。
(Comparative Example 7)
5 parts by mass of first inorganic fine particles, 5 parts by mass of second inorganic fine particles, 73 parts by mass of copolymer of tetrafluoroethylene and hydroxyl group-containing vinyl monomer (converted to solid content), 16 parts by mass of Sumidule N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 1 part by mass (in terms of solid content).
 <水の接触角(静的接触角)>
 水の接触角は、接触角計(協和界面科学社「Drop Master 701」用いた。具体的には、水(2μLの液滴)を用いて、1サンプルに対して5点の測定を行った。静的接触角が150℃以上になると、その液体は自立して基材表面に存在することができなくなる場合はシリンジのニードルを支持体として静的接触角を測定し、その時の得られた値を静的接触角とした。
<Water contact angle (static contact angle)>
The contact angle of water was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. "Drop Master 701"). Specifically, using water (droplet of 2 μL), 5 points were measured for one sample. When the static contact angle reaches 150° C. or more, the liquid cannot stand on its own and exist on the substrate surface. The value was taken as the static contact angle.
 <耐摩耗性評価>
 耐摩耗性の評価は、以下に記載するラビング試験にて実施した。実施例又は比較例で得られた各被膜の試験片について、対水接触角を測定して初期接触角を求めた。その後、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:1cm)に紙製ウエスとしてキムワイプ(商標名:キムワイプ、日本製紙クレシア製)を装着し、荷重100g/cmで一定回数塗擦した。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。この試験において、接触角は、<水の接触角(静的接触角)>と同様の方法で実施した。
<Abrasion resistance evaluation>
Abrasion resistance was evaluated by a rubbing test described below. The initial contact angle was obtained by measuring the contact angle with water of the test piece of each coating obtained in Examples or Comparative Examples. After that, Kimwipe (trade name: Kimwipe, manufactured by Nippon Paper Crecia Co., Ltd.) as a paper waste was placed on the holder (area in contact with the sample: 1 cm 2 ) of the rubbing tester (Imoto Seisakusho's rubbing tester "wear resistance tester 151E triple specification"). It was worn and rubbed a certain number of times with a load of 100 g/cm 2 . After that, the water contact angle was measured to evaluate the abrasion resistance against wiping. Abrasion resistance here means the number of times of abrasion that can maintain a super water-repellent state (an average static contact angle value of 5 times is 150° or more, or an average of 140° or more and a standard deviation of 150° or more). Defined. In this test, the contact angle was measured in the same manner as <water contact angle (static contact angle)>.
 <着雪試験>
 1~2℃の範囲で恒温に保った試験室内の試験台に、着雪面が地面に対して鉛直になるように評価サンプル(被膜)を設置し、該サンプルに対し、風速10m/sec、衝突量110kg/m/hの条件下で、予め作製した人工雪を吹きつけた。この吹きつけは、サンプル(被膜)表面に人口雪が衝突するようにした。この吹きつけ開始時から、サンプルの吹き付け面全面を動画撮影して試験終了後に得られた映像から被膜表面の着雪の有無を目視で確認し、吹きつけ開始から着雪までの時間を着雪開始時間(つまり、無着雪時間)とした。
<Snow accretion test>
An evaluation sample (film) is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the sample is subjected to a wind speed of 10 m / sec, Artificial snow prepared in advance was blown under the condition of a collision amount of 110 kg/m 2 /h. This blowing caused the artificial snow to impinge on the sample (coating) surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. The start time (that is, the non-snow accretion time) was used.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
 表1には、水の静的接触角(水20μL)、耐摩耗性評価及び着雪開始時間の結果を示している。実施例で得られた被膜はいずれも耐摩耗性及び着雪防止性能の両方に優れるものであることが確認された。これに対し、比較例で得られた被膜は、無機微粒子の配合が適切でない組成物から形成されているので、耐摩耗性が顕著に悪化するものであった。 Table 1 shows the results of the static contact angle of water (20 μL of water), wear resistance evaluation, and snow accretion start time. It was confirmed that all of the films obtained in Examples were excellent in both abrasion resistance and snow adhesion prevention performance. On the other hand, the coatings obtained in the comparative examples were formed from a composition in which the inorganic fine particles were not appropriately blended, so the wear resistance was remarkably deteriorated.

Claims (11)

  1. 無機微粒子と、重合性成分と、撥水性成分とを含み、
    前記無機微粒子は、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含み、
    前記第1の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、3~25質量部であり、
    前記第2の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、12~27質量部であり、
    前記第1の無機微粒子及び前記第2の無機微粒子の総含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、20質量部以上であり、
    前記撥水性成分は、下記一般式(1):
    Figure JPOXMLDOC01-appb-C000001
    (式中、Xは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX基(但し、XおよびXは、同一又は異なって、水素原子、フッ素原子又は塩素原子である。)、シアノ基、炭素数1~6の直鎖状又は分岐状のフルオロアルキル基、置換又は非置換のベンジル基、置換又は非置換のフェニル基、もしくは炭素数1~20の直鎖状または分岐状アルキル基であり、Yは、直接結合、酸素原子を有していてもよい炭素数1~10の炭化水素基、-CHCHN(R)SO-基(但し、Rは炭素数1~4のアルキル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、-CHCH(OY)CH-基(但し、Yは水素原子またはアセチル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、又は-(CHSO-基(nは1~10であり、式の右端がRに、左端がOにそれぞれ結合している。)であり、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、分子量300~50000のポリシロキサン、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である。)で表される化合物に基づく構造単位を少なくとも有する重合体である、被膜形成用組成物。
    including inorganic fine particles, a polymerizable component, and a water-repellent component,
    The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
    The content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
    The content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
    The total content of the first inorganic fine particles and the second inorganic fine particles per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component, 20 parts by mass or more,
    The water-repellent component has the following general formula (1):
    Figure JPOXMLDOC01-appb-C000001
    (Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, 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 (with the proviso that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R a and the left end is bonded to O.), —CH 2 CH(OY 1 )CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R a and the left end is bonded to O.), or a —(CH 2 ) n SO 2 — group (where n is 1 to 10). , The right end of the formula is bonded to Ra , and the left end is bonded to O.), where Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.). A film-forming composition, which is a polymer.
  2. 前記第2の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、15~27質量部であり、
    前記式(1)中、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である、請求項1に記載の被膜形成用組成物。
    The content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
    In the above formula (1), R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 or a fluoropolyether group having a molecular weight of 400 to 5,000.
  3. 前記撥水性成分の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記重合性成分及び前記撥水性成分の総質量100質量部あたり、0.1~30質量部である、請求項1又は2に記載の被膜形成用組成物。 The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component. The film-forming composition according to claim 1 or 2.
  4. 前記重合性成分は、架橋性官能基を有する重合体及び硬化剤である、請求項1~3のいずれか1項に記載の被膜形成用組成物。 The film-forming composition according to any one of claims 1 to 3, wherein the polymerizable component is a polymer having a crosslinkable functional group and a curing agent.
  5. 請求項1~4のいずれか1項に記載の被膜形成用組成物の硬化物を含む、被膜。 A film comprising a cured product of the film-forming composition according to any one of claims 1 to 4.
  6. 無機微粒子と、バインダー成分と、撥水性成分とを含み、
    前記無機微粒子は、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含み、
    前記第1の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、3~25質量部であり、
    前記第2の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、12~27質量部であり、
    前記第1の無機微粒子及び前記第2の無機微粒子の総含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、20質量部以上であり、
    前記撥水性成分は、下記一般式(1):
    Figure JPOXMLDOC01-appb-C000002
    (式中、Xは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX基(但し、XおよびXは、同一又は異なって、水素原子、フッ素原子又は塩素原子である。)、シアノ基、炭素数1~6の直鎖状又は分岐状のフルオロアルキル基、置換又は非置換のベンジル基、置換又は非置換のフェニル基、もしくは炭素数1~20の直鎖状または分岐状アルキル基であり、Yは、直接結合、酸素原子を有していてもよい炭素数1~10の炭化水素基、-CHCHN(R)SO-基(但し、Rは炭素数1~4のアルキル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、-CHCH(OY)CH-基(但し、Yは水素原子またはアセチル基であり、式の右端がRに、左端がOにそれぞれ結合している。)、又は-(CHSO-基(nは1~10であり、式の右端がRに、左端がOにそれぞれ結合している。)であり、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、分子量300~50000のポリシロキサン、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である。)で表される化合物に基づく構造単位を少なくとも有する重合体である、被膜。
    including inorganic fine particles, a binder component, and a water-repellent component,
    The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
    The content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
    The content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
    The total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component. Part by mass or more,
    The water-repellent component has the following general formula (1):
    Figure JPOXMLDOC01-appb-C000002
    (Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, 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 (with the proviso that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R a and the left end is bonded to O.), —CH 2 CH(OY 1 )CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R a and the left end is bonded to O.), or a —(CH 2 ) n SO 2 — group (where n is 1 to 10). , The right end of the formula is bonded to Ra , and the left end is bonded to O.), where Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.). A coating that is a polymer.
  7. 前記第2の無機微粒子の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、15~27質量部であり、
    前記式(1)中、Rは炭素数20以下の直鎖状又は分岐状のアルキル基、炭素数6以下の直鎖状又は分岐状のフルオロアルキル基、若しくは分子量400~5000のポリエーテル基又は分子量400~5000のフルオロポリエーテル基である、請求項6に記載の被膜。
    The content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
    In the above formula (1), R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 or a fluoropolyether group with a molecular weight of 400-5000.
  8. 前記撥水性成分の含有量は、前記第1の無機微粒子、前記第2の無機微粒子、前記バインダー成分及び前記撥水性成分の総質量100質量部あたり、0.1~30質量部である、請求項6又は7に記載の被膜。 The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component. Item 8. The coating according to item 6 or 7.
  9. 無機微粒子を含む被膜において、
    前記無機微粒子は、平均粒子径が1nm以上100nm以下である第1の無機微粒子、及び、平均粒子径が500nm以上5μm以下である第2の無機微粒子を含み、
    水の接触角が、150°以上であり、
    紙製ウエスを荷重100g/cmで少なくとも50回塗擦した後の水の接触角が、150°以上である、被膜。
    In a coating containing inorganic fine particles,
    The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
    The contact angle of water is 150° or more,
    A film having a water contact angle of 150° or more after being rubbed with a paper waste cloth at least 50 times with a load of 100 g/cm 2 .
  10. 下記着雪試験により測定される着雪開始時間が5分以上である、請求項5~9のいずれか1項に記載の被膜。
    <着雪試験>
    1~2℃の範囲で恒温に保った試験室内の試験台に、着雪面が地面に対して鉛直になるように被膜を設置し、該被膜に対し、風速10m/sec、衝突量110kg/m/hの条件下で、予め作製した人工雪を吹きつける。この吹きつけは、被膜表面に人口雪が衝突するようにする。この吹きつけ開始時から、サンプルの吹き付け面全面を動画撮影して試験終了後に得られた映像から被膜表面の着雪の有無を目視で確認し、吹きつけ開始から着雪までの時間を着雪開始時間(無着雪時間)として計測する。
    The coating according to any one of claims 5 to 9, wherein the snow accretion start time measured by the following snow accretion test is 5 minutes or longer.
    <Snow accretion test>
    A coating is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the coating is subjected to a wind speed of 10 m / sec and a collision amount of 110 kg /. Pre-made artificial snow is blown under the condition of m 2 /h. This blowing causes the artificial snow to impinge on the covering surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. Measured as the start time (no snow accretion time).
  11. 請求項1~4のいずれか1項に記載の被膜形成用組成物を含む、薬液。 A chemical solution comprising the film-forming composition according to any one of claims 1 to 4.
PCT/JP2022/037026 2021-10-08 2022-10-03 Coating-forming composition, coating, and chemical liquid WO2023058621A1 (en)

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