Film forming composition, film, product, and film formation method

Abstract

The present invention provides: a film forming composition capable of forming a film having excellent water and oil repellent properties, antifouling properties, and non-adhesiveness, and having excellent resistance to heat and water; a film formed by means of said film forming composition; a product having the film; and a film formation method for forming said film. Provided is a film forming composition characterized by containing (A) a polymer having a siloxane bond, and (B) a silicone oil.

Description

Composition for film formation, film, article, and method for forming film

[0001] The present invention relates to a composition for film formation, a film, an article, and a method for forming a film.

[0002] Conventionally, articles such as cooking utensils and food manufacturing equipment have problems in that oil, powder, etc. adhere to the surface due to heating or the like and are difficult to remove. In addition, if food easily adheres to the surface, there is a problem that it takes time to clean the dirt. Furthermore, powders derived from food and equipment generated in factories such as food require a better powder adhesion suppressing effect because the production efficiency and hygienic environment decrease when the powders remain adhered to the equipment.

[0003] In order to solve the above problems, a coating containing fluorine is applied to the surface of the article. However, in recent years, from the viewpoint of environmental problem improvement, the use of fluorine compounds is regulated (PFAS regulation), and there is a demand for the study of a fluorine-free composition for film formation as a substitute for a coating composition containing fluorine.

[0004] As a fluorine-free composition for film formation as a substitute for the above-mentioned coating composition containing fluorine, a method of coating a coating film mainly composed of ceramic particles has been proposed (see Patent Document 1).

[0005] However, in the method of forming a coating film mainly composed of ceramic particles described in Patent Document 1, the water and oil repellency, antifouling property, and non-stickiness required for cooking utensils and the like to suppress the adhesion of food and the like have not been sufficiently studied, and there is a problem that these properties are inferior.

[0006] In addition, articles such as cooking utensils may be poured with water, and may be heated, poured with hot water, or immersed in hot water. Therefore, the coating film formed on the surface of such cooking utensils and the like is required to have durability against heat and water such that the properties do not change and the film does not peel off from the surface of the article even in the above cases. In Patent Document 1, such durability against heat and water has not been studied, and there is a problem that the properties are inferior.

[0007] Therefore, there is a need for the development of a film-forming composition that can form a film with excellent water-repellent, oil-repellent, stain-resistant, and non-stick properties, as well as excellent durability against heat and water.

[0008] Publication No. 2016-93535

[0009] The present invention aims to provide a film-forming composition capable of forming a film that is excellent in water-repellent, oil-repellent, stain-resistant, and non-stick properties, as well as excellent in heat and water resistance; a film formed by the film-forming composition; an article having the film; and a method for forming the film.

[0010] As a result of diligent research, the inventors have discovered that the above objective can be achieved by a film-forming composition containing (A) a polymer having siloxane bonds and (B) silicone oil, and have completed the present invention.

[0011] That is, the present invention relates to the following film-forming compositions, films, articles, and methods for forming films: 1. A film-forming composition characterized by containing (A) a polymer having siloxane bonds and (B) a silicone oil. 2. The film-forming composition according to item 1, wherein the content of (A) the polymer having siloxane bonds is 50% by mass or less, based on 100% by mass of the film-forming composition. 3. The film-forming composition according to item 1 or 2, wherein (B) the silicone oil is a straight silicone oil and / or a modified silicone oil. 4. The film-forming composition according to any one of claims 1 to 3, wherein the (B) silicone oil is at least one straight silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, or at least one modified dimethyl silicone oil selected from the group consisting of amino-modified dimethyl silicone oil, epoxy-modified dimethyl silicone oil, carbinol-modified dimethyl silicone oil, mercapto-modified dimethyl silicone oil, carboxyl-modified dimethyl silicone oil, methacrylic-modified dimethyl silicone oil, acrylic-modified dimethyl silicone oil, polyether-modified dimethyl silicone oil, phenol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, carboxylic acid anhydride-modified dimethyl silicone oil, diol-modified dimethyl silicone oil, aralkyl-modified dimethyl silicone oil, long-chain alkyl-modified dimethyl silicone oil, higher fatty acid ester-modified dimethyl silicone oil, higher fatty acid-modified dimethyl silicone oil, and phenyl-modified dimethyl silicone oil.5. The film-forming composition according to any one of claims 1 to 4, wherein the (B) silicone oil is at least one modified dimethyl silicone oil selected from the group consisting of amino-modified dimethyl silicone oil, epoxy-modified dimethyl silicone oil, carbinol-modified dimethyl silicone oil, mercapto-modified dimethyl silicone oil, carboxyl-modified dimethyl silicone oil, methacrylic-modified dimethyl silicone oil, acrylic-modified dimethyl silicone oil, polyether-modified dimethyl silicone oil, phenol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, carboxylic acid anhydride-modified dimethyl silicone oil, diol-modified dimethyl silicone oil, aralkyl-modified dimethyl silicone oil, long-chain alkyl-modified dimethyl silicone oil, higher fatty acid ester-modified dimethyl silicone oil, higher fatty acid-modified dimethyl silicone oil, and phenyl-modified dimethyl silicone oil. 6. The film-forming composition according to any one of claims 1 to 5, wherein the (B) silicone oil is at least one modified dimethyl silicone oil selected from the group consisting of carbinol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, and diol-modified dimethyl silicone oil. 7. 10. The film-forming composition according to any one of claims 1 to 6, wherein the number average molecular weight Mn of the (B) silicone oil is 1000 or more. 8. The film-forming composition according to any one of claims 1 to 7, wherein the content of the (B) silicone oil is 5.0% by mass or less, based on 100% by mass of the film-forming composition. 9. The film-forming composition according to any one of claims 1 to 8, further containing (C) an inorganic filler. 10. The film-forming composition according to claim 9, wherein the (C) inorganic filler is at least one inorganic filler selected from the group consisting of titanium dioxide, silica, alumina, titania, zirconia, zinc oxide, carbon black, silicon carbide, silicon nitride, iron oxide, ultramarine, Prussian blue, calcium carbonate, clay minerals, talc, glass beads, glass flakes, mica, diamond, boron nitride, tungsten carbide, molybdenum carbide, molybdenum disulfide, boron carbide, graphite, graphene, fullerene, carbon nanotubes, and carbon fibers.11. A film formed by curing a film-forming composition according to any one of items 1 to 10. 12. The film according to item 11, wherein the film has a water contact angle of 80° or more. 13. The film according to item 11 or 12, wherein the film has an oleic acid contact angle of 20° or more. 14. An article having a film formed by curing a film-forming composition according to any one of items 1 to 10. 15. The articles are cooking utensils, industrial machinery, food manufacturing equipment, kitchen equipment, medical equipment, medical instruments, hypodermic needles, molding dies, paint manufacturing equipment, painting jigs, tableware, cutlery, electronic products, home appliances, communication equipment, mobile phones, monitors, vehicles, aircraft, ships, window glass, traffic infrastructure, signals, road signs, convex mirrors, buildings, factory equipment, housing equipment, roofs, kitchen sinks, door knobs, toilets, washbasins, bathtubs, automobile bodies, mirror covers, door handles, grills, range hoods, bumpers, or spoilers, as described in item 14. 16. A method for forming a film, comprising: (1) step 1 of applying a film-forming composition to the surface of a substrate to form a film-forming composition layer; and (2) step 2 of heating the film-forming composition layer to form a film on the surface of the substrate, wherein the film-forming composition contains (A) a polymer having siloxane bonds, and (B) silicone oil.

[0012] The film-forming composition of the present invention can form a film that is excellent in water-repellent, oil-repellent, stain-resistant, and non-stick properties, as well as excellent in heat and water resistance. Furthermore, the film of the present invention is excellent in water-repellent, oil-repellent, stain-resistant, and non-stick properties, as well as excellent in heat and water resistance. Moreover, since the article of the present invention has a film formed on a substrate by curing the above-mentioned film-forming composition, it is excellent in water-repellent, oil-repellent, stain-resistant, and non-stick properties, as well as excellent in heat and water resistance. Furthermore, the method for forming the film of the present invention allows for the easy formation of the above-mentioned film on a substrate.

[0013] The film-forming composition of the present invention is characterized by containing (A) a polymer having siloxane bonds (hereinafter also referred to as "component (A)") and (B) silicone oil (hereinafter also referred to as "component (B)"). Here, in the present invention, component (A) and component (B) are distinguished and different components are used. Because the film-forming composition of the present invention contains component (A), it can form a film on a substrate of an article, and because it contains component (B), it can impart excellent water-repellent, oil-repellent, anti-fouling, and non-stick properties to the surface of the film formed using the film-forming composition.

[0014] In other words, since the composition of the present invention contains (A) a polymer having siloxane bonds and (B) silicone oil, when the composition is applied to a substrate and heated, (B) silicone oil does not mix with (A) the polymer having siloxane bonds and harden, but instead floats to the surface of the film (opposite side from the substrate) and hardens, so that the surface of the film formed by the hardening can exhibit excellent water-repellent, oil-repellent, stain-resistant, and non-stick properties. Furthermore, because component (B) is selectively present on the surface of the film formed by the above composition, changes in the above properties are suppressed even under high-temperature conditions such as when water is poured on it, when it is heated, when hot water is poured on it, or when it is immersed in hot water, and peeling from the surface of the article is suppressed.

[0015] The present invention will be described in detail below.

[0016] 1. Film-forming composition The film-forming composition of the present invention is characterized by containing (A) a polymer having siloxane bonds and (B) silicone oil. The components of the present invention will be described below.

[0017] ((A) Polymer having siloxane bonds) Component (A) is not particularly limited as long as it is a polymer having siloxane bonds. In the compositions of the present invention, it is preferable to use a silicone resin as such a polymer having siloxane bonds. In the present invention, the term "silicone resin" refers to a three-dimensional network polymer mainly composed of trifunctional siloxane units or tetrafunctional siloxane units. Among silicone resins, it is more preferable to use an alkoxysilane oligomer.

[0018] The alkoxysilane oligomer is not particularly limited, and for example, one can be prepared by adding an alkoxysilane to water, alcohol, glycol, or glycol ether, and then mixing it with a catalyst such as an acid, base, or organometallic compound to carry out hydrolysis and condensation reactions.

[0019] In the film-forming composition of the present invention, the alkoxysilane oligomer can be used as an alkoxysilane oligomer solution obtained by hydrolyzing and condensing an alkoxysilane beforehand, adding the resulting alkoxysilane condensate to a solvent, and mixing it with a catalyst.

[0020] The above-mentioned alkoxysilane oligomer can be used as an alkoxysilane oligomer solution obtained by adding an alkoxysilane, or a low-level condensate of an alkoxysilane and an alkoxysilane, to a solvent and mixing it with water and a catalyst. In this case, the alkoxysilane oligomer is formed by a so-called sol-gel method, in which the hydrolysis and condensation reactions of the alkoxysilane proceed in the alkoxysilane oligomer solution.

[0021] The above alkoxylan is, for example, formulated with the formula: (R １ ) ｍ Si ( OR ２ ) ４－ｍ (In the formula, R １ R is a functional group. ２is a lower alkyl group. m is an integer from 0 to 3). In the above chemical formula, functional groups include methyl, dimethyl, phenyl, dimethoxydiphenyl, n-propyl, hexyl, decyl, 1,6-bis(trimethoxysilyl), vinyl, 3-glycidoxypropyl, 3-glycidoxypropylmethyl, 2-(3,4-epoxycyclohexyl)ethyl, p-styryl, 3-methacryloxypropyl, 3-methacryloxypropylmethyl, 3-acryloxypropyl, 3-aminopropyl, N-2-(aminoethyl)-3-aminopropyl, N-2-(aminoethyl)-3-aminopropylmethyl, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyl, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyl, 3-mercaptopropyl, 3-mercaptopropylmethyl, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyl, 3-trimethoxypropylpropyl succinic anhydride, etc.

[0022] As the lower alkyl group, specifically, there are linear or branched alkyl groups with about 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1-ethylpropyl, isopentyl, neopentyl, etc.

[0023] Specific examples of the alkoxysilane represented by the above chemical formula include (CH ３ ) ２ Si(OCH ３ ) ２ 、Si(OCH ３ ) ４ 、Si(OC ２ H ５ ) ４ 、CH ３ Si(OCH ３ ) ３ 、CH ３ Si(OC ２ H ５ ) ３ 、C ２ H ５ Si(OCH３ ) ３ , C ２ H ５ Si(OC ２ H ５ ) ４ ienCHCH ２ Si(OCH) ３ ) ３ ,CH ２ CHOCH ２ O(CH ２ ) ３ Si(CH ３ O) ３ ,CH ２ C (CH ３ ) COO (CH ２ ) ３ Si(OCH) ３ ) ３ ,CH ２ CHCOO (CH ２ ) ３ Si(OCH) ３ ) ３ , C ６ H ５ Si(OCH) ３ ) ３ NH ２ (CH ２ ) ３ Si(OCH) ３ ) ３ SH(CH ２ ) ３ Si(CH ３ ) ３ , NCO (CH ２ ) ３ Si (C ２ H ５ O) ３ These are some examples.

[0024] In other words, it is preferable to use an alkoxylane oligomer obtained by polymerizing the above-mentioned alkoxysilane as component (A).

[0025] Acids, bases, organometallic compounds, and the like can be used as catalysts.

[0026] Examples of acids include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and boric acid; and organic acids such as formic acid, acetic acid, citric acid, and oxalic acid.

[0027] Examples of bases include alkali metal or alkaline earth metal hydroxides such as potassium hydroxide and sodium hydroxide; primary amines such as monoethylamine, secondary amines such as diethylamine, tertiary amines such as triethylamine, and amine compounds such as ammonia.

[0028] Examples of organometallic compounds include water-soluble organometallic chelate compounds and metal alkoxides containing metal components such as titanium, zirconium, aluminum, and tin.

[0029] Examples of organometallic chelate compounds include titanium chelate compounds such as titanium diisopropoxy bisacetylacetonate, titanium tetraacetylacetonate, titanium dioctyloxy bisethylacetonate, titanium octylene glycolate, titanium diisopropoxy bisethylacetylacetonate, titanium lactate, titanium lactate ammonium salt, and titanium diisopropoxy bistriethanolamine; zirconium chelate compounds such as zirconium tetraacetylacetonate, zirconium triphtoxy monoacetylacetonate, zirconium dibutoxy bisethylacetoacetate, and zirconium triphtoxy monostearate; and aluminum chelate compounds such as ethylacetoacetate aluminum diisopropylate, aluminum trisethylacetate, alkylacetoacetate aluminum diisopropylate, and aluminum monoacetylacetonate bisethylacetoacetate.

[0030] Examples of metal alkoxides include titanium alkoxide compounds such as tetraisopropyl titanate, tetran-butyl titanate, butyl titanate dimer, tetratert-butyl titanate, and tetraoctyl titanate; zirconium alkoxide compounds such as n-propyl zirconate and n-butyl zirconate; and aluminum alkoxide compounds such as aluminum isopropylate, monobutoxyaluminum diisopropylate, and aluminum butyrate.

[0031] The above catalysts may be used individually or as a mixture of two or more.

[0032] The amount of catalyst is not particularly limited, but is preferably 0.01% to 20% by mass, and more preferably 0.1% to 10% by mass, based on 100% by mass of the film-forming composition of the present invention.

[0033] The degree of polymerization of the alkoxysilane oligomer is not particularly limited, but is preferably between 1,000 and 10,000. In the film-forming composition of the present invention, hydrolysis and condensation reactions of the alkoxysilane proceed, but it is preferable that these do not hinder smooth application when applying to a substrate. Because the degree of polymerization of the alkoxysilane oligomer is within the above range, the film-forming composition of the present invention can be easily applied to the surface of a substrate.

[0034] The content of alkoxysilane oligomer in the above alkoxysilane oligomer solution is preferably 1% to 80% by mass, more preferably 5% to 50% by mass, and even more preferably 10% to 40% by mass, based on 100% by mass of the alkoxysilane oligomer solution. When the content of alkoxysilane oligomer in the alkoxysilane oligomer solution is within the above range, a film can be sufficiently formed.

[0035] The content of alkoxysilane oligomer in the film-forming composition of the present invention is preferably 0.5% to 75% by mass, more preferably 5% to 45% by mass, and even more preferably 10% to 35% by mass, based on 100% by mass of the film-forming composition. When the content of alkoxysilane oligomer in the film-forming composition is within the above range, a film can be sufficiently formed on the substrate of the article.

[0036] The content of component (A) in the composition of the present invention is preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less, based on 100% by mass of the surface film-forming composition. Furthermore, the content of component (A) is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, particularly preferably 10% by mass or more, and most preferably 20% by mass or more, based on 100% by mass of the surface film-forming composition. By setting the lower limit of the concentration of component (A) within the above range, a film is more sufficiently formed on the substrate. Furthermore, by setting the upper limit of the concentration of component (A) within the above range, the content of component (B) can be relatively increased, further improving the water-repellent, oil-repellent, anti-fouling, and non-stick properties of the film, as well as further improving its durability against heat and water.

[0037] (B) Silicone Oil The film-forming composition of the present invention contains silicone oil. In the present invention, the term "silicone oil" refers to a linear polymer having a bifunctional siloxane unit as its main backbone, and is distinguished from silicone resin. That is, component (B) is a component other than component (A) and does not contain component (A). Because the film-forming composition of the present invention contains silicone oil (B), the film formed by curing the film-forming composition of the present invention can exhibit excellent water-repellent and oil-repellent properties, stain-resistant properties, and non-stick properties, and the film has excellent durability against heat and water.

[0038] (B) For example, straight silicone oil and / or modified silicone oil can be used as component (B).

[0039] (B) Component includes non-reactive straight silicone oils such as dimethyl silicone oil and methylphenyl silicone oil; non-reactive modified silicone oils such as polyether-modified dimethyl silicone oil, aralkyl-modified dimethyl silicone oil, long-chain alkyl-modified dimethyl silicone oil, higher fatty acid ester-modified dimethyl silicone oil, higher fatty acid-modified dimethyl silicone oil, and phenyl-modified dimethyl silicone oil; reactive straight silicone oils such as methyl hydrogen silicone oil; and reactive modified silicone oils such as amino-modified dimethyl silicone oil, epoxy-modified dimethyl silicone oil, carbinol-modified dimethyl silicone oil, mercapto-modified dimethyl silicone oil, carboxyl-modified dimethyl silicone oil, methacrylic-modified dimethyl silicone oil, acrylic-modified dimethyl silicone oil, phenol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, carboxylic acid anhydride-modified dimethyl silicone oil, and diol-modified dimethyl silicone oil. It is preferable to use a reactive straight silicone oil or a reactive modified silicone oil.

[0040] To ensure longer-lasting non-stick properties, it is preferable to use a modified dimethyl silicone oil as component (B), such as amino-modified dimethyl silicone oil, epoxy-modified dimethyl silicone oil, carbinol-modified dimethyl silicone oil, mercapto-modified dimethyl silicone oil, carboxyl-modified dimethyl silicone oil, methacrylic-modified dimethyl silicone oil, acrylic-modified dimethyl silicone oil, polyether-modified dimethyl silicone oil, phenol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, carboxylic acid anhydride-modified dimethyl silicone oil, diol-modified dimethyl silicone oil, aralkyl-modified dimethyl silicone oil, long-chain alkyl-modified dimethyl silicone oil, higher fatty acid ester-modified dimethyl silicone oil, higher fatty acid-modified dimethyl silicone oil, or phenyl-modified dimethyl silicone oil. It is more preferable to use a reactive modified dimethyl silicone oil. In particular, using a reactive modified dimethyl silicone oil with highly reactive substituents can improve the durability of the film. Therefore, it is even more preferable to use carbinol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, or diol-modified dimethyl silicone oil as component (B), and most preferable to use diol-modified dimethyl silicone oil.

[0041] To further improve non-stick properties, the number-average molecular weight Mn of component (B) is preferably 1000 or more, more preferably 3000 or more, even more preferably 4000 or more, and most preferably 5000 or more. On the other hand, there is no particular upper limit to the number-average molecular weight Mn of component (B). The number-average molecular weight Mn of component (B) can be set to, for example, 1000 to 20000, 3000 to 10000, etc. The number-average molecular weight can be measured by known methods, such as gel permeation chromatography.

[0042] To further improve non-stick properties, the kinematic viscosity of component (B) used with respect to the number-average molecular weight Mn is 2 mm per 100 units of number-average molecular weight. ２ Preferably 3 mm or more ２ More preferably 5 mm or more ２A value of 1 / s or higher is even more preferable. On the other hand, the upper limit of the kinematic viscosity with respect to the number average molecular weight Mn of component (B) is not particularly limited, for example, 150 mm per 100 number average molecular weight. ２ / s or less, 120mm ２ / s or less, 100mm ２ It can be less than or equal to / s. For example, when using component (B) with a number average molecular weight Mn of 1000, its kinematic viscosity is 20 mm². ２ / s or more 1500mm ２ / s or less, 30mm ２ / s or more 1200mm ２ / s or less, 50mm ２ / s or more 1000mm ２ It can be set to less than or equal to / s. Kinematic viscosity can be measured by known methods, such as in accordance with ASTM D 445:2024 or JIS Z 8803:2020, using a capillary viscometer, falling ball viscometer, rotational viscometer, or vibrating viscometer.

[0043] The content of component (B) in the film-forming composition is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 1.0% by mass or less, based on 100% by mass of the film-forming composition. Furthermore, the content of component (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, based on 100% by mass of the surface film-forming composition. By setting the lower limit of the concentration of component (B) within the above range, the water-repellent, oil-repellent, anti-fouling, and non-stick properties of the film are further improved, as is its durability against heat and water. Furthermore, by setting the upper limit of the concentration of component (B) within the above range, the content of component (A) can be relatively increased, and the film is formed more sufficiently on the substrate.

[0044] ((C) Inorganic Filler) The film-forming composition of the present invention may contain (C) an inorganic filler (hereinafter also referred to as "component (C)"). By containing component (C) in the film-forming composition of the present invention, it is possible to impart superior water-repellent, oil-repellent, stain-resistant, and non-stick properties to the surface of the film formed using the film-forming composition.

[0045] The inorganic filler is not particularly limited, and known inorganic fillers can be used. Suitable inorganic fillers include, for example, titanium oxide, silica, alumina, titania, zirconia, zinc oxide, carbon black, silicon carbide, silicon nitride, iron oxide, ultramarine, Prussian blue, calcium carbonate, clay minerals, talc, glass beads, glass flakes, mica, diamond, boron nitride, tungsten carbide, molybdenum carbide, molybdenum disulfide, boron carbide, graphite, graphene, fullerene, carbon nanotubes, and carbon fibers.

[0046] The content of component (C) in the composition of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on 100% by mass of the surface film-forming composition. Furthermore, the content of component (C) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 1.5% by mass or more, based on 100% by mass of the surface film-forming composition. By setting the lower limit of the content of component (C) within the above range, the water-repellent, oil-repellent, anti-fouling, and non-stick properties of the film are further improved, and the durability against heat and water is further improved. Furthermore, by setting the upper limit of the concentration of component (C) within the above range, the content of component (A) can be relatively increased, and the film is formed more sufficiently on the substrate.

[0047] The average particle size of component (C) is preferably 0.005 μm or more, more preferably 0.01 μm or more, and even more preferably 0.1 μm or more. Furthermore, the average particle size of component (C) is preferably 20.0 μm or less, more preferably 15.0 μm or less, even more preferably 10.0 μm or less, and particularly preferably 5 μm or less. By having the lower limit of the average particle size within the above range, the surface of the film formed using the film-forming composition can be given better water-repellent, oil-repellent, anti-fouling, and non-stick properties. By having the upper limit of the average particle size within the above range, the non-stick properties of the surface of the film formed using the film-forming composition can be further improved.

[0048] The average particle size of the powder of the present invention described above is the average particle size measured by a laser diffraction or dynamic light scattering particle size distribution analyzer.

[0049] (D) Solvent The film-forming composition of the present invention may contain a solvent. The solvent may be a solvent added to the composition of the present invention, or it may be a solvent to which water, alcohol, glycol, glycol ether, etc., used when preparing the alkoxysilane oligomer of component (A) above are added together with component (A).

[0050] The solvent used in the composition of the present invention includes water and / or water-soluble organic solvents. When water is used alone as the solvent, the pH of the film-forming composition of the present invention is preferably 1 to 5, and more preferably 2 to 4. When the pH is within the above range, the film-forming composition of the present invention can exhibit excellent stability when water is used as the solvent.

[0051] The water-soluble organic solvent is not particularly limited, and conventionally known water-soluble organic solvents can be used. Examples of such water-soluble organic solvents include alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and ether-alcohol-based solvents. Among these, propylene glycol and propylene glycol monomethyl ether are preferred due to their excellent affinity for water.

[0052] The water and water-soluble organic solvents mentioned above may be used individually or as a mixture of two or more.

[0053] The solvent content in the film-forming composition of the present invention is preferably 50% to 95% by mass, and more preferably 60% to 85% by mass, based on 100% by mass of the film-forming composition. When the solvent content in the film-forming composition is within the above range, it is excellent in terms of film-forming properties.

[0054] (Other Components) The compositions of the present invention may contain other components in addition to the components described above. Such other components include common additives used in coating agents in fields such as cooking utensils, industrial machinery, food manufacturing equipment, kitchen equipment, medical equipment, medical instruments, hypodermic needles, molding dies, paint manufacturing equipment, painting jigs, tableware, cutlery, electronic products, home appliances, communication equipment, mobile phones, monitors, vehicles, aircraft, ships, window glass (window glass of vehicles, aircraft, ships, buildings, etc.), traffic infrastructure, traffic signals, road signs, convex mirrors, buildings, factory equipment, housing equipment, roofs, kitchen sinks, door knobs, toilets, washbasins, bathtubs, automobile bodies, mirror covers, door handles, grills, range hoods, bumpers, spoilers, etc. Examples of such other components include antioxidants, ultraviolet absorbers, antistatic agents, dispersants, anti-settling agents, anti-sagging agents, surfactants, defoamers, preservatives, leveling agents, etc.

[0055] The content of the additive in the composition of the present invention is not particularly limited as long as it does not inhibit the formation of a film. Preferably, it is 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less, based on 100% by mass of the composition. Furthermore, the lower limit of the content of the additive is not particularly limited and may be 0%, 0.1%, or 0.3% by mass.

[0056] According to the film-forming composition of the present invention described above, a film can be formed on the surface of a substrate, and a film can be formed on the surface of the substrate that is excellent in water-repellent, oil-repellent, stain-resistant, and non-stick properties, as well as having excellent durability against heat and water.

[0057] 2. The coating of the present invention is a coating formed by curing the above-described coating-forming composition of the present invention.

[0058] The thickness of the coating is preferably 0.1 μm to 100 μm, and more preferably 1 μm to 50 μm. A coating thickness within this range allows for easier formation of the coating on the substrate surface, improving the water-repellent, oil-repellent, stain-resistant, and non-stick properties of the coating, as well as its resistance to heat and water. Furthermore, a lower limit of the coating thickness within this range improves the abrasion resistance of the coating.

[0059] The water contact angle of the film is preferably 80° or higher, more preferably 85° or higher, even more preferably 90° or higher, and particularly preferably 95° or higher. Furthermore, there is no particular upper limit to the water contact angle of the film, and it may be 120°, 110°, or 100°.

[0060] In this specification, the water contact angle of the above-mentioned film is measured according to the water- and oil-repellent properties measurement method described in the examples below.

[0061] The oleic acid contact angle of the film is preferably 20° or more, more preferably 25° or more, even more preferably 30° or more, and particularly preferably 40° or more. Furthermore, there is no particular upper limit to the oleic acid contact angle of the film, and it may be 70°, 65°, or 55°.

[0062] In this specification, the oleic acid contact angle of the above-mentioned film is measured according to the water- and oil-repellent properties measurement method described in the examples below.

[0063] 3. Article The article of the present invention is an article having a coating formed by curing the above-described coating-forming composition of the present invention.

[0064] In the article of the present invention, the above-mentioned film-forming composition and the above-mentioned film are the same as the above-described film-forming composition and film of the present invention.

[0065] The articles are not particularly limited as long as they have a film formed by the curing of the film-forming composition of the present invention described above, but examples include articles that may come into contact with organic matter such as food, cell tissue, and excrement, and for which water-repellent, oil-repellent, antifouling, and non-stick properties are required. Articles that come into contact with the aforementioned organic matter in a heated environment are also examples. Furthermore, as will be described later, examples of articles include those used outdoors (vehicles, etc.), and these articles may be subject to the adhesion of rain, snow, mud, etc. The film-forming composition and film of the present invention can exhibit particularly high water-repellent, oil-repellent, antifouling, and non-stick properties with respect to organic matter.

[0066] Examples of items include cooking utensils, industrial machinery, food processing equipment, kitchen equipment, medical equipment, medical instruments, hypodermic needles, molding dies, paint manufacturing equipment, painting jigs, tableware, cutlery, electronic products, home appliances, communication equipment, mobile phones, monitors, vehicles, aircraft, ships, window glass (window glass of vehicles, aircraft, ships, buildings, etc.), traffic infrastructure, traffic signals, road signs, convex mirrors, buildings, factory equipment, housing equipment, roofs, kitchen sinks, doorknobs, toilets, washbasins, bathtubs, automobile bodies, mirror covers, door handles, grills, range hoods, bumpers, spoilers, etc.

[0067] 4. Method for Forming a Film The method for forming a film according to the present invention comprises: (1) step 1, applying a film-forming composition to the surface of a substrate to form a film-forming composition layer; and (2) step 2, heating the film-forming composition layer to form a film on the surface of the substrate, wherein the film-forming composition contains (A) a polymer having siloxane bonds and (B) silicone oil. The method for forming a film according to the present invention is a method for manufacturing a film on a substrate.

[0068] According to the formation method of the present invention, in step 1, the above-mentioned film-forming composition is applied to the surface of a substrate to form a film-forming composition layer, and in step 2, the film-forming composition layer is heated. As a result, the (B) silicone oil does not mix with the (A) polymer having siloxane bonds and harden, but floats to the surface of the film (opposite side from the substrate) and hardens. Therefore, the surface of the film formed by this hardening can exhibit excellent water-repellent, oil-repellent, stain-resistant, and non-stick properties. Furthermore, because the (B) component is selectively present on the surface of the film formed by the formation method of the present invention, even under high-temperature conditions such as when water is poured on it, when it is heated, when hot water is poured on it, or when it is immersed in hot water, changes in the above properties are suppressed, and peeling from the surface of the article is suppressed.

[0069] The following provides a detailed explanation of each step.

[0070] (Step 1) Step 1 is a step of applying a film-forming composition to the surface of a substrate to form a film-forming composition layer.

[0071] The object on which a film is formed by the method of forming the present invention is a substrate. Examples of substrates include substrates made of metals that make up cooking utensils, etc. Examples of such metals include stainless steel, iron, zinc, aluminum, magnesium, cobalt, nickel, copper, tin, gold, and alloys thereof; inorganic materials such as glass, ceramics, and pottery; and organic materials such as resins. The film-forming composition and film of the present invention can be suitably used among the above substrates in that they can impart high water-repellent, oil-repellent, anti-fouling, and non-stick properties to metals, and the method of forming the present invention is particularly useful when the substrate is metal. Among these, stainless steel, iron, and aluminum are suitable as objects to be treated because they are used in cooking utensils, etc.

[0072] The above-mentioned substrate can be suitably used as a target for processing when it is used in cooking utensils, industrial machinery, food manufacturing equipment, kitchen equipment, medical equipment, medical instruments, injection needles, molding dies, paint manufacturing equipment, painting jigs, tableware, cutlery, electronic products, home appliances, communication equipment, mobile phones, monitors, vehicles, aircraft, ships, traffic infrastructure, traffic signals, road signs, convex mirrors, buildings, factory equipment, housing equipment, roofs, kitchen sinks, door knobs, bathtubs, automobile bodies, mirror covers, door handles, grills, range hoods, bumpers, spoilers, etc.

[0073] The above-mentioned substrate should be present on the surface of the article to be treated so as to be in sufficient contact with the film-forming composition. For example, the article may consist solely of the above-mentioned metal, or it may be a composite product combining the metal with other materials, such as ceramic materials or plastic materials. Furthermore, it may be a plated product in which a plating film is formed on the surface of the above-mentioned metal. For example, a steel sheet with zinc plating or zinc alloy plating can be used as the substrate.

[0074] As the film-forming composition used in step 1, the film-forming composition of the present invention described above can be used.

[0075] Conventional known methods can be used to apply the film-forming composition to the surface of a substrate. Examples include known methods such as dip coating, dip-spin coating, spray coating, roll coating, spin coating, and bar coating. Among these, the dip-spin coating and spray coating methods are preferred because they allow for uniform application regardless of the shape of the substrate.

[0076] By applying the film-forming composition using the above application method, a film-forming composition layer is formed on the surface of the substrate. The thickness of the film-forming composition layer is preferably 0.1 μm to 100 μm, and more preferably 1 μm to 50 μm. By having the film-forming composition layer thickness within the above range, the thickness of the film formed in step 2 described later can be adjusted to an appropriate range, thereby suppressing the loss of dimensional accuracy of the substrate while providing the substrate with water-repellent, oil-repellent, stain-resistant, non-stick properties, and durability against heat and water.

[0077] By step 1 described above, a film-forming composition can be applied to the surface of the substrate to form a film-forming composition layer.

[0078] (Step 2) Step 2 is a step of heating the film-forming composition layer to form a film on the surface of the substrate.

[0079] The heating method for heating the film-forming composition layer formed on the surface of the substrate is not limited and can be any conventionally known method. For example, one heating method involves placing the substrate and the film-forming composition layer together in a dryer and holding them there for a certain period of time.

[0080] The heating temperature is preferably 20°C or higher, more preferably 50°C or higher, even more preferably 100°C or higher, and particularly preferably 150°C or higher. Furthermore, the heating temperature is preferably 400°C or lower, more preferably 300°C or lower, and even more preferably 250°C or lower.

[0081] Furthermore, if the room temperature is around 20°C, heating in step 2 does not necessarily require the use of a dryer or the like; it may be left at room temperature for a certain period of time.

[0082] The heating time is preferably 10 minutes or more, and more preferably 20 minutes or more. Furthermore, the heating time is preferably 120 minutes or less, and more preferably 60 minutes or less.

[0083] Furthermore, if the room temperature is around 20°C, heating in step 2 does not necessarily require the use of a dryer or the like; it may be left at room temperature for a certain period of time.

[0084] As described above in step 2, a film is formed on the surface of the substrate.

[0085] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

[0086] (Substrate) As a substrate for forming a film using a film-forming composition, an aluminum alloy A1050 substrate (100 mm x 50 mm x 0.2 mm) was prepared.

[0087] Example 1 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a polyether group having a number average molecular weight Mn of 1000 and a kinematic viscosity of 75 mmHg were added per 100 parts by mass of the mixture. ２ A film-forming composition was prepared by adding 0.5 parts by mass of non-reactive modified dimethyl silicone oil at 0 / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0088] Example 2 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a diol group-containing material with a number average molecular weight Mn of 5000 and a kinematic viscosity of 300 mmHg were added per 100 parts by mass of the mixture. ２ A film-forming composition was prepared by adding 0.5 parts by mass of reactive modified dimethyl silicone oil at 0 / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0089] Example 3 A mixture was prepared consisting of 25% by mass of silicone resin, 5% by mass of dimethyldimethoxysilane, and 70% by mass of propylene glycol monoethyl ether. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a diol group-containing material with a number average molecular weight Mn of 5000 and a kinematic viscosity of 300 mmHg were added per 100 parts by mass of the mixture. ２ A film-forming composition was prepared by adding 0.5 parts by mass of reactive modified dimethyl silicone oil at 0 / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 15 μm on the substrate.

[0090] Example 4 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a diol group-containing material with a number average molecular weight Mn of 5000 and a kinematic viscosity of 300 mmHg were added per 100 parts by mass of the mixture. ２ 0.5 parts by mass of reactive modified dimethyl silicone oil at 0 / s was added. Furthermore, 30 parts by mass of a solution in which titanium dioxide particles (average particle size 0.3 μm) were dispersed in propylene glycol monoethyl ether to a concentration of 50% by mass was added to prepare a film-forming composition. Next, the prepared film-forming composition was spray-coated onto the substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 20 μm on the substrate.

[0091] Example 5 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a diol group-containing material with a number average molecular weight Mn of 5000 and a kinematic viscosity of 300 mmHg were added per 100 parts by mass of the mixture. ２0.5 parts by mass of reactive modified dimethyl silicone oil at 0 / s was added. Furthermore, 30 parts by mass of a solution in which alumina particles (average particle size 0.6 μm) were dispersed in propylene glycol monoethyl ether to a concentration of 50% by mass was added to prepare a film-forming composition. Next, the prepared film-forming composition was spray-coated onto the substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 20 μm on the substrate.

[0092] Example 6 A mixture consisting of 60% by mass of silicone resin and 40% by mass of propylene glycol monoethyl ether was prepared. Then, 1.0 part by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a polyether group having a number average molecular weight Mn of 1000 and a kinematic viscosity of 75 mmHg were added per 100 parts by mass of the mixture. ２ A film-forming composition was prepared by adding 1.0 part by mass of non-reactive modified dimethyl silicone oil at a concentration of / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0093] Example 7 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a carbinol group-containing compound with a number average molecular weight Mn of 1000 and a kinematic viscosity of 70 mmHg were added per 100 parts by mass of the mixture. ２ A film-forming composition was prepared by adding 0.5 parts by mass of reactive modified dimethyl silicone oil at 0 / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0094] Example 8 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a diol group-containing material with a number average molecular weight Mn of 1000 and a kinematic viscosity of 50 mmHg were added per 100 parts by mass of the mixture. ２0.5 parts by mass of a reactive modified dimethyl silicone oil with a kinematic viscosity of 500 mm ２ / s was added to prepare a film-forming composition. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200 °C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0095] Example 9 A mixed solution consisting of 30% by mass of a silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Next, 0.5 parts by mass of aluminum monoacetylacetonate bis(ethylacetoacetate) and 0.5 parts by mass of a reactive modified dimethyl silicone oil having a diol group, a number average molecular weight Mn of 8000, and a kinematic viscosity of 500 mm ２ 0.5 parts by mass of a reactive modified dimethyl silicone oil with a kinematic viscosity of 500 mm ２ / s was added to prepare a film-forming composition. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200 °C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0096] Example 10 A mixed solution consisting of 30% by mass of a silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Next, 0.5 parts by mass of aluminum monoacetylacetonate bis(ethylacetoacetate) and 0.5 parts by mass of a reactive modified dimethyl silicone oil having a diol group, a number average molecular weight Mn of 12000, and a kinematic viscosity of 500 mm ２ 0.5 parts by mass of a reactive modified dimethyl silicone oil with a kinematic viscosity of 500 mm ２ / s was added to prepare a film-forming composition. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200 °C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0097] Example 11 A mixed solution consisting of 30% by mass of a silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Next, 0.5 parts by mass of aluminum monoacetylacetonate bis(ethylacetoacetate) and 0.5 parts by mass of a reactive modified dimethyl silicone oil having a number average molecular weight Mn of 1000 and a kinematic viscosity of 1000 mm ２A film-forming composition was prepared by adding 0.5 parts by mass of non-reactive straight silicone oil (dimethyl silicone oil) with a concentration of / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0098] Example 12 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a carbinol group-containing material with a number average molecular weight Mn of 900 and a kinematic viscosity of 40 mmHg were added per 100 parts by mass of the mixture. ２ A film-forming composition was prepared by adding 0.5 parts by mass of reactive modified dimethyl silicone oil at 0 / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0099] Example 13 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate and a polyether group having a number average molecular weight Mn of 600 and a kinematic viscosity of 75 mmHg were added per 100 parts by mass of the mixture. ２ A film-forming composition was prepared by adding 0.5 parts by mass of non-reactive modified dimethyl silicone oil at 0 / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0100] Example 14 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Then, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate, with a number average molecular weight Mn of 2000 and a kinematic viscosity of 25 mm² was added per 100 parts by mass of the mixture. ２A film-forming composition was prepared by adding 0.5 parts by mass of reactive straight silicone oil (methyl hydrogen silicone oil) at 0 / s. Next, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0101] Comparative Example 1 A mixture consisting of 30% by mass of silicone resin and 70% by mass of propylene glycol monoethyl ether was prepared. Next, 0.5 parts by mass of aluminum monoacetylacetonate bisethyl acetoacetate was added to 100 parts by mass of the mixture to prepare a film-forming composition. Then, the prepared film-forming composition was spray-coated onto a substrate and heat-treated at 200°C for 30 minutes using a dryer to form a film with a thickness of 10 μm on the substrate.

[0102] (Evaluation Method) The following evaluations were performed on the examples and comparative examples.

[0103] The water-repellent and oil-repellent properties of the water-repellent and oil-repellent coating were measured using a contact angle meter DMs-301 manufactured by Kyowa Interface Science Co., Ltd. Water repellency was evaluated by measuring the contact angle of water, and oil repellency was evaluated by measuring the contact angle of oleic acid.

[0104] The stain resistance of the stain-resistant coating was evaluated using ZEBRA Corporation's oil-based magic marker, Maki (product name). Specifically, lines were drawn on the surface of the coating with the magic marker, and the magic marker ink was wiped off with a cloth. The ease of removal was evaluated according to the following evaluation criteria. A rating of △ or higher indicates that there are no problems in actual use. ◎: Ink is repelled and can be easily wiped off. 〇: Ink is not repelled, but can be wiped off. △: Ink is not repelled, but can be wiped off with strong rubbing. ×: Ink is not repelled and cannot be wiped off.

[0105] Non-adhesion (peel strength): A 20mm cloth tape SLIONTEC (product name) manufactured by Maxell Corporation was attached to the film with a load of 2kg, and the non-adhesion strength was measured using a 90° peel test with a lifting speed of 10mm / min using a universal testing machine Autograph AGS-X manufactured by Shimadzu Corporation.

[0106] Non-stick properties (rice adhesion suppression effect): The film-forming compositions prepared in the examples and comparative examples were spray-coated onto the inner surface of an aluminum mess tin (for 2 cups of rice), and heat-treated in a dryer at 200°C for 30 minutes to form a film on the inside. Next, 2 cups of white rice were cooked in the mess tin with the film formed on it, and immediately after cooking, the mess tin containing the rice was turned upside down and shaken, and the number of shakes until the rice fell out was measured.

[0107] In the durability test examples and comparative examples, the coated substrate or mess kit was subjected to hot water immersion treatment by immersing it in 90°C hot water for 100 hours or 300 hours. Subsequently, the above-described tests were performed using the hot water immersion treated substrate and mess kit to evaluate durability.

[0108] Non-stick properties (improvement in the cleaning and removal of oil mist) In the examples and comparative examples, the substrate with the film formed on it was attached to the panel of a range hood and used for one month. The oil mist adhering to the substrate was wiped off with a cloth and the ease of removal was evaluated according to the evaluation criteria below. Note that an evaluation of △ or higher indicates that there are no problems in actual use. ◎: Easily wiped off with a cloth. 〇: Can be wiped off by rubbing with a cloth. △: Can be wiped off by rubbing hard with a cloth. ×: Cannot be wiped off with a cloth, and the oil spreads.

[0109] Non-stick properties (effect of suppressing flour adhesion) In the examples and comparative examples, flour was sprinkled on and attached to the substrates that had a film formed on them. The ease of removal of the flour attached to the substrates was wiped off with a cloth and evaluated according to the evaluation criteria below. Note that an evaluation of △ or higher indicates that there are no problems in actual use. ◎: Easily removed with a cloth. 〇: Removable with a cloth. △: Removable by rubbing hard with a cloth. ×: Flour remains attached even when rubbed hard with a cloth.

[0110] The results are shown in Table 1.

[0111]

[0112] The results from the examples showed that the film-forming composition of the present invention, which contains (A) a polymer having siloxane bonds and (B) silicone oil, can form a film that is excellent in water-repellent and oil-repellent properties, stain-resistant properties, and non-stick properties, and also has excellent durability against heat and water.

[0113] Furthermore, the results from the examples showed that including a modified silicone oil as (B) silicone oil improved the durability of the film. Moreover, it was found that including a modified silicone oil with a large number-average molecular weight as (B) silicone oil particularly improved the water-repellent, oil-repellent, anti-fouling, non-stick properties, and durability of the film.

[0114] In contrast, the results from Comparative Example 1 showed that the film formed by (B) a film-forming composition that does not contain silicone oil had poor water-repellent and oil-repellent properties, stain-resistant properties, and non-stick properties, as well as poor durability against heat and water.

Claims

1. A film-forming composition characterized by containing (A) a polymer having siloxane bonds, and (B) silicone oil.

2. The film-forming composition according to claim 1, wherein the content of the polymer having a siloxane bond (A) is 80% by mass or less, with the film-forming composition being 100% by mass.

3. The film-forming composition according to claim 1, wherein the (B) silicone oil is a straight silicone oil and / or a modified silicone oil.

4. The film-forming composition according to claim 1, wherein the (B) silicone oil is at least one straight silicone oil selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, or at least one modified dimethyl silicone oil selected from the group consisting of amino-modified dimethyl silicone oil, epoxy-modified dimethyl silicone oil, carbinol-modified dimethyl silicone oil, mercapto-modified dimethyl silicone oil, carboxyl-modified dimethyl silicone oil, methacrylic-modified dimethyl silicone oil, acrylic-modified dimethyl silicone oil, polyether-modified dimethyl silicone oil, phenol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, carboxylic acid anhydride-modified dimethyl silicone oil, diol-modified dimethyl silicone oil, aralkyl-modified dimethyl silicone oil, long-chain alkyl-modified dimethyl silicone oil, higher fatty acid ester-modified dimethyl silicone oil, higher fatty acid-modified dimethyl silicone oil, and phenyl-modified dimethyl silicone oil.

5. The film-forming composition according to claim 1, wherein the (B) silicone oil is at least one modified dimethyl silicone oil selected from the group consisting of amino-modified dimethyl silicone oil, epoxy-modified dimethyl silicone oil, carbinol-modified dimethyl silicone oil, mercapto-modified dimethyl silicone oil, carboxyl-modified dimethyl silicone oil, methacrylic-modified dimethyl silicone oil, acrylic-modified dimethyl silicone oil, polyether-modified dimethyl silicone oil, phenol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, carboxylic acid anhydride-modified dimethyl silicone oil, diol-modified dimethyl silicone oil, aralkyl-modified dimethyl silicone oil, long-chain alkyl-modified dimethyl silicone oil, higher fatty acid ester-modified dimethyl silicone oil, higher fatty acid-modified dimethyl silicone oil, and phenyl-modified dimethyl silicone oil.

6. The film-forming composition according to claim 1, wherein the (B) silicone oil is at least one modified dimethyl silicone oil selected from the group consisting of carbinol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, and diol-modified dimethyl silicone oil.

7. The film-forming composition according to claim 1, wherein the number average molecular weight Mn of the (B) silicone oil is 1000 or more.

8. The film-forming composition according to claim 1, wherein the content of (B) silicone oil is 5.0% by mass or less, with the film-forming composition being 100% by mass.

9. The film-forming composition according to claim 1, further comprising (C) an inorganic filler.

10. The film-forming composition according to claim 9, wherein the (C) inorganic filler is at least one inorganic filler selected from the group consisting of titanium dioxide, silica, alumina, titania, zirconia, zinc oxide, carbon black, silicon carbide, silicon nitride, iron oxide, ultramarine, Prussian blue, calcium carbonate, clay minerals, talc, glass beads, glass flakes, mica, diamond, boron nitride, tungsten carbide, molybdenum carbide, molybdenum disulfide, boron carbide, graphite, graphene, fullerene, carbon nanotubes, and carbon fibers.

11. A film obtained by curing the film-forming composition described in claim 1.

12. The coating according to claim 11, wherein the coating has a water contact angle of 80° or more.

13. The coating according to claim 11, wherein the coating has an oleic acid contact angle of 20° or more.

14. An article having a coating obtained by curing the coating composition described in claim 1.

15. A method for forming a film, comprising: (1) step 1 of applying a film-forming composition to the surface of a substrate to form a film-forming composition layer; and (2) step 2 of heating the film-forming composition layer to form a film on the surface of the substrate, wherein the film-forming composition contains (A) a polymer having siloxane bonds and (B) silicone oil.

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