Material having surface-treated coating film

Abstract

The present invention addresses the problem of providing a material having a new surface-treated coating film with excellent antifouling and low-temperature drying properties. The problem is resolved by a material having a coating film at or on the surface thereof, wherein the coating film contains a silicone polymer (A) and at least one metal element (B) selected from titanium, zirconium, and aluminum, and has a specific infrared absorption spectrum peak intensity.

Description

Materials with surface treatment coatings

[0001] The present invention relates to a material having a surface treatment coating formed using a surface treatment agent that can be suitably applied to components of industrial products such as medical equipment, kitchen equipment, cooking utensils, and food packaging containers.

[0002] Industrial products such as medical devices, kitchen appliances, cooking utensils, and food packaging containers use metals, resins, and fiber materials as their constituent components. Because these industrial products are used in a variety of environments, the materials used in these products are required to have a variety of performance characteristics. Therefore, in order to impart various performance characteristics to these materials, techniques for providing surface treatment coatings with various performance characteristics on or over the surface of the material have been developed. For example, Patent Document 1 discloses a technique relating to a metal surface treatment composition and a treatment method therefor, which comprises a predetermined phosphoric acid compound, a fluoroacid having at least four fluorine atoms and a predetermined element, a silane coupling agent having at least one active hydrogen-containing amino group, and a silane coupling agent having at least one epoxy group, all blended in a dissolved or dispersed state in predetermined amounts.

[0003] Japanese Patent Application Laid-Open No. 2006-213958

[0004] In recent years, further improvements in performance have been required for materials used in the above-mentioned elemental members. An object of the present invention is to provide a material having a new surface treatment coating that is excellent in stain resistance and low-temperature drying properties.

[0005] As a result of extensive research into solving the above-mentioned problems, the present inventors discovered that the above-mentioned problems can be solved by a surface treatment coating that contains a specified silicone polymer and a specified metal element and that exhibits a specified peak intensity in its infrared absorption spectrum, thereby completing the present invention.

[0006] That is, the present invention provides: [1] a material having a coating on or at a surface thereof, wherein the coating contains a silicone polymer (A) and at least one metal element (B) selected from titanium, zirconium, and aluminum, and satisfies the following (I) and (II): (I) The coating has a peak at 950 cm in an infrared absorption spectrum.－１ ~1080cm －１ and a peak (α) in the range of 720 cm －１ ~830cm －１ and a peak (β) in the range of the peak intensity (α Ａ ) with respect to the peak intensity of the peak β (β Ａ ) ratio (β Ａ / α Ａ (II) The mass (A) of the silicone polymer (A) in the coating in terms of Si is 0.22 or more and 0.72 or less. Ｍ ) to the converted mass (B Ｍ ) ratio (B Ｍ / A Ｍ ) is in the range of 0.001 or more and 0.880 or less; [2] the material having a coating according to [1], wherein the material is one selected from a metal material, a resin material, and a fiber material; [3] the material having a coating according to [1] or [2], wherein an undercoat containing at least one selected from the group consisting of a silane coupling agent having an amino group, a polymer of the silane coupling agent, and a copolymer of the silane coupling agent and the polymer, and / or a phosphate is present between the material and the coating; [4] the material having a coating according to any one of [1] to [3], wherein the thickness of the coating is 0.3 μm or more and 10 μm or less;

[0007] According to the present invention, a material having a surface treatment coating film that is excellent in antifouling properties and low-temperature drying properties can be provided.

[0008] The surface treatment agent, the material having the surface treatment film, and the manufacturing method thereof are described below. In this specification, a numerical range expressed using "to" means a range including the numerical values ​​before and after "to" as the lower and upper limits, and "X to Y" means at least X and at most Y.

[0009] (Surface Treatment Agent) A surface treatment agent capable of forming a coating on the surface of a material on which the surface treatment coating is to be formed can also be one embodiment of the present invention. The surface treatment agent according to this embodiment contains a silicone polymer (A) and a compound containing at least one metal element (B) selected from titanium, zirconium, and aluminum. By using this surface treatment agent, a surface treatment coating having excellent antifouling properties (especially suppressing contamination caused by animals and plants in high-temperature environments) and low-temperature drying properties can be formed on the surface of the material. Therefore, it is useful as an antifouling coating forming agent. In this embodiment, the high-temperature environment in terms of antifouling properties refers to an atmosphere of 100°C to 200°C, and the low temperature in terms of low-temperature drying properties refers to a temperature of 20°C to 80°C. Furthermore, surface treatment coatings having excellent antifouling properties and low-temperature drying properties formed by the surface treatment agent are useful for materials used in machine components constituting industrial products such as medical equipment, kitchen equipment, cooking utensils, and food packaging containers.

[0010] <Silicone polymer (A)> As for the silicone polymer (A), as described below, it is possible to form a coating film having a specific infrared absorption spectrum absorption peak, and it is not particularly limited as long as it has a plurality of siloxane bonds and an organopolysiloxane structure in which an organic group is bonded to silicon (Si), but it is preferable to have an organopolysiloxane structure in which at least one organic group bonded to Si is present in one molecule.The position at which the organic group is bonded is not particularly limited, and it may be bonded to the main chain, side chain, or terminal.The silicone polymer (A) may be a homopolymer having the above-mentioned organopolysiloxane structure, a mixture of a homopolymer having the above-mentioned organopolysiloxane structure and a homopolymer having a polysiloxane structure, or a copolymer (block copolymer or graft polymer) having the above-mentioned organopolysiloxane structure and a polysiloxane structure.The silicone polymer (A) may be an addition type or a condensation type. Furthermore, the silicone polymer (A) may be any of a heat-curing type, a room temperature curing type (RVT) and a UV-curing type.

[0011] Examples of organic groups bonded to Si in the organopolysiloxane structure include, but are not limited to, saturated hydrocarbon groups, unsaturated hydrocarbon groups, halogenated alkyl groups, and epoxycycloalkyl groups. Examples of saturated hydrocarbon groups include, but are not limited to, linear or branched alkyl groups and cycloalkyl groups. Examples of unsaturated hydrocarbon groups include, but are not limited to, linear or branched alkenyl groups, cycloalkenyl groups, cycloalkenylalkyl groups, and aryl groups.

[0012] Examples of halogenated alkyl groups include a chloromethyl group, a 3-chloropropyl group, a 1-chloro-2-methylpropyl group, and a 3,3,3-trifluoropropyl group. Examples of linear or branched alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, a 3-pentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of cycloalkyl groups include a cyclopentyl group and a cyclohexyl group. Examples of linear or branched alkenyl groups include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, and a hexenyl group. Examples of cycloalkenyl groups include cyclopentenyl groups and cyclohexenyl groups. Examples of cycloalkenylalkyl groups include cyclopentenylethyl groups, cyclohexenylethyl groups, and cyclohexenylpropyl groups. Examples of aryl groups include phenyl groups, toluyl groups, and naphthyl groups.

[0013] The polysiloxane structure is not particularly limited as long as it is different from the above-mentioned organopolysiloxane structure, and examples thereof include a polysiloxane structure having at least two oxygen atoms bonded to Si in one molecule, and a polysiloxane structure having at least two alkoxy groups bonded to Si in one molecule. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The alkoxy group may be linear or branched.

[0014] The above-mentioned various silicone polymers (A) may be used alone or in combination of two or more in preparing the surface treatment agent.

[0015] In particular, from the viewpoint of forming a coating film having a specific infrared absorption spectrum, which will be described later, it is preferable that the silicone polymer (A) contains a structure having three reactive functional groups per Si atom. By using such a silicone polymer, the infrared absorption spectrum of the formed coating film is Ａ / α Ａ tends to be lower than in the past. This indicates that the silicone polymer in the coating has fewer Si—C bonds relative to Si—O bonds, and therefore fewer organic groups in the side chains, which makes it possible to impart suitable antifouling properties and low-temperature drying properties to the coating. The organic groups in the side chains that impart functionality to the silicone polymer preferably have an alkyl group from the viewpoint of antifouling properties, and preferably have an alkoxy group from the viewpoint of low-temperature drying properties.

[0016] The content of the silicone polymer (A) in the surface treatment agent according to this embodiment is not particularly limited as long as the desired coating can be formed, but is preferably 5 to 20 mass %, more preferably 7 to 20 mass %, and even more preferably 15 to 20 mass %. When two or more silicone polymers are used in the surface treatment agent, the mass % content refers to the total of the silicone polymers.

[0017] <Compound Containing Metal Element (B)> The surface treatment agent according to this embodiment contains a compound containing at least one metal element (B) selected from titanium, zirconium, and aluminum (hereinafter referred to as compound (B)).

[0018] The titanium-containing compound is not particularly limited as long as it contains titanium as an element, and may be either an inorganic titanium compound or an organic titanium compound. Examples of inorganic titanium compounds include, but are not limited to, titanyl sulfate, titanyl nitrate, titanium nitrate, titanyl chloride, titanium chloride, titania sol, and titanium oxide. Examples of organic titanium compounds include, but are not limited to, potassium oxalate titanate, titanium lactate, tetraisopropyl titanate, tetra-normal-butyl titanate, butyl titanate dimer, titanium acetylacetonate, diisopropyl titanium bisacetylacetone, and titanium diisopropoxybis(acetylacetonate). Of these, organic titanium compounds are preferred. These compounds may be used alone or in combination in the preparation of the surface treatment agent.

[0019] The zirconium-containing compound is not particularly limited as long as it contains zirconium as an element, and may be either an inorganic zirconium compound or an organic zirconium compound. Examples of inorganic zirconium compounds include, but are not limited to, zirconyl sulfate, zirconyl nitrate, zirconium nitrate, zirconyl chloride, zirconium chloride, zirconia sol, and zirconium oxide. Examples of organic zirconium compounds include, but are not limited to, zirconium lactate, zirconium tetraisopropoxide, zirconium acetylacetonate, normal propyl zirconate, normal butyl zirconate, and zirconium tetraacetylacetonate. Of these, it is preferable to use an organic zirconium compound. These compounds may be used alone or in combination of two or more in the preparation of the surface treatment agent.

[0020] The aluminum-containing compound is not particularly limited as long as it contains aluminum as an element, and may be either an inorganic aluminum compound or an organic aluminum compound. Examples of inorganic aluminum compounds include, but are not limited to, aluminum sulfate, aluminum nitrate, aluminum chloride, alumina sol, and aluminum oxide. Examples of organic aluminum compounds include, but are not limited to, aluminum lactate, aluminum tetraisopropoxide, aluminum acetylacetonate, normal propyl aluminate, normal butyl aluminate, and aluminum tetraacetylacetonate. Of these, it is preferable to use an organic aluminum compound. These compounds may be used alone or in combination of two or more in the preparation of the surface treatment agent.

[0021] The content of compound (B) in the surface treatment agent according to this embodiment is not particularly limited as long as the desired coating can be formed, but is preferably 0.02 to 18 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.2 to 10 mass %. When two or more compounds are used in the surface treatment agent, the mass % content refers to the total amount thereof.

[0022] In the surface treatment agent according to this embodiment, the silicone polymer (A) is Ｍ ) the metal element equivalent mass (B Ｍ ) ratio (B Ｍ / A Ｍ ) is 0.001 to 0.880, preferably 0.005 to 0.750, more preferably 0.010 to 0.487, and even more preferably 0.010 to 0.265.

[0023] <Solvent> The solvent used in the surface treatment agent according to this embodiment is not particularly limited and may be an organic solvent or a mixture of an organic solvent and water. Examples of the organic solvent include hydrocarbon solvents, alcohol solvents, ester solvents, nitrile solvents, and ketone solvents. Examples of the hydrocarbon solvent include benzene, ethylbenzene, toluene, xylene, and cyclohexane. Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 3-methyl-1-butanol, 2,2-dimethyl-1-propanol, 2-pentanol, 3-methyl-2-butanol, 3-pentanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-2-but ...1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-2-butanol, 1-hexanol, 2- Examples of the solvent include methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, and 2-ethyl-1-butanol. Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, and 2-ethoxyethyl acetate. Examples of the nitrile solvent include acetonitrile. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone, but are not limited to these. Furthermore, one type of organic solvent may be used, or two or more types may be used in combination. The alcohol solvent is preferably an alcohol having 1 to 5 carbon atoms.

[0024] The water concentration of the surface treatment agent is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably substantially free of water. By adjusting the water content to such a level, the stability of the surface treatment agent is excellent. The water concentration of the surface treatment agent can be measured, for example, using an MKV-710 manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[0025] When the surface treatment agent according to the present embodiment contains an alcohol-based solvent as a solvent, the content of the alcohol-based solvent is preferably 65 to 85 mass %, more preferably 70 to 85 mass %, and even more preferably 75 to 85 mass %, relative to the mass of the surface treatment agent.

[0026] The surface treatment agent according to the present embodiment preferably contains fluoride ions at a concentration of 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably substantially no fluoride ions. The fluoride ion concentration can be measured, for example, by using a Primus IV (manufactured by Rigaku Corporation) by a drop filter paper method and comparing the fluorescent X-ray intensity of each element with a known calibration curve.

[0027] <Other Additives> The surface treatment agent according to this embodiment may contain various additives as needed. Examples of additives include, but are not limited to, surfactants, antifoaming agents, leveling agents, thickeners, antibacterial and antifungal agents, and colorants. Adding these additives to the surface treatment agent can improve the storage properties and drying properties of the surface treatment agent, improve the workability in producing a surface treatment coating using the surface treatment agent, and improve the appearance (particularly the design) of the produced surface treatment coating. These additives may be added within a range that does not impair the effects of the present invention, and the content of the additives is at most several mass % relative to the mass of the surface treatment agent.

[0028] (Method for Producing Surface Treatment Agent) The method for producing the surface treatment agent according to this embodiment is not particularly limited, and the surface treatment agent can be produced by mixing the silicone polymer (A), a compound containing at least one metal element (B) selected from titanium, zirconium, and aluminum, a solvent, additives, and the like.

[0029] <Surface Treatment Coating> The surface treatment coating according to this embodiment has a wavelength of 950 cm in an infrared absorption spectrum. －１ From 1060cm －１ and a peak in the range (α) of 720 cm －１ From 830cm －１ and a peak (β) in the range of absorbance (α Ａ ) with respect to the absorbance of the peak β (β Ａ) ratio (β Ａ / α Ａ ) is 0.22 to 0.72, preferably in the range of 0.30 to 0.62, more preferably in the range of 0.30 to 0.55, and even more preferably in the range of 0.30 to 0.45.

[0030] Peak α indicates the presence of, for example, Si—O stretching vibration. Peak β indicates the presence of, for example, Si—C stretching vibration. The infrared absorption spectrum of the surface treatment film can be measured by a reflectance method, which is a type of infrared spectroscopy. Examples of the device used include an FT-IR (Spectrum Two) manufactured by Perkin Elmer.

[0031] The surface treatment film contains a silicone polymer (A) and a metal element (B), and the mass of the silicone polymer (A) converted to Si (A Ｍ ) to the converted mass of the metal element (B) (B Ｍ ) ratio (B Ｍ / A Ｍ ) is in the range of 0.001 to 0.880. It is preferably in the range of 0.005 to 0.750, more preferably in the range of 0.010 to 0.487, and even more preferably in the range of 0.010 to 0.265. (β Ａ / α Ａ ) and (B Ｍ / A Ｍ ) in the above range, a coating film excellent in antifouling properties and low-temperature drying properties can be obtained.

[0032] (Material Having a Surface Treatment Coating and Manufacturing Method Thereof) The manufacturing method for a material having a surface treatment coating according to this embodiment includes a contacting step of bringing the surface treatment agent into contact with the surface or on the surface of a material, and a drying step of drying the surface treatment agent that has been brought into contact with the material to form a surface treatment coating. By carrying out these steps, a material having a surface treatment coating can be manufactured.

[0033] Before the contact step, the material may be pretreated to remove oil and dirt adhering to the surface of the material. The pretreatment method is not particularly limited, and examples thereof include washing with hot water, washing with a solvent, and alkaline degreasing.

[0034] As a method for contacting the surface treatment agent in the contacting step, various contacting methods can be used, but it is preferable to appropriately select the most suitable method depending on the shape of the material to be treated, etc. Specific examples include immersion treatment, spray treatment, pouring treatment, brush coating, roll coating, bar coating, etc., but are not limited to these methods. Furthermore, application may be performed using one or more coating devices such as a spin coater, slit coater, die coater, blade coater, dispenser, etc.

[0035] The drying temperature (ambient temperature) in the drying step is not particularly limited, but may be 20°C or higher, 30°C or higher, 50°C or higher, 250°C or lower, 180°C or lower, 100°C or lower, or 80°C or lower. That is, the drying temperature in the drying step may be 20°C to 250°C, 30°C to 180°C, 50°C to 180°C, 50°C to 100°C, or 50°C to 80°C. The drying method is not particularly limited, and examples include natural drying at room temperature and normal pressure, and methods in which the surface treatment agent in contact with the material is heated using hot air, an induction heater, infrared rays, near-infrared rays, or the like to dry the surface treatment agent. The drying time is not particularly limited, and optimal conditions may be set appropriately depending on the type of material used, the surface of the material, or the amount of surface treatment agent adhered to the surface.

[0036] The method for producing a material having a surface treatment film according to this embodiment may further include the steps of contacting the surface or the surface of the material with a primer containing at least one selected from a silane coupling agent having an amino group, a polymer of the silane coupling agent, and a copolymer of the polymer with the silane coupling agent, and / or phosphoric acid, before the step of contacting the surface treatment agent (or after the pretreatment, if pretreatment is performed), and rinsing the primer that has been contacted with the material with water, or drying it without rinsing, to form a primer film. After these steps, a material having a surface treatment film and a primer film can be produced by performing the surface treatment agent contacting step and the drying step.

[0037] The primer contains at least one selected from a silane coupling agent having an amino group, a polymer of the silane coupling agent, and a copolymer of the polymer, and / or a phosphate ion. The silane coupling agent having an amino group is not particularly limited as long as it has one or more amino groups, and examples thereof include 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. The source of the phosphate ion is not particularly limited, and examples thereof include manganese phosphate, iron phosphate, zinc phosphate, zinc calcium phosphate, and phosphoric acid. Of these, manganese phosphate is preferred.

[0038] The solvent contained in the primer treatment agent is not particularly limited, and examples thereof include organic solvents such as alcohol, acetone, acetonitrile, benzene, cyclohexane, methyl acetate, ethyl acetate, and methyl ethyl ketone; mixtures of these organic solvents with water; and the like. The organic solvent is preferably an alcohol having 5 or fewer carbon atoms. The mass proportion of water contained in the primer treatment agent is preferably less than 5 mass%. The primer treatment agent may also contain additives such as a leveling agent for improving wettability to metal materials, a film-forming aid for improving film-forming properties, an organic or inorganic crosslinking agent for making the primer coating stronger, an antifoaming agent for suppressing foaming, a thickener for controlling viscosity, and a rust inhibitor. These additives may be incorporated within a range that does not impair the effects of the present invention.

[0039] Various contact methods can be used as the method for contacting the surface treatment agent, but it is preferable to select an optimum method as appropriate depending on the shape of the metal material to be treated, etc. Specifically, in addition to the method of application using the above-mentioned application device, methods such as immersion treatment, spray treatment, pouring treatment, roll coater method, bar coating method, and electrolytic deposition method can be mentioned, but the method is not limited to these.

[0040] Methods for drying after contact with the primer include, but are not limited to, methods of heating and drying using hot air, an induction heater, infrared rays, near-infrared rays, etc., and methods of drying by distillation under reduced pressure. The temperature during heating and drying is not particularly limited, but is preferably within the range of 20°C to 250°C (ambient temperature), and more preferably within the range of 30°C to 180°C (ambient temperature). The heating time is not particularly limited, and optimal conditions may be set as appropriate depending on the type of material used, the surface of the metal material, or the amount of primer attached to the surface, etc.

[0041] <Material> The material for forming a coating on or on the surface is not particularly limited, but metal materials, resin materials, and fiber materials are preferred. Examples of metal materials include, but are not limited to, iron-based metal materials, zinc-plated metal materials, aluminum-based metal materials, magnesium-based metal materials, nickel-based metal materials, titanium-based metal materials, zirconium-based metal materials, copper-based metal materials, tin-based metal materials, tungsten-based metal materials, chromium-based metal materials, manganese-based metal materials, molybdenum-based metal materials, and cobalt-based metal materials. In the present invention, iron-based metal materials are preferred, and stainless steel is more preferred. The following description will be given using metal materials as an example of the material to which the surface treatment agent is applied. However, the material to which the surface treatment agent of this embodiment is applied is not limited to metal materials and may be any material that requires an antifouling coating.

[0042] Furthermore, the material having the surface treatment coating according to this embodiment may have a base coating between the material and the surface treatment coating. This base coating contains at least one selected from a silane coupling agent having an amino group, a polymer of the silane coupling agent, and a copolymer of the polymer and the silane coupling agent, and / or a phosphate. Note that when the above-mentioned additives are blended into the base treatment agent that forms the base coating, the base coating may further contain the additives.

[0043] The material having the surface treatment coating can be produced by the above-mentioned production method. The thickness of the surface treatment coating is not particularly limited, but is preferably 0.3 μm to 10 μm per side, and more preferably 0.5 μm to 5 μm. The thickness of the base coating is also not particularly limited, but is preferably 0.5 μm to 15 μm per side. Metal materials having the surface treatment coating have excellent antifouling properties and are therefore suitable for industrial products such as medical equipment, kitchen equipment, cooking utensils, and food packaging containers.

[0044] The effects of the present invention will be specifically demonstrated below by way of examples, but the present invention is not limited to these examples.

[0045] Test Materials (Materials) The following commercially available materials were used as test materials: (M1) Stainless steel plate SUS304: thickness 0.8 mm (M2) Cold-rolled steel plate SPCC-SD: thickness 0.8 mm (M3) Aluminum plate A1050P: thickness 0.8 mm (M4) Copper plate C1020P: thickness 0.8 mm

[0046] Pretreatment (alkaline degreasing and cleaning) The surfaces of the various test materials were degreased by immersing them in a 2% aqueous solution of an alkaline degreasing agent (Fine Cleaner E6406 manufactured by Nippon Parkerizing Co., Ltd.) at 60°C for 30 seconds to remove oil and dirt from the surface. Next, they were rinsed with tap water, further poured with pure water, and the surfaces of the test materials were dried at 100°C.

[0047] Preparation of Surface Treatment Agents Surface treatment agents X1 to X30 were prepared by mixing the components shown in Table 1 to obtain the specified mass ratios. Note that the mass percentages of "silicone polymer (A)," "compound containing metal element (B)," and "solvent" in Table 1 indicate the mass ratio of each component to their total mass. Furthermore, the mass percentage of silicone polymer (A) in Table 1 refers to the mass of the silicone polymer, not the mass of the product. The types of each component shown in Table 1 are shown in Tables 2 to 4.

[0048]

[0049]

[0050]

[0051]

[0052] Materials Having a Surface Treatment Coating The surfaces of various test materials that had been pretreated (by alkaline degreasing) were brought into contact with various surface treatment agents shown in Table 5. Thereafter, without rinsing with water, the surface treatment agents that had been brought into contact with the test materials were dried at the drying temperatures shown in Table 5 to prepare test materials (test plates) according to Examples 1 to 38 and Comparative Examples 1 to 5, each having a surface treatment coating with a predetermined thickness.

[0053] The surface treatment (Y) in Table 5 was specifically performed as follows: Various test materials were immersed for 30 seconds in a surface conditioner prepared by diluting a manganese phosphate treatment surface treatment conditioner ("Preparen 55" manufactured by Nihon Parkerizing Co., Ltd.) with tap water to 0.3% by mass. Next, a manganese phosphate-based surface treatment agent ("Palphos M1A" manufactured by Nihon Parkerizing Co., Ltd.) with tap water to 14% by mass, and the total acidity was adjusted to 50 points, the free acidity to 8.6 points, the acid ratio (total acidity / free acidity) to 5.8, and the iron concentration to 1.5 g / L. The surface-conditioned iron-based metal materials were then immersed for 900 seconds in this chemical conversion treatment agent, which had been heated to 97°C. Next, the test piece was washed with tap water, and then pure water was poured over it. The surface of the test piece was dried at 100°C (ambient temperature) for 10 minutes to form a base film (thickness = 3 μm) mainly composed of manganese phosphate and manganese iron phosphate.

[0054]

[0055] Coating Analysis The positions of the peaks and absorbances of the silicone polymer (A) in the dried coating in the infrared absorption spectrum were determined by infrared spectroscopy. Ｍ ) the mass (B) of at least one metal element (B) selected from titanium, zirconium, and aluminum in terms of metal element equivalent. Ｍ ) ratio (B Ｍ / A Ｍ ) was determined by X-ray fluorescence spectroscopy.

[0056] <X-ray fluorescence spectroscopy (B Ｍ / A ＭThe analysis was carried out by fluorescent X-ray spectrometry. The equipment used was a Primus IV manufactured by Rigaku Corporation, and quantitative analysis was carried out by comparing the fluorescent X-ray intensity of each element with a known calibration curve. The quantitative analysis results obtained by subtracting the quantitative analysis results of the test material before surface treatment were used as the converted mass (A Ｍ or B Ｍ ) and B Ｍ / A Ｍ was calculated and the obtained values ​​are shown in Table 6.

[0057] <Fourier transform infrared spectroscopy (β Ａ / α Ａ ) Analysis was performed by the reflectance method, which is a type of infrared spectroscopy. The device used was a Perkin Elmer FT-IR (Spectrum Two), and the sample surface was pressed against the measurement area to perform the measurement. After the measurement, automatic baseline correction was performed using software. In this case, the absorbance of the peak α (α Ａ ) with respect to the absorbance of the peak β (β Ａ ) ratio (β Ａ / α Ａ The values ​​of (a) and (b) were the average values ​​of three measurements. The obtained values ​​are shown in Table 6.

[0058] Evaluation Tests The following evaluation tests were carried out on the test plates of Examples 1 to 38 and Comparative Examples 1 to 5. The results of each evaluation test are shown in Table 6. From a practical standpoint, those without a D in each evaluation item shown in Table 6 were deemed to have passed.

[0059] <Blood Stain Resistance> Five drops (approximately 50 microliters per drop) of porcine blood (Tokyo Shibaura Organ Co., Ltd.) were dropped onto various test plates and forced to dry in a hot air drying oven at 200°C for 3 minutes to adhere to the surface of the test plate. After cooling at room temperature, a 2.5 kg load was placed on a 1.2 cm diameter gauze, and the blood adhering to the coating film was wiped off five times. The gauze was replaced after each drop was wiped off. Each drop was evaluated according to the following criteria: the area of ​​blood remaining after wiping relative to the area of ​​blood remaining after drying and adhering. Table 6 shows the average evaluation values, excluding the best and worst evaluations among the five drops. It can be seen that the test pieces of the examples exhibited excellent stain resistance, even in a high-temperature environment of 200°C. On the other hand, the test pieces of the comparative examples exhibited significantly inferior stain resistance. AA: Residual rate less than 5% A: Residual rate 5% to less than 15% B: Residual rate 15% to less than 30% C: Residual rate 30% to less than 45% D: Residual rate 45% or more or peeling of coating is present

[0060] <Film-forming ability> The hardness of various test pieces was measured in accordance with JIS K 5600-5-4:1999. The measurement results were evaluated according to the following criteria, and the results are shown in Table 6. It can be seen that a film was formed on the test pieces of the examples even at drying temperatures of 20°C or 30°C. On the other hand, in the comparative examples, some of the test pieces did not form a film even at a drying temperature of 80°C. AA: Film hardness of 4H or more A: Film hardness less than 4H to H or more B: Film hardness less than H to 2B or more C: Film hardness less than 2B and film formed D: Film not formed

[0061]

[0062] Although the present invention will be described in detail with reference to specific examples, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. The present invention provides a material having a coating that not only has excellent antifouling properties but also has excellent low-temperature drying properties, making it possible to reduce the energy required to dry the coating, and is an invention that contributes to the SDGs.

Claims

1. A material having a coating on or at a surface thereof, wherein the coating contains a silicone polymer (A) and at least one metal element (B) selected from titanium, zirconium, and aluminum, and satisfies the following (I) and (II): (I) The coating has a peak at 950 cm in an infrared absorption spectrum. －１ ~1080cm －１ and a peak (α) in the range of 720 cm －１ ~830cm －１ and a peak (β) in the range of the peak intensity (α Ａ ) with respect to the peak intensity of the peak β (β Ａ ) ratio (β Ａ / α Ａ (II) The Si-equivalent mass (A) of the silicone polymer (A) in the coating is 0.22 to 0.

72. Ｍ ) the converted mass (B) of the metal element (B) Ｍ ) ratio (B Ｍ / A Ｍ ) is in the range of 0.001 to 0.880 2. The material having a coating according to claim 1, wherein the material is one selected from the group consisting of metal materials, resin materials, and fiber materials.

3. A material having a coating according to claim 1 or 2, which has an undercoating between the material and the coating, which contains at least one selected from the group consisting of a silane coupling agent having an amino group, a polymer of the silane coupling agent, and a copolymer of the polymer and the silane coupling agent, and / or a phosphate.

4. A material having a coating according to claim 1 or 2, wherein the coating has a thickness of 0.3 μm or more and 10 μm or less.

Images