Material having surface-treated coating film

Abstract

To provide a material having a new surface-treated coating film with excellent antifouling and low-temperature drying properties.SOLUTION: Disclosed is a material having a coating film at or on the surface thereof, where 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.SELECTED DRAWING: None

Description

[Technical Field]

[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. [Background technology]

[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 have been developed for providing surface treatment coatings with various performance characteristics on or over the surface of the material. For example, Patent Document 1 discloses a technique relating to a metal surface treatment composition and a treatment method therefor, which comprises a predetermined phosphate 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. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-213958 Summary of the Invention [Problem to be solved by the invention]

[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. [Means for solving the problem]

[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 is [1] A material having a coating on or at its surface, The coating comprises a silicone polymer (A) and and at least one metal element (B) selected from titanium, zirconium, and aluminum, and satisfying the following (I) and (II): (I) The coating has a wavelength of 950 cm in the infrared absorption spectrum. -1 ~1080cm -1 and a peak 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 ) is between 0.22 and 0.72 (II) The Si-equivalent mass (A) of the silicone polymer (A) in the coating M ) to the converted mass (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 [1], wherein the material is one selected from a metal material, a resin material, and a fiber material; [3] Between the material and the coating, 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 is added. a material having a coating according to [1] or [2], which has a base coating containing one of the above and / or a phosphate; [4] The material having a coating according to any one of [1] to [3], wherein the coating has a thickness of 0.3 μm or more and 10 μm or less; And so on. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a material having a surface treatment coating film that is excellent in antifouling properties and low-temperature drying properties. DETAILED DESCRIPTION OF THE INVENTION

[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) One embodiment of the present invention also includes 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. 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 film that is excellent in antifouling properties (particularly in inhibiting contamination caused by animals and plants in high-temperature environments) and low-temperature drying properties can be formed on the surface of a material. Therefore, it is useful as an agent for forming an antifouling film. In this embodiment, the high-temperature environment for antifouling properties refers to an atmosphere of 100°C to 200°C, and the low temperature for low-temperature drying refers to 20°C to 80°C. Furthermore, surface treatment films that are excellent in antifouling properties and low-temperature drying properties and are formed by the surface treatment agent are useful for materials used in machine components that constitute industrial products such as medical equipment, kitchen equipment, cooking utensils, and food packaging containers.

[0010] <Silicone polymer (A)> The silicone polymer (A) is not particularly limited as long as it is capable of forming a coating having a specific infrared absorption peak, as described below, and has an organopolysiloxane structure containing multiple siloxane bonds and an organic group bonded to silicon (Si). Preferably, however, the silicone polymer (A) has an organopolysiloxane structure containing at least one organic group bonded to Si per molecule. The position at which the organic group is bonded is not particularly limited, and the organic group may be bonded to the main chain, side chain, or terminal. The silicone polymer (A) may be a homopolymer having the organopolysiloxane structure, a mixture of a homopolymer having the organopolysiloxane structure and a homopolymer having a polysiloxane structure, or a copolymer (block copolymer or graft polymer) having the organopolysiloxane structure and a polysiloxane structure. The silicone polymer (A) may be either an addition type or a condensation type. Furthermore, the silicone polymer (A) may be any of a heat-curable type, a room temperature curable type (RVT), and a UV-curable 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 chloromethyl, 3-chloropropyl, 1-chloro-2-methylpropyl, and 3,3,3-trifluoropropyl. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 3-pentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Examples of cycloalkyl groups include cyclopentyl and cyclohexyl. Examples of linear or branched alkenyl groups include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, and hexenyl. 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 β A / α A This indicates that the silicone polymer in the coating has fewer Si-C bonds relative to Si-O bonds, and fewer organic groups in the side chains, which gives the coating good antifouling properties and low-temperature drying properties. The organic group in the side chain that imparts functionality to the silicone polymer preferably has an alkyl group from the viewpoint of antifouling properties, and preferably has 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] <Compounds containing metal element (B)> The surface treatment agent according to this embodiment contains a compound (hereinafter referred to as compound (B)) containing at least one metal element (B) selected from titanium, zirconium, and aluminum.

[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 the inorganic titanium compound include titanyl sulfate, titanyl nitrate, titanium nitrate, titanyl chloride, titanium chloride, titanium dioxide ... Examples of the organic titanium compound 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, it is preferable to use an organic titanium compound. These compounds may be used alone or in combination of two or more 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, organic aluminum compounds are preferably used. 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 silicon equivalent mass of the silicone polymer (A) (A 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 the present 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, and 3-hexanol. Examples of suitable solvents include ethanol, 2-methyl-1-pentanol, 3-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 suitable ester solvents include methyl acetate, ethyl acetate, butyl acetate, and 2-ethoxyethyl acetate. Examples of suitable nitrile solvents include acetonitrile. Examples of suitable ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone, but are not limited to these. One type of organic solvent may be used, or two or more types may be used in combination. The alcoholic 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 this 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 surface treatment agent.

[0026] The surface treatment agent according to this 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 the present 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 stability and drying properties of the surface treatment agent, improve the workability in producing a surface treatment film using the surface treatment agent, and improve the appearance (particularly the design) of the produced surface treatment film. 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 percent by mass relative to the mass of the surface treatment agent.

[0028] (Method of manufacturing surface treatment agent) The method for producing the surface treatment agent according to this embodiment is not particularly limited, and the 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 film according to this embodiment has a wavelength of 950 cm in the infrared absorption spectrum. -1 From 1060cm -1 The peak in the range (α) and 720 cm-1 From 830cm -1 and a peak (β) in the range of absorbance (α A ) 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. The range of 0.30 to 0.55 is more preferable, and the range of 0.30 to 0.45 is even more preferable.

[0030] Peak α indicates the presence of, for example, Si—O stretching vibration, and 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, using an apparatus such as Perkin Elmer's FT-IR (Spectrum Two).

[0031] The surface treatment film contains silicone polymer (A) and metal element (B), and the Si-equivalent mass of silicone polymer (A) (A M ) to the equivalent mass of metal element (B) (B M ) ratio (B M / A M ) is in the range of 0.001 to 0.880, 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, the antifouling property and low-temperature drying property are improved. It is possible to obtain an excellent coating.

[0032] (Materials with surface treatment coatings and their manufacturing methods) The method for producing a material having a surface treatment film according to this embodiment includes a contacting step of bringing the surface treatment agent into contact with the surface of the material or on the surface thereof, and a drying step of drying the surface treatment agent that has been brought into contact with the material to form a surface treatment film. By performing these steps, a material having a surface treatment film can be produced.

[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 atmospheric pressure, and methods in which the surface treatment agent in contact with the material is heated and dried using hot air, an induction heater, infrared rays, near-infrared rays, or the like. 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 attached 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 of the material or the surface thereof 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, prior to the step of contacting the surface treatment agent (or after the pretreatment, if any), 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. Among these, manganese phosphate is preferred.

[0038] The solvent contained in the primer 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 is preferably less than 5 mass%. The primer 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] Drying methods 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 the optimum conditions may be set appropriately depending on the type of material used, the surface of the metal material, or the amount of primer attached to the surface.

[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 film according to this embodiment may have a base film between the material and the surface treatment film. This base film 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. The base treatment agent that forms the base film may contain the above-mentioned additives. If incorporated, the base coating may further contain the additive.

[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. The metal material having the above surface treatment coating has excellent antifouling properties and is therefore suitable for industrial products such as medical equipment, kitchen equipment, cooking utensils, and food packaging containers. [Example]

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

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

[0047] Preparation of surface treatment agent Surface treatment agents X1 to X30 were prepared by mixing the components shown in Table 1 to obtain the prescribed mass ratios. In Table 1, the mass percentages of "silicone polymer (A)," "compound containing metal element (B)," and "solvent" indicate the mass ratio of each component to their total mass. In addition, the mass percentage of silicone polymer (A) in Table 1 indicates 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] [Table 1]

[0049] [Table 2]

[0050] [Table 3]

[0051] [Table 4]

[0052] Materials with surface treatment coatings As shown in Table 5, various surface treatment agents were brought into contact with the surfaces of various pretreated test materials. Thereafter, without rinsing with water, the surface treatment agents brought into contact with the test materials were dried at the drying temperatures shown in Table 5 to obtain test materials (including those according to Examples 1 to 38 and Comparative Examples 1 to 5) having surface treatment films with predetermined thicknesses. Test plates were prepared.

[0053] The surface treatment (Y) in Table 5 was specifically carried out 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.) was diluted 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 material was immersed for 900 seconds in this chemical conversion treatment agent heated to 97 °C. Next, the material was rinsed with tap water, further poured with pure water, and the surface of the test material was dried at 100 °C (ambient temperature) for 10 minutes to form a base coating (thickness = 3 μm) mainly composed of manganese phosphate and manganese iron phosphate.

[0054] [Table 5]

[0055] Film analysis The positions of the peaks and absorbances of the silicone polymer (A) in the dried coating in the infrared absorption spectrum were analyzed by infrared spectroscopy. M) relative to the mass (B M ) ratio (B M / A M ) was determined by X-ray fluorescence spectroscopy.

[0056] X-ray fluorescence spectroscopy (B M / A M )> The analysis was carried out by X-ray fluorescence spectrometry. The Rigaku Primus IV was used, and quantitative analysis was carried out by comparing the X-ray fluorescence intensity of each element with a known calibration curve. The quantitative analysis results obtained were subtracted from the quantitative analysis results of the test material before surface treatment to obtain 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 )> The analysis was carried out by the reflectance method, which is a type of infrared spectroscopy. The instrument used was a Perkin Elmer FT-IR (Spectrum Two), and the sample surface was pressed against the measurement area to carry out the measurement. After the measurement, automatic baseline correction was carried out using software. In this case, the absorbance of the peak α (α A ) to the absorbance of the peak β (β A ) ratio (β A / α A The values ​​for ) were the average of three measurements. The obtained values ​​are shown in Table 6.

[0058] Evaluation Test 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 pass.

[0059] <Blood stain resistance> Five drops of pig blood (Tokyo Shibaura Organ Co., Ltd.) were placed on each test plate (1 drop: approximately 50 microliters). (Iron) was dropped onto the test plate and forcedly dried for 3 minutes in a hot air drying oven at 200°C to adhere to the surface. 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. The area of ​​blood remaining after wiping relative to the area of ​​blood after drying and adhering for each drop was evaluated according to the following criteria. 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 example exhibited excellent antifouling properties, even in a high-temperature environment of 200°C. On the other hand, the test pieces of the comparative example exhibited significantly inferior antifouling properties. AA: Less than 5% remaining 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: Remaining rate is 45% or more or the coating is peeling off

[0060] <Film forming properties> The hardness of each test piece 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 coating was formed on the test pieces of the examples even at drying temperatures of 20°C or 30°C. On the other hand, in some of the comparative examples, no coating was formed even at a drying temperature of 80°C. AA: Coating hardness 4H or higher A: Coating hardness less than 4H to more than H B: Coating hardness less than H ~ 2B or more C: Coating hardness less than 2B and coating formed D: No film formation

[0061] [Table 6]

[0062] Although the present invention will be described in detail with reference to specific embodiments, 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. This invention not only provides a material with excellent antifouling properties, but also a coating that dries at low temperatures, making it possible to reduce the energy required to dry the coating, and thus contributing to the SDG It is an invention that contributes to s.

Claims

1. A material having a coating on or at a surface thereof, The coating comprises a silicone polymer (A) and and at least one metal element (B) selected from titanium, zirconium, and aluminum, and satisfying the following (I) and (II): (I) The coating has an infrared absorption spectrum of 950 cm －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 ) is 0.22 to 0.72 (II) The mass (A) of the silicone polymer (A) in the coating in terms of Si 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. 2. The material having a coating according to claim 1, wherein the material is one selected from the group consisting of a metal material, a resin material, and a fiber material.

3. Between the material and the coating 3. The material having a coating according to claim 1 or 2, which has an undercoating film 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 polymer and the silane coupling agent, and / or a phosphate.

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

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