Surface treatment agent, treated material having a coating, and method for manufacturing the same.

Abstract

To provide a novel surface treatment agent containing a polysiloxane compound.SOLUTION: There is provided a surface treatment agent which contains a polysiloxane compound (A) having a urea group and an X group [the X group is one or more groups selected from -COOR, -SO3R and -NR2, in which R is a hydrogen atom or an alkyl group which may have an alkoxy group or a hydroxyl group] and the ratio (urea group / X group) of the number of urea groups and X groups in one molecule is in the range of 0.01 to 0.45, a metal compound (B) containing a metal selected from the group consisting of Zr, Ti, Hf and Bi and / or a water-soluble or water-dispersible resin (C) selected from the group consisting of a polyvinyl resin, an acrylic resin, a polyvinylidene chloride resin, an epoxy resin, a urethane resin, a polyester resin, a polyamide resin, a polyimide resin, a phenol resin, a silicone resin and a fluorine resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a surface treatment agent for forming a film on a material to be treated. It also relates to a material to be treated having a film.

Background Art

[0002] In recent years, various polysiloxane compounds have been used in various fields, and it has been disclosed that they can also be used as components for forming a film on the surface or on the surface of a metal material or the like. For example, in Patent Document 1, an aqueous metal surface treatment agent is disclosed which is formulated with a specific organosilicon compound (P) and at least one organic polymer (Q) selected from urethane resins, epoxy resins, acrylic resins, phenolic resins, polyester resins and polyolefin resins. It is disclosed that the metal material treated with this surface treatment agent has excellent corrosion resistance, adhesion, as well as both acid resistance and alkali resistance. Further, in Patent Document 2, a polysiloxane compound (A) having a urea group and an X group [the X group is one or more groups selected from -COOR, -SO3R and -NR2, and R is a hydrogen atom, or an alkyl group which may have an alkoxy group or a hydroxyl group] is disclosed, and it is disclosed that a film excellent in acid resistance, solvent resistance and corrosion resistance after painting can be formed by using a composition containing the polysiloxane compound (A).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] As described above, surface treatment agents containing polysiloxane compounds have been developed, but there is a demand for even higher functionality and performance. The surface-treated metal material disclosed in Patent Document 1 still has room for improvement in solvent resistance, and the film formed by the composition in Patent Document 2 still has room for improvement in alkali resistance. The present invention provides a new surface treatment agent containing a polysiloxane compound that achieves both solvent resistance and alkali resistance. [Means for solving the problem]

[0005] The present invention [1] A surface treatment agent comprising: a polysiloxane compound (A) having a urea group and an X group [where the X group is one or more groups selected from -COOR, -SO3R, and -NR2, and R is a hydrogen atom or an alkyl group which may have an alkoxy group or a hydroxyl group], wherein the ratio of the number of urea groups to X groups in one molecule (urea group / X group) is in the range of 0.01 to 0.45; a metal compound (B) containing a metal selected from the group consisting of Zr, Ti, Hf, and Bi; and / or a water-soluble or water-dispersible resin (C) selected from the group consisting of polyvinyl resin, acrylic resin, polyvinylidene chloride resin, epoxy resin, urethane resin, polyester resin, polyamide resin, polyimide resin, phenol resin, silicone resin, and fluororesin. [2] The surface treatment agent according to [1], wherein the water-soluble or water-dispersible resin (C) is a resin selected from the group consisting of urethane resin, acrylic resin, and phenolic resin. [3] The surface treatment agent according to [1] or [2], wherein the metal compound (B) is a metal compound containing Zr. A method for producing a workpiece having a coating, comprising the steps of: bringing a surface treatment agent described in any of [4][1] to [3] into contact with the surface of the workpiece or onto a surface; and drying the surface treatment agent that has been brought into contact with the surface of the workpiece or onto a surface. A coated material manufactured by the method described in [5][4]. And so on. [Effects of the Invention]

[0006] According to the present invention, a novel surface treatment agent containing a polysiloxane compound that achieves both solvent resistance and alkali resistance can be provided. Furthermore, since the novel surface treatment agent forms a film with excellent rust prevention and post-coating corrosion resistance, the lifespan of the treated object can be extended, and resources can be used efficiently. [Modes for carrying out the invention]

[0007] The surface treatment agent according to the present invention will be described below. <Surface treatment agent> The surface treatment agent according to this embodiment contains a polysiloxane compound (A), a metal compound (B), and / or a water-soluble or water-dispersible resin (C). The surface treatment agent may also contain other components.

[0008] <Polysiloxane compound (A)> The polysiloxane compound (A) has a urea group (urea bond) and an X group [the X group is one or more groups selected from -COOR, -SO3R, and -NR2, and R is a hydrogen atom or an alkyl group which may have an alkoxy group or a hydroxyl group], and the ratio of the number of urea groups to the number of X groups in one molecule (urea group / X group) is in the range of 0.01 to 0.45.

[0009] Furthermore, the polysiloxane compound has one or more Si groups to which a hydroxyl group or alkoxy group is attached. The polysiloxane compound may also have an epoxy group, or a structure (-CH(OH)CH2OH) formed by ring-opening of the epoxy group through hydrolysis.

[0010] Here, the X group is, for example, a carboxyl group, an alkoxycarbonyl group, a sulfone group, an alkylsulfone group, an amino group, an N-alkylamino group, an N,N-dialkylamino group, an N-(alkoxyalkyl)amino group, an N-(hydroxyalkyl)amino group, an N,N-di(alkoxyalkyl)amino group, an N,N-di(hydroxyalkyl)amino group, etc., and the polysiloxane compound may have one of these groups, or two or more of these groups.

[0011] Examples of combinations of two or more groups include: a carboxyl group and an amino group; an alkoxycarbonyl group and an amino group; a sulfone group and an amino group; an alkylsulfone group and an amino group; a carboxyl group and an N-alkylamino group; an alkoxycarbonyl group and an N-alkylamino group; a sulfone group and an N-alkylamino group; an alkylsulfone group and an N-alkylamino group; a carboxyl group and an N,N-dialkylamino group; an alkoxycarbonyl group and an N,N-dialkylamino group; a sulfone group and an N,N-dialkylamino group; an alkylsulfone group and an N,N-dialkylamino group; a carboxyl group and an N-(alkoxyalkyl)amino group; an alkoxycarbonyl group and an N-(alkoxyalkyl)amino group; a sulfone group and an N-(alkoxyalkyl)amino group; an alkylsulfone group and an N-(alkoxyalkyl)amino group; a carboxyl group and an N-(alkoxyalkyl) Examples of combinations include, but are not limited to, those with a hydroxyalkyl)amino group, an alkoxycarbonyl group and an N-(hydroxyalkyl)amino group, a sulfone group and an N-(hydroxyalkyl)amino group, an alkylsulfone group and an N-(hydroxyalkyl)amino group, a carboxyl group and an N,N-di(alkoxyalkyl)amino group, an alkoxycarbonyl group and an N,N-di(alkoxyalkyl)amino group, a sulfone group and an N,N-di(alkoxyalkyl)amino group, an alkylsulfone group and an N,N-di(alkoxyalkyl)amino group, a carboxyl group and an N,N-di(hydroxyalkyl)amino group, an alkoxycarbonyl group and an N,N-di(hydroxyalkyl)amino group, a sulfone group and an N,N-di(hydroxyalkyl)amino group, and an alkylsulfone group and an N,N-di(hydroxyalkyl)amino group.

[0012] In this specification, the alkyl group, as well as the alkyl and alkylene portions of the alkoxy group, alkoxycarbonyl group, alkylsulfone group, N-alkylamino group, N,N-dialkylamino group, N-(alkoxyalkyl)amino group, N-(hydroxyalkyl)amino group, N,N-di(alkoxyalkyl)amino group, and N,N-di(hydroxyalkyl)amino group, may be linear or branched. Examples of the alkyl group and alkyl portion include alkyl groups having 1 to 20 carbon atoms, but alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, are preferred. Furthermore, examples of the alkylene portion include alkylene chains having 1 to 20 carbon atoms, but it is preferable that the alkylene chains having 1 to 12 carbon atoms are such as methylene chains, ethylene chains, propylene chains, butylene chains, pentylene chains, hexylene chains, peptylene chains, octylene chains, nonylene chains, decylene chains, undecylene chains, and dodecylene chains. Note that for the N,N-dialkylamino group, N,N-di(alkoxyalkyl)amino group, and N,N-di(hydroxyalkyl)amino group, the two alkyl, alkoxyalkyl, and hydroxyalkyl portions may be the same or different.

[0013] The weight-average molecular weight of the polysiloxane compound is not particularly limited, but is, for example, in the range of 1,000 to 1,000,000, preferably in the range of 5,000 to 500,000, and more preferably in the range of 10,000 to 100,000. The above weight-average molecular weight is a value obtained by measuring, for example, gel permeation chromatography (GPC) and expressing it as the molecular weight on a polystyrene basis.

[0014] <Method for producing polysiloxane compound (A)> The polysiloxane compound (A) can be produced, for example, by sequentially blending an isocyanate compound (a1), an aminosilane compound (a2), and an aqueous medium in a predetermined ratio and reacting them at a predetermined temperature (preferably 40 to 80°C). In the production of the polysiloxane compound, an amine compound (a3) may be further blended in addition to the isocyanate compound (a1) and the aminosilane compound (a2). Further, if necessary, an alkyl halide or an alkylene oxide may be reacted with the amino group of the polysiloxane compound obtained by production to produce a polysiloxane compound having an N-alkylamino group or an N,N-dialkylamino group. The examples of the alkyl portion of the alkyl halide are the same as above. Examples of the halogen of the alkyl halide include a fluorine atom, a chlorine atom, a bromine atom, etc. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., but are not limited thereto. The ratio (urea group / X group) of the number of urea groups and X groups in the polysiloxane compound is 1 -NH- derived from the urea group by 1H NMR analysis, or 13 13C NM the peak intensity (I1) of -C=O- derived from the urea group by R analysis, and 1 the ratio (I1 / I2) with the peak intensity [when there are two or more X groups, the sum of the peak intensities of various X groups] (I2) of the X group by 1H NMR analysis can be determined by calculating.

[0015] In order to accelerate the above reaction, for example, a polycondensation catalyst such as dibutyltin diacetate, dibutyltin dilaurate, lead naphthenate; a known hydrolysis catalyst such as an acidic catalyst; an amine-based catalyst which is a polycondensation catalyst and a hydrolysis catalyst may be used.

[0016] Isocyanate compound (a1) The isocyanate compound (a1) means a compound having one or more isocyanate groups. The isocyanate compound (a1) may have two or more isocyanate groups. Further, the isocyanate compound (a1) may further have a Si group to which a hydroxyl group or an alkoxy group is bonded. Examples of the isocyanate compound (a1) include, but are not limited to, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. These isocyanate compounds may be used alone or in combination of two or more.

[0017] Aminosilane compound (a2) The aminosilane compound (a2) means a compound having one or more amino groups and a Si group to which a hydroxyl group or an alkoxy group is bonded. Examples of the aminosilane compound (a2) include, but are not limited to, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-[2-(2-aminoethylaminoethylamino)propyl]trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, etc. These aminosilane compounds may be used alone or in combination of two or more.

[0018] ]> Amine compound (a3) The amine compound (a3) ​​is a compound having one or more amino groups and is not particularly limited as long as it does not fall under the category of aminosilane compound (a2), and may further have a COOR group and / or an SO3R group. Examples of amine compounds (a3) ​​include alkylamines such as methylamine and ethylamine; alkylenediamines such as ethylenediamine and hexamethylenediamine; compounds having an amino group and a sulfone group, such as aminomethanesulfonic acid and 4-aminobenzenesulfonic acid; methyl 2-aminobenzene-1-sulfonic acid, methyl Compounds having an amino group and an SO3R group (where R is an alkyl group), such as 4-aminobenzene-1-sulfonic acid; compounds having an amino group and a carboxyl group, such as amino acids like glycine and alanine; esterified compounds of compounds having an amino group and a carboxyl group (compounds having an amino group and an alkoxycarbonyl group); compounds having an amino group and an N-alkylamino group, such as 1-methylguanidine, N-butylethylenediamine, N-methyl-1,3-propanediamine, and N-ethyl-1,3-propanediamine; 4-dimethylamine Compounds having an amino group and an N,N-dialkylamino group, such as anoaniline, 4-amino-N,N-diethylaniline, 1,1-diethylguanidine, 2-(dibutylamine)ethylamine, N,N-dimethyl-1,3-propanediamine, and N,N-diethyl-1,3-propanediamine; compounds having an amino group and an N-(alkoxyalkyl)amino group, such as 4-[(2-methoxyethyl)amino]-aniline; p-(p-hydroxymethylaminobenzyl)aniline, 3-nitro-4-(2-hydroxyethylamino)aniline Examples include compounds having an amino group and an N-(hydroxyalkyl)amino group, such as phosphorus, N-(2-hydroxyethyl)-1,3-propanediamine, and N-(2-methoxyethyl)-1,3-propanediamine; compounds having an amino group and an N,N-di(alkoxyalkyl)amino group, such as 4-[di(methoxymethyl)amino]-6-phenyl-1,3,5-triazine-2-amine; compounds having an amino group and an N,N-di(hydroxyalkyl)amino group, such as N,N-bis(2-hydroxyethyl)-1,4-phenylenediamine, N,N-bis(2-hydroxyethyl)-1,3-propanediamine, and N,N-bis(2-methoxyethyl)-1,3-propanediamine; and others. These compounds may be used individually or in combination of two or more.

[0019] A urea group is obtained by the reaction of the isocyanate group in the above isocyanate compound (a1) with the amino group in the aminosilane compound (a2) or amine compound (a3). The ratio of the number of urea groups to the number of X groups in one molecule (urea groups / X groups) is not particularly limited as long as it is within the range of 0.01 to 0.45, but is preferably within the range of 0.05 to 0.4, and more preferably within the range of 0.1 to 0.35. By setting the ratio of the number of urea groups to the number of X groups in one molecule within the above range, the film formed by the surface treatment agent can be made to have excellent solvent resistance. Furthermore, polysiloxane compounds containing urea groups and X groups in a ratio (urea group / X group) within the range of 0.01 to 0.45 can be produced by appropriately adjusting the amounts of isocyanate compounds (a1), aminosilane compounds (a2), amine compounds (a3), etc.

[0020] In the production of the above polysiloxane compound, a silicon-containing compound (a4) may be further added to the isocyanate compound (a1) and aminosilane compound (a2), or to the isocyanate compound (a1), aminosilane compound (a2) and amine compound (a3). The silicon-containing compound (a4) does not correspond to the isocyanate compound (a1) and aminosilane compound (a2), but rather refers to a compound containing Si, and preferably, it is a compound in which a hydroxyl group, an alkoxy group, or a halo group is bonded to Si.Examples of silicon-containing compounds (a4) include vinyltrichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxyoctyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyl Examples include, but are not limited to, dimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, dimethoxydimethylsilane, phenylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methyl-3-(trimethoxysilyl)propylamine, N-ethyl-3-(trimethoxysilyl)propylamine, N,N-dimethyl-3-(trimethoxysilyl)propylamine, N,N-diethyl-3-(trimethoxysilyl)propylamine, N-hydroxyethyl-3-(trimethoxysilyl)propylamine, N,N-dihydroxyethyl-3-(trimethoxysilyl)propylamine, N,N-methoxyethyl-3-(trimethoxysilyl)propylamine, and N,N-dimethoxyethyl-3-(trimethoxysilyl)propylamine. One of these silicon-containing compounds may be used, or two or more may be used in combination.

[0021] The aqueous medium is particularly limited to water or a mixture of water and a water-miscible organic solvent. It is not that. Furthermore, the mass percentage of water in the mixture should be 50% by mass or more, and is more preferable in the order of 80% by mass or more, 90% by mass or more, 95% by mass or more, and 99% by mass or more.

[0022] The water-miscible organic solvent is not particularly limited as long as it is miscible with water, and examples include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone. One of these water-miscible organic solvents may be mixed with water, or two or more may be mixed with water.

[0023] The content of polysiloxane compound (A) in the surface treatment agent is not particularly limited, but the solid content mass concentration (meaning the total solid content mass concentration when two or more compounds are blended) is usually 50 mg / L or more, preferably 5,000 mg / L or more, and usually 100,000 mg / L or less, preferably 50,000 mg / L or less. By forming a film using a surface treatment agent in which the concentration of polysiloxane compound (A) is within the above range, and then forming a coating film, a film with better corrosion resistance can be formed.

[0024] <Metal compound (B)> Metal compound (B) is a compound containing a metal element selected from the group consisting of Zr, Ti, Hf, and Bi. In the surface treatment agent, metal compound (B) dissolves, and the metal element exists as an ion. The ion may be a metal ion, a complex ion, or an oxide ion.

[0025] Specific examples of metal compound (B) include hexafluorozirconium acid, zirconium nitrate, zirconyl nitrate, zirconium carbonate, zirconium acetate, zirconium hydroxide, zirconium oxide, hexafluorotitanium acid, titanium nitrate, titanyl nitrate, titanium hydroxide, titanium oxide, hexafluorohafnium acid, hafnium nitrate, hafnium oxide, hexafluorobismuth acid, bismuth nitrate, bismuth carbonate, bismuth hydroxide, bismuth oxide, etc. If these can take the form of a salt, then the salt may be used. These metal compounds (B) may be contained in the surface treatment agent by one or by two or more.

[0026] The content of metal compound (B) in the surface treatment agent is not particularly limited, but the metal equivalent mass concentration (meaning the total metal equivalent mass concentration when two or more compounds are blended) is usually 10 mg / L or more, preferably 1,000 mg / L or more, and usually 20,000 mg / L or less, preferably 10,000 mg / L or less. By forming a film using a surface treatment agent in which the concentration of metal compound (B) is within the above range, and then forming a coating film, a film with better corrosion resistance can be formed.

[0027] <Water-soluble or water-dispersible resin (C)> Resin (C) is a water-soluble or water-dispersible resin, selected from the group consisting of polyvinyl resin, acrylic resin, polyvinylidene chloride resin, epoxy resin, urethane resin, polyester resin, polyamide resin, polyimide resin, phenolic resin, silicone resin, and fluororesin. It may be a modified product obtained by modifying the side chains of monopolymers of these resins with other compounds, or a copolymer obtained by combining two or more of these resins or modified products. The weight-average molecular weight of resin (C) is not particularly limited as long as it is 2,000 or more, but it is preferably 4,000 or more, and more preferably 10,000 or more. The upper limit is preferably 1,000,000 or less. These resins (C) may be contained in the surface treatment agent by one type or by two or more types.

[0028] The content of resin (C) in the surface treatment agent is not particularly limited, but the solid content equivalent mass concentration (meaning the total solid content equivalent mass concentration when two or more resins are blended) is usually 10 mg / L or more, preferably 1,000 mg / L or more, and usually 20,000 mg / L or less, preferably 10,000 mg / L or less. By forming a film using a surface treatment agent with a resin (C) concentration within the above range, and then forming a coating film, a film with better corrosion resistance can be formed.

[0029] <Other ingredients> The surface treatment agent of this embodiment typically contains water and / or an organic solvent, and may consist only of the above components (A) to (C) and water and / or an organic solvent, or it may contain other components. Examples of other components include preservatives, surfactants, thickeners, pigments, dyes, crosslinking agents, antibacterial agents, antifungal agents, etc.

[0030] Examples of organic solvents include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone. These organic solvents may be mixed individually with water, or two or more may be mixed with water.

[0031] As for preservatives, known ones can be used. The surfactant is not particularly limited as long as it can improve the wettability of the composition containing the polysiloxane compound, and cationic, anionic, amphoteric, nonionic, and other types of surfactants can be used. Specifically, examples include cationic surfactants such as alkylamine salts and alkyltrimethylammonium halides; anionic surfactants such as alkyl sulfonic acid esters, polyoxyethylene alkylphenyl ether sulfates, sodium dodecyldiphenyl ether disulfonate, and sodium dodecyl sulfate; amphoteric surfactants such as alkylaminopropionates and alkyldimethyl betaine; and nonionic surfactants such as polyoxyethylene alkylphenyl ethers, polyoxyalkylene fatty acid esters, fatty acid glycerol esters, sorbitan fatty acid esters, polyoxyethylene glycerol fatty acids, and polyoxyethylene propylene glycol fatty acid esters. These may be used individually or in combination of two or more types. Regarding thickeners, pigments, dyes, crosslinking agents, antibacterial agents, and antifungal agents, known ones can also be used.

[0032] <Method for manufacturing surface treatment agents> The surface treatment agent according to this embodiment can be manufactured by mixing the above components (A) to (C) with water and / or an organic solvent. If other components are included, the agent can also be manufactured by mixing the other components together.

[0033] <Method for manufacturing a coated material> The surface treatment agent of this embodiment can form a film with durability, corrosion resistance, and paint adhesion, as well as an excellent appearance, by contacting the surface of the material to be treated or onto the surface by methods such as coating or immersion, and then drying it. The contact time, drying temperature, and drying time are not particularly limited and can be carried out under conditions that are normally applied. The material to be treated is typically a metal material, but is not limited thereto and includes plastics, rubber, ceramics, glass, fibers, magnetic materials, etc. Specifically, it can form a film on electronic components and micro-device components that make up industrial products such as automobiles, home appliances, office automation equipment, medical devices, and medical instruments, as well as materials used in cooking utensils, ships, building materials, etc. Before the surface treatment agent comes into contact with the material to be treated, the material to be treated must be degreased or pickled. Alternatively, rinsing may be performed after each process, or drying may be performed after rinsing. Furthermore, chemical conversion treatment may be performed after degreasing or pickling, or chemical conversion treatment may be performed without degreasing or pickling. The type of chemical conversion treatment is not particularly limited, and one or more types of treatments such as chromate conversion treatment, zinc phosphate conversion treatment, bismuth substitution plating, iron phosphate conversion treatment, zirconium conversion treatment, titanium conversion treatment, and hafnium conversion treatment may be performed.

[0034] The surface of the film formed by the surface treatment agent of this embodiment may be further coated. The coating method is not particularly limited, and known methods such as rolling, spray coating, hot spray coating, airless spray coating, electrostatic coating (e.g., electrostatic powder coating), roller coating, curtain flow coating, brush coating, bar coating, fluid immersion method, and electrodeposition coating can be applied. After coating, the coating on the surface of the coated substrate may be dried. Furthermore, the surface of the material to be treated having a film formed by the polysiloxane compound of this embodiment or a composition containing the same may or may not be washed with water before coating. Furthermore, the surface of the substrate, after washing with water or before washing, may or may not be dried before coating.

[0035] Examples of known paints include oil-based paints, cellulose derivative paints, phenolic resin paints, alkyd resin paints, amino alkyd resin paints, urea resin paints, unsaturated resin paints, vinyl resin paints, acrylic resin paints, epoxy resin paints, polyurethane resin paints, silicone resin paints, fluororesin paints, rust-inhibiting paints, antifouling paints, powder coatings, water-based paints, solvent-based paints, and electrodeposition paints. Painting may be performed using the same or different types of paints in one application, or in two or more applications. Drying is the process of drying and curing the applied paint. Examples of drying methods include natural drying, reduced-pressure drying, convection-type heat drying (e.g., natural convection-type heat drying, forced convection-type heat drying), radiant drying (e.g., near-infrared drying, far-infrared drying), ultraviolet curing drying, electron beam curing drying, vapor curing, and baking drying. These drying methods may be performed individually or in combination of two or more.

[0036] Known coating methods such as spray coating, electrostatic powder coating, and fluid immersion can be applied using powder coatings. Examples of powder coatings include those containing a polyester resin and a curing agent such as a blocked isocyanate curing agent, a β-hydroxyalkylamide curing agent (see, for example, Japanese Patent Application Publication No. 2011-88083), or triglycidyl isocyanurate. Baking is performed for a certain period of time within a predetermined temperature range. For example, it is performed at 150-250°C for 20 minutes.

[0037] For coating methods using solvent-based paints, known methods such as spray painting, electrostatic painting, and bar coating can be applied. Examples of solvent-based paints include those containing resins such as melamine resin, acrylic resin, urethane resin, and polyester resin, and organic solvents such as thinner. Baking is performed for a certain period of time within a predetermined temperature range. For example, it is performed at 130°C for 20 minutes.

[0038] For electrodeposition coating using electrodeposition paint, known methods can be used. Examples of electrodeposition paints include those containing resins such as epoxy resin and acrylic resin. Baking is performed for a certain period of time within a predetermined temperature range. For example, it is performed at 130-250°C for 20 minutes.

[0039] The coating obtained by painting may be a single layer or multiple layers. In the case of multiple layers, the paints used to form the various coatings, the painting method using the paints, and the drying method of the painted substrate may be the same or different. [Examples]

[0040] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The units of the blending amounts of each raw material listed in the table are parts by mass.

[0041] <Preparation of polysiloxane compound (A)> Based on the compositions shown in Table 1, predetermined amounts of various components were mixed with water. The mixture was reacted at 60°C for 5 hours, then cooled to 25°C to produce various polysiloxane compounds (A). The components listed in Table 1 are as follows: • Isocyanate compound (a1) (a1-1):3-Isocyanate-propyltriethoxysilane (a1-2): 1,4-Diisocyanatebutane • Aminosilane compound (a2) (a2-1):3-aminopropyltriethoxysilane (a2-2):N-2-(aminoethyl)-3-aminopropyltrimethoxysilane • Amino compounds (a3) (a3-1): Ethylenediamine (a3-2): 4-aminobenzenesulfonic acid • Silicon-containing compounds (a4) (a4-1):3-Glycidoxypropyltriethoxysilane (a4-2): Tetraethoxysilane

[0042] [Table 1]

[0043] <Preparation of surface treatment agent> Based on the compositions shown in Tables 2 to 4, predetermined amounts of various polysiloxane compounds (A), metal compounds (B), water-soluble or water-dispersible resins (C), and water were mixed to prepare the surface treatment agents for Examples 1 to 79 and Comparative Examples 1 to 6. The components listed in Table 2 are as follows: ·Metal compounds (B) (B-1) Zirconium acetate (zirconium compound, ZrO2 equivalent content 30%, manufactured by Nippon Light Metal Co., Ltd.) (B-2) Zirconium nitrate (zirconium compound, ZrO2 equivalent content 20%, manufactured by Nippon Light Metal Co., Ltd.) (B-3) Zircon Hydrofluoric Acid 40% (Zirconium compound, manufactured by Morita Chemical Industries Co., Ltd.) (B-4) TC-400 (Titanium compound, Ti content 8.2%, manufactured by Matsumoto Fine Chemical Co., Ltd.) (B-5) 40% Titanium Hydrofluoric Acid (Titanium compound, manufactured by Morita Chemical Industries Co., Ltd.) ·Resin (C) (C-1) F-2125D (urethane resin, solids content: 30%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (C-2) A-655 (Acrylic resin, solids content: 45%, manufactured by Kusumoto Kasei Co., Ltd.) (C-3) IG-1002 (Phenolic resin, solids content: 48%, manufactured by DIC Corporation) (C-4) Denka Poval K-05 (Polyvinyl resin, solids content: 95%, manufactured by Denka Co., Ltd.) (C-5) Saran Latex L232A (Polyvinylidene chloride resin, solids content: 48%, manufactured by Asahi Kasei Chemicals)

[0044] <Film formation> Cold-rolled steel sheets (Examples 1-77 and Comparative Examples 1-6), hot-dip galvanized steel sheets (Example 78), and aluminum alloy sheets (Example 79) were degreased by spraying an alkaline degreasing agent [Fine Cleaner E6406, manufactured by Nippon Parkerizing Co., Ltd.; aqueous solution diluted with water to a concentration of 20 g / L] onto their surfaces at 60°C for 10 seconds, followed by rinsing with water for 10 seconds and drying.

[0045] The compositions of Examples 1-79 and Comparative Examples 1-6 were appropriately diluted and applied to the surface of the washed and dried workpiece using the bar coating method. The workpieces were then dried at a maximum plate temperature (PMT) of 150°C to produce workpieces with various coatings (Examples 1-79 and Comparative Examples 1-6). The weight of the dried coatings was 50 mg / m² for each. 2 The one with 1000 mg / m² 2 Two types were prepared. Coating weight: 50 mg / m² 2 The treated material having the following properties was used in the initial rust prevention evaluation, the corrosion resistance evaluation after solvent coating, the corrosion resistance evaluation after powder coating, and the corrosion resistance evaluation after electrodeposition coating, respectively, with a film weight of 1000 mg / m². 2 The treated material possessing this characteristic was used for alkali resistance evaluation.

[0046] <Preparation of solvent-coated substrates> On the coatings of the treated materials in Examples 1-79 and Comparative Examples 1-6, an amino alkyd resin coating [Amirac 1000, Kansai Paint Co., Ltd.] was applied by bar coating to a coating thickness of 30 μm after drying. The coatings were then baked at 150°C for 20 minutes to produce treated materials with the coating.

[0047] <Preparation of powder-coated materials> An epoxy polyester powder coating [Nippon Paint Co., Ltd., Bulysia Alticolor] was applied to the coatings of the materials in Examples 1-79 and Comparative Examples 1-6 using a corona-charged electrostatic coating gun [Parker Ionics Co., Ltd. GX-8000 manual gun], so that the thickness of the coating after drying was 80 μm. Then, the materials were baked at 180°C for 20 minutes to produce materials with a coating.

[0048] <Preparation of electrodeposited coating material> On the coatings of the materials to be treated in Examples 1-79 and Comparative Examples 1-6, an amine-added epoxy resin coating [GT-10HT, manufactured by Kansai Paint Co., Ltd.] was applied by controlling the voltage so that the thickness of the coating after drying was 20 μm. After that, the materials were washed with deionized water and baked at 180°C for 20 minutes to produce materials with a coating.

[0049] <Performance Evaluation> The following performance evaluations were conducted to assess the corrosion resistance and alkali resistance of the coating. A rating of B or higher in the evaluation indicates that the coating meets the requirements for practical performance.

[0050] <Temporary corrosion prevention evaluation> The treated materials of Examples 1-79 and Comparative Examples 1-6 were kept in an atmosphere of 95% relative humidity and 50°C for 5 hours, then dried, and the corrosion state was visually observed and the rust occurrence area percentage was measured. The corrosion resistance was evaluated based on the following evaluation criteria. (Evaluation Criteria) A: Rust occurrence area rate is less than 10% B: Rust occurrence area ratio 10% or more but less than 30% C: Rust occurrence rate of 30% or more

[0051] <Corrosion resistance evaluation after solvent coating> The treated materials of Examples 1-79 and Comparative Examples 1-6 were coated with solvent paint, and then cross-cuts (X-shaped cuts) were made in accordance with JIS K 5600:2014. The treated materials were then evaluated by a salt spray test. The salt spray test was conducted according to JIS-Z-2371, held for 120 hours, lightly rinsed with pure water, dried, adhesive tape was applied to the cross-cut areas, and then the adhesive tape was removed to measure the paint film peel width. The corrosion resistance after solvent coating was evaluated based on the evaluation criteria below. (Evaluation Criteria) A: Peel width less than 1 mm B: Peel width 1 mm or more but less than 3 mm C: Peeling width 3mm or more

[0052] <Corrosion resistance evaluation after powder coating> The treated materials of Examples 1-79 and Comparative Examples 1-6 were powder coated, and cross-cuts (X-shaped cuts) were made in accordance with JIS K 5600:2014. The coatings were then evaluated by a salt spray test. The salt spray test was conducted according to JIS-Z-2371, held for 120 hours, lightly rinsed with pure water, dried, and then adhesive tape was applied to the cross-cut areas. The adhesive tape was then removed, and the coating peel width was measured. The corrosion resistance after powder coating was evaluated based on the following evaluation criteria. (Evaluation Criteria) A: Peel width less than 1 mm B: Peel width 1 mm or more but less than 3 mm C: Peeling width 3mm or more

[0053] <Corrosion resistance after electrodeposition coating> The treated materials of Examples 1-79 and Comparative Examples 1-6 were electrodeposited and then cross-cut (X-shaped cuts) were made in accordance with JIS K 5600:2014. The salt spray test was then performed. The salt spray test was conducted in accordance with JIS-Z-2371, held for 120 hours, lightly rinsed with pure water, dried, adhesive tape was applied to the cross-cut areas, and then the adhesive tape was removed to measure the paint film peel width. The corrosion resistance after electrodeposition coating was evaluated based on the evaluation criteria below. (Evaluation Criteria) A: Peel width less than 1 mm B: Peel width 1 mm or more but less than 3 mm C: Peeling width 3mm or more

[0054] <Alkali resistance evaluation> The treated materials with the coatings of Examples 1-79 and Comparative Examples 1-6 were immersed in 0.1 mol / L sodium hydroxide for 30 minutes, then washed with water and dried. After that, the presence or absence of coating peeling was visually observed, and alkali resistance was evaluated based on the evaluation criteria below. (Evaluation Criteria) A: Visual inspection reveals that the remaining coating area is 90% or more. B: Visual inspection reveals that the remaining coating area is between 50% and 90%. C: Visual inspection reveals that less than 50% of the coating remains.

[0055] Table 2

[0056] Table 3

[0057] Table 4

Claims

1. Urea group and X group [X group is -COOR, -SO] ３ R and -NR ２ A surface treatment agent for cold-rolled steel sheets comprising: a polysiloxane compound (A) having one or more groups selected from, where R is a hydrogen atom, or an alkyl group which may have an alkoxy group or a hydroxyl group, and the ratio of the number of urea groups to X groups in one molecule (urea group / X group) is in the range of 0.05 to 0.4; a metal compound (B) containing a metal selected from the group consisting of Zr, Ti, Hf and Bi; and / or a water-soluble or water-dispersible resin (C) selected from the group consisting of polyvinyl resin, acrylic resin, polyvinylidene chloride resin, epoxy resin, urethane resin, polyester resin, polyamide resin, polyimide resin, phenolic resin, silicone resin and fluororesin.

2. The surface treatment agent for cold-rolled steel sheets according to claim 1, wherein the water-soluble or water-dispersible resin (C) is a resin selected from the group consisting of urethane resin, acrylic resin, and phenolic resin.

3. The surface treatment agent for cold-rolled steel sheets according to claim 1 or 2, wherein the metal compound (B) is a metal compound containing Zr.

4. A method for manufacturing a cold-rolled steel sheet having a coating, comprising the steps of: bringing a surface treatment agent for cold-rolled steel sheets described in any one of claims 1 to 3 into contact with the surface of a cold-rolled steel sheet or onto a surface; and drying the surface treatment agent that has been brought into contact with the surface of the cold-rolled steel sheet or onto a surface.

5. A cold-rolled steel sheet having a coating, manufactured by the method described in claim 4.

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