TWI643918B - Surface-treated agent for metal material - Google Patents

Abstract

An object of the present invention is to provide a surface treatment agent for a metal material which can produce a surface-treated metal material which exhibits excellent electrical conductivity, workability, load resistance and scratch resistance and which is excellent in storage stability. The surface treatment agent for a metal material of the present invention contains: a cerium compound dispersion (W) obtained by mixing colloidal cerium oxide (A) and an organoalkoxy decane (B), and containing an organoalkoxy decane ( B) Alcohol produced by hydrolysis (C); resin compound (X); colloidal cerium oxide (Y); lubricant (Z); and alcohol (C).

Description

Surface treatment agent for metal materials

The present invention relates to a surface treatment agent for metal materials, and more particularly to a surface treatment agent for metal materials for electrical machines.

A surface treatment is performed to impart various properties to the metal material. For example, as its performance, it is possible to suppress corrosion, or to prevent peeling of the coating film in the case of coating, or to avoid corrosion from the portion even if the coating film is peeled off.

Among them, in many cases, metal materials (especially aluminum plates) used for electrical equipment are required to have conductivity, workability, load resistance, scratch resistance, and the like. In many cases, there are trade-offs between the three properties of workability, load resistance, and scratch resistance. More specifically, in many cases, if the thickness of the film obtained by surface-treating the surface of the metal material is thick, the scratch resistance is excellent, but the conductive property is poor, and if the thickness of the film is thin, the conductive property is excellent but the scratch resistance is excellent. Poor.

Various studies have been conducted on surface treatment agents for metallic materials. For example, Patent Document 1 discloses a surface treatment agent for a metal material comprising: a citric acid compound (A); an organoalkoxy decane (B); and a metal compound (C) containing a group selected from Zr, Ti, Among the groups consisting of Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr, and Zn One less metal element; at least one compound (D) selected from the group consisting of a phosphoric acid compound and a fluorine compound; water (E); and alcohol (F), which is derived from an organoalkoxydecane (B) Produced by hydrolysis.

[Patent Document 1] International Publication No. 2010/070728

In recent years, in response to an increase in the required characteristics of electronic equipment, the required characteristics of metal materials for electronic equipment have also been improved. In particular, it is required to develop a metal material that satisfies conductivity, workability, load resistance, and scratch resistance at a higher level.

The inventors of the present invention evaluated the above-described characteristics of the metal material obtained by using the surface treatment agent for a metal material described in Patent Document 1, and as a result, the characteristics satisfy the conventionally required level, but did not reach the higher level recently required. In order to seek further improvement.

In view of the above circumstances, an object of the present invention is to provide a surface treatment agent for a metal material which can produce a surface-treated metal material which exhibits excellent electrical conductivity, workability, load resistance and scratch resistance and which has excellent storage stability.

As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by the following constitution.

(1) A surface treatment agent for a metal material, comprising: a ruthenium compound dispersion (W) obtained by mixing colloidal ruthenium dioxide (A) and an organoalkoxy decane (B), and containing the above-mentioned organoalkane An alcohol (C) produced by hydrolysis of oxydecane (B); a resin compound (X) selected from at least one selected from the group consisting of an urethane resin, an acrylic resin, and an epoxy resin; Cerium oxide (Y); and lubricant (Z); and the molar concentration (mol/L) (C _A ) of the above alcohol (C) and all alkoxylates contained in the above organoalkoxydecane (B) The ratio (C _A /C _B ) of the molar concentration (mol/L) (C _B ) of the alcohol produced when the base is hydrolyzed is in the range of 0.05 to 0.9.

(2) The surface treatment agent for a metal material according to the above aspect, wherein the mass ratio (X/W) of the mass of the solid content of the bismuth compound dispersion (W) to the mass of the resin compound (X) is 0.30. ~0.65.

(3) The surface treatment agent for metal materials according to (1) or (2), wherein the zeta potential of the bismuth compound dispersion (W) is higher than the zeta potential of the colloidal cerium oxide (Y).

(4) The surface treatment agent for a metal material according to any one of the above aspects, wherein the colloidal cerium oxide (Y) contains two or more kinds of colloidal cerium oxide having different average particle diameters.

(5) The surface treatment agent for metal materials according to any one of (1) to (4), wherein the mass ratio of the colloidal cerium oxide (A) to the organoalkoxy decane (B) is (A/ B) is 0.50~3.00.

(6) The surface treatment agent for metal materials according to any one of (1) to (5), wherein the mass of the solid content of the bismuth compound dispersion (W) and the mass of the colloidal cerium oxide (Y) The mass ratio (Y/W) is 0.10 to 0.50.

(7) The surface treatment agent for metal materials according to any one of (1) to (6) wherein the lubricant (Z) is selected from the group consisting of polyethylene wax, polypropylene wax, carnauba wax, and PTFE. At least one of the group.

(8) The surface treatment agent for a metal material according to any one of (1) to (7), wherein the content of the lubricant (Z) is 1.0 to 40% by mass based on the total solid content.

According to the present invention, it is possible to provide a surface treatment agent for a metal material which can produce a surface-treated metal material which exhibits excellent electrical conductivity, workability, load resistance and scratch resistance and which is excellent in storage stability.

Hereinafter, preferred aspects of the surface treatment agent for a metal material of the present invention will be described.

First, it is presumed that the surface-treated metal material (surface-treated metal material) having excellent properties can be produced by using the surface treatment agent for a metal material as follows, but the present invention is not limitedly explained by the estimation. The invention and the effects of the invention. The ruthenium compound dispersion (W) used for the surface treatment agent for metal materials is obtained by mixing colloidal silica and organoalkoxy decane, and it is presumed that at the same time, an inorganic component and an organic component are mixed. The film having the characteristics of an inorganic film, that is, a film having a hard and high density film and an organic film, that is, both lubricity and flexibility, achieves excellent scratch resistance (damage resistance) and workability. On the other hand, it is formed by a bismuth compound dispersion (W) having excellent film forming properties. A film having a very small gap and an extremely high density forms a dense and thin film, and as a result, the non-conduction point at the time of conductivity measurement is small, so that it is a film excellent in conductivity. Further, when it is mixed with a resin compound and a general colloidal cerium oxide in an appropriate amount, since the composition of the ruthenium compound is relatively close to each other, the film can be uniformly present in the film, and the mechanical properties of the film can be effectively improved. . In particular, if colloidal cerium oxide (Y) having a particle diameter of 50 nm or more is used, the surface is exposed on the surface of the film, so that the hardness of only the surface of the film can be remarkably improved. It is considered that further improvement in lubricity and electrical conductivity such as workability or scratch resistance (damage resistance) can be achieved.

Hereinafter, various components of the surface treatment agent for a metal material will be described in detail first, and then a method of producing a surface-treated metal material using a surface treatment agent for a metal material will be described in detail.

(矽 compound dispersion (W))

The surface treatment agent for metal materials contains the following cerium compound dispersion (W) obtained by mixing colloidal cerium oxide (A) and organoalkoxy decane (B), and containing an alkoxy decane (B) The alcohol (C) produced by the hydrolysis.

Hereinafter, each component in the ruthenium compound dispersion (W) will be described in detail.

The type of the colloidal cerium oxide (A) is not particularly limited, and examples thereof include Snowtex C, Snowtex CS, Snowtex CM, Snowtex O, Snowtex OS, Snowtex OM, Snowtex NS, Snowtex N, and Snowtex NM manufactured by Nissan Chemical Industries. Snowtex S, Snowtex 20, Snowtex 30, Snowtex 40, and, for example, Snowtex UP, Snowtex OUP, Snowtex PS-S, Snowtex PS-SO, Snowtex PS-M, Snowtex PS-MO processed into a special chain shape , Snowtex PS-L, Snowtex PS-LO, etc. Further, Adelite AT-20N, Adelite AT-20A, and Adelite AT-20Q equivalent grade manufactured by ADEKA Co., Ltd. can also be used.

The particle diameter of the colloidal cerium oxide (A) is preferably 4 to 200 nm, more preferably 4 to 100 nm, and most preferably 4 to 20 nm.

The type of the organoalkoxydecane (B) is not particularly limited, and examples thereof include tetramethoxynonane, tetraethoxydecane, trimethylmethoxydecane, trimethylethoxysilane, and dimethyl group. Dimethoxydecane, dimethyldiethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, cyclohexylmethyldimethoxydecane, n-hexyltrimethoxydecane, diphenyl Dimethoxy decane, diphenyl diethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, decyl trimethoxy decane, octadecyl trimethoxy decane, octadecyl Triethoxy decane, isobutyl trimethoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethyl Oxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-甲Propylene methoxypropyl methyl dimethoxy decane, γ-methyl propylene methoxy propyl methyl diethoxy decane, γ-mercaptopropyl methyl dimethoxy decane, p-styryl trimethyl Oxydecane, γ-acryloxypropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, γ-chloropropyl Trimethoxy decane, bis(triethoxymethyl propyl) tetrasulfide, γ-isocyanate propyl triethoxy decane, γ-triethoxy fluorenyl-N-(1,3-dimethyl Base-butylene) propylamine, N-(vinylbenzylamine)-β-aminoethyl-γ-aminopropyltrimethoxydecane, and the like. Among them, from the viewpoint of easily adjusting the concentration of the following alcohol (C), a trialkoxysilane having an alkoxy group having 3 mol of activity is preferable.

One of the preferred embodiments of the organoalkoxydecane (B) is a compound represented by the following formula (I).

In the formula (I), X represents any one selected from the group consisting of an epoxy group, an amine group, a fluorenyl group, a (meth) acryloxy group, a ureide group, an isocyanate group, and a vinyl group. base. Among them, an epoxy group or an amine group is preferred. Furthermore, when n is 2 or more, X may be the same or different.

L represents a divalent linking group or only represents a bonding bond. Examples of the linking group represented by L include an alkylene group (preferably having a carbon number of 1 to 20), -O-, -S-, an extended aryl group, -CO-, -NH-, and -SO _{2 .} -, -COO-, -CONH- or a combination of these. Among them, an alkyl group is preferred. In the case of only a bonding bond, it is meant that X of the formula (I) is directly bonded to Si (germanium atom). Further, when n is 2 or more, L may be the same or different.

R independently represents an alkyl group (preferably having a carbon number of 1 to 4) or a hydrogen atom.

n represents an integer from 1 to 3. Among them, it is preferably 1.

Preferably, the organoalkoxydecane (B) has at least one functional group selected from the group consisting of an amine group and an epoxy group. Further, the organoalkoxydecane (B) may be a hydrolyzate obtained by hydrolyzing a part of an alkoxy group. It is presumed that the organoalkoxydecane (B) has such functional groups, thereby promoting the coupling of the colloidal cerium (A) with the organo alkoxy decane (B) to form a dense three-dimensional crosslink. The film.

Further, the organoalkoxydecane (B) may be a hydrolyzate and/or a condensate obtained by hydrolyzing a part of an alkoxy group.

The cerium compound dispersion (W) is obtained by mixing the above colloidal cerium oxide (A) And the above organoalkoxydecane (B), which is obtained by hydrolysis and condensation of the organoalkoxydecane (B), and contains the following organoalkoxydecane (B) in the cerium compound dispersion (W). The alcohol (C) produced by the hydrolysis. The hydrolysis reaction and the condensation reaction of the organoalkoxydecane (B) are not particularly limited, and a known method can be employed.

The mass ratio (A/B) of the colloidal cerium oxide (A) to the organoalkoxy decane (B) is not particularly limited, and is preferably from 0.01 to 3.50, more preferably from 0.05 to 3.00, still more preferably from 0.10 to 2.50. . When it is in the above range, the continuous workability is excellent, and the adhesion between the formed film and the surface of the metal material is improved, and various characteristics of the surface-treated metal material are enhanced.

Further, the content of the organoalkoxydecane (B) in the surface treatment agent for a metal material is not particularly limited, and from the viewpoint of further superior properties of the surface-treated metal material, relative to all solids in the treatment agent The composition of the component is preferably from 0.1 to 70% by mass, more preferably from 1 to 50% by mass.

Further, all the solid content means the total amount of the components of the film formed on the metal material, and does not contain the alcohol (C), the solvent, or the like.

The alcohol (C) is produced by hydrolysis of an organoalkoxydecane (B).

The type of the alcohol (C) depends on the type of the alkoxy group of the organoalkoxydecane (B) to be used, and examples thereof include methanol, ethanol, and propanol.

The molar concentration (mol/L) (C _A ) of the alcohol (C) in the surface treatment agent for metal materials is when the alkoxy group contained in the organoalkoxydecane (B) is completely hydrolyzed. The obtained metal material was adjusted in such a manner that the molar concentration (mol/L) (C _B ) of the alcohol (C) in the surface treatment agent satisfies C _A /C _B = 0.05 to 0.9. Among them, it is preferably from 0.1 to 0.8, more preferably from 0.2 to 0.6. If it is in the above range, various characteristics of the surface-treated metal material obtained are more excellent.

When the above molar concentration ratio (C _A /C _B ) is less than 0.05, the effect of the reactive functional group required for the colloidal cerium oxide (A) and the organoalkoxy decane (B) to form a siloxane coupling Since the organoalkoxydecane (B) disappears, the surface-treated metal material obtained is inferior in workability, load resistance, and scratch resistance. Further, when the molar concentration ratio (C _A /C _B ) exceeds 0.9, the effect of the reactive functional group is high, and thus the organoalkoxydecane (B) forms a decane bond with each other and is difficult to form a dense one. The three-dimensionally crosslinked film has a poor conductivity and scratch resistance of the surface-treated metal material obtained, and the storage stability of the surface treatment agent for the metal material is also poor.

The method of adjusting the molar concentration (mol/L) of the alcohol derived from the alkoxy group of the organoalkoxydecane (B) is not particularly limited, and for example, a decyl alcohol condensation is mixed in the organoalkoxysilane. In a solution of a catalyst and water, a method of controlling the amount of alcohol by-produced to adjust the concentration; a method of removing the by-produced alcohol and water to adjust the concentration. In addition, the measuring method of the alcohol concentration is not particularly limited, and examples thereof include a chromatography method such as a gas chromatography method or an ion chromatography method, and a nuclear magnetic resonance analysis method.

(resin compound (X))

The surface treatment agent for a metal material contains at least one resin compound (X) selected from the group consisting of an amine ester resin, an acrylic resin, and an epoxy resin. Among them, the resin compound (X) is preferably an amine ester resin and/or an acrylic resin, and more preferably an amine ester resin, from the viewpoint that the characteristics of the surface-treated metal material obtained are more excellent.

The kind of the urethane resin is not particularly limited, and any amine ester resin which can be obtained by a conventionally known production method can be used. For example, a dispersion in which a compound which is usually used for producing an amine ester resin, such as a polyol, a polyisocyanate or a compound having two or more hydroxyl groups or amine groups and one or more carboxyl groups, can be used. Previously known method The amine ester polymer obtained by the polymerization is obtained by adding it to water and dispersing it together with a basic compound such as ammonia or a polyamine.

The urethane resin may be used singly or in combination of two or more.

As the polyol, a polyester polyol, a polyether polyol, a polycarbonate polyol, or the like can be used alone or in combination of two or more.

Examples of the polyester polyol include those obtained by direct esterification reaction and/or transesterification reaction of a low molecular weight polyol with a polyvalent carboxylic acid or an ester-forming derivative thereof such as an ester, an anhydride or a halide; A polycondensation of a hydroxycarboxylic acid compound obtained by a lactone or a hydrolyzed ring opening thereof, or the like.

Examples of the low molecular weight polyol used for producing the polyester polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and neopentyl glycol. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, 1,2-propanediol, 1 , 3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl- 2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-Diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2- An aliphatic diol such as methyl-1,8-octanediol, 1,9-nonanediol or 1,10-decanediol; trimethylolethane, trimethylolpropane, hexitol, A trivalent or higher aliphatic or alicyclic alcohol such as pentitol, glycerin, diglycerin, polyglycerin, neopentyl alcohol, dipentaerythritol or tetramethylolpropane.

Examples of the polyvalent carboxylic acid used for producing the polyester polyol include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and sebacic acid. Dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipate, 3-methyladipate, 3-methylglutaric acid, An aliphatic dicarboxylic acid such as 2-methylsuberic acid, 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, dimer acid or hydrogenated dimer acid; cyclohexane dicarboxyl An alicyclic dicarboxylic acid such as an acid; an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid or naphthalene dicarboxylic acid; trimellitic acid, trimesic acid, and castor oil fatty acid a tricarboxylic acid such as a polymer; a polycarboxylic acid having a tetracarboxylic acid or higher such as pyromellitic acid. Examples of the ester-forming derivative of a polyvalent carboxylic acid include an acid anhydride of such a polyvalent carboxylic acid, a halide (such as a chloride or a bromide), and an ester of a lower aliphatic alcohol (methyl ester, ethyl ester, propyl ester, and the like). Isopropyl ester, butyl ester, isobutyl ester, amyl ester, etc.).

Examples of the lactone used for producing the polyester polyol include γ-caprolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, and δ-valerolactone.

Examples of the polyether polyol include ethylene oxide adducts such as ethylene glycol, diethylene glycol, and triethylene glycol; and propylene oxide adducts such as propylene glycol, dipropylene glycol, and tripropylene glycol; and the above polyols. Ethylene oxide and / or propylene oxide adduct; polytetramethylene glycol and the like.

Examples of the polycarbonate polyol include diols such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanedimethanol, and diphenyl carbonate, phosgene. Wait for the reaction to be obtained.

Examples of the polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, leucine diisocyanate, hydrogenated dimethyl diisocyanate, 1,4-cyclohexyl diisocyanate, and 4, 4'. -dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 3,3'-dimethoxy-4,4'-extended biphenyl diisocyanate, 1 , 5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate , 2,4'-diphenylmethane diisocyanate, phenyl diisocyanate, xylylene diisocyanate, tetramethylbenzene Dimethyl diisocyanate and the like. Among these, as a more preferable one, tetramethylene diisocyanate, hexamethylene diisocyanate, diazonic acid diisocyanate, hydrogenated dimethyl dimethyl diisocyanate, 1,4-cyclohexyl diisocyanate are mentioned. 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate or the like.

Examples of the compound having two or more hydroxyl groups or amine groups and one or more carboxyl groups include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dihydroxyl. a dihydroxycarboxylic acid such as methylvaleric acid, 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid, or a diaminocarboxylic acid such as aminic acid or arginine. Further, a carboxyl group-containing polyester polyol obtained by reacting the above dihydroxycarboxylic acid with a polyvalent carboxylic acid can also be used.

The kind of the acrylic resin is not particularly limited, and an acrylic resin obtainable by a conventionally known production method can be used. For example, the acrylic resin can be produced by a method in which a mixed polymerization initiator, water, an emulsifier, and a monomer are polymerized, a monomer dropping method, a pre-emulsion method, or the like, which is previously known. Further, it is also possible to perform heterogeneous structuring of the particles by multistage polymerization such as seed polymerization, core-shell polymerization, or power feed polymerization. The polymerization temperature is usually from 0 to 100 ° C, preferably from 40 to 95 ° C, and the polymerization time is suitably from 1 to 10 hours.

The type of the monomer is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and butyl (meth)acrylate. Isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid An ester of (meth)acrylic acid such as isooctyl ester, 2-ethylhexyl (meth)acrylate or decyl (meth)acrylate with an alkanol having 1 to 10 carbon atoms (especially 1 to 8 carbon atoms), An ester of (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate with an alkanediol having 2 to 6 carbon atoms (especially 2 to 4 carbon atoms); As containing The oxime monomer may, for example, be vinyltrimethoxydecane, vinyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxy Baseline, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxy a decane or the like; examples of the carboxylic acid-containing monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid, and the like; and as a monomer having a cyclic skeleton, Examples thereof include an ester of (meth)acrylic acid such as styrene, cyclohexyl acrylate or cyclohexyl methacrylate with a cycloalkanol having 5 or 6 carbon atoms, isodecyl acrylate or isodecyl methacrylate.

The kind of the polymerization initiator is not particularly limited, and for example, the following well-known ones may be used: ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, benzammonium peroxide, and tert-butylperoxybenzoic acid. Ester, lauric acid peroxide, tert-butyl hydroperoxide, and the like.

The type of the emulsifier is not particularly limited, and examples thereof include a vinyl sulfonate, a styrene sulfonate, a sulfoethyl methacrylate, an alkylallyl sulfosuccinate, and an alkenyl sulfosuccinate. , α-sulfo-ω-(1-(alkoxy)methyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl) salt, etc. Aliphatic reactive emulsifier of sulfonic acid group; polyoxyalkylene alkyl alkenyl ether sulfate, polyoxyethylene alkyl propenyl phenyl ether sulfate, polyoxyethylene-1-(allyloxymethyl) An aliphatic reactive emulsifier having a sulfate group such as an alkyl ether sulfate; a polyoxyalkylene alkyl alkenyl ether, a polyoxyethylene alkyl propenyl phenyl ether, and an α-[1-{(allyl) An aliphatic reactive emulsifier having an ether group such as oxy)methyl}-2-(nonylphenoxy)ethyl]-ω-hydroxypolyoxyethylene.

The kind of the epoxy resin is not particularly limited, and an epoxy resin obtainable by a conventionally known production method can be used. For example, a dispersion obtained by repeatedly performing bisphenol A, bisphenol F, novolak resin or the like for producing an aqueous epoxy resin can also be used. The compound is obtained by dispersing an epoxy resin obtained by an addition reaction, an epihalohydric alcohol such as epichlorohydrin or an epoxy compound having two or more epoxy propylene, or a condensation reaction or an addition reaction.

The epoxy resin may be obtained by reacting an epoxy group or a hydroxyl group in the resin with a modifier, and examples thereof include an epoxy ester resin obtained by reacting an unsaturated fatty acid, and (meth)acrylic acid or An acrylic acid modified epoxy resin obtained by reacting an ester, an amine ester modified epoxy resin obtained by reacting an isocyanate compound, a decane modified epoxy resin obtained by reacting a decane coupling agent, or a phosphoric acid or A phosphoric acid-modified epoxy resin obtained by reacting the ester.

(colloidal cerium oxide (Y))

Colloidal cerium oxide (Y) is contained in the surface treatment agent for metal materials.

The type of the colloidal cerium oxide (Y) is not particularly limited, and may be, for example, SiO ₂ having a particle diameter of about 4 to 200 nm, and further containing sodium, potassium, ammonia, or the like as a stabilizer. Further, as the colloidal cerium oxide (Y), a commercially available product such as Snowtex and/or Adelite is preferably used. For example, Snowtex C, Snowtex CS, Snowtex CM, Snowtex O, Snowtex OS, Snowtex OM, Snowtex NS, Snowtex N, Snowtex NM, Snowtex S, Snowtex 20, Snowtex 30, Snowtex 40 manufactured by Nissan Chemical Industries, Ltd. , Adelite AT-20N, Adelite AT-20A, Adelite AT-20Q manufactured by ADEKA Co., Ltd. Moreover, it is also preferably a Snowtex UP, a Snowtex OUP, a Snowtex PS-S, a Snowtex PS-SO, a Snowtex PS-M, a Snowtex PS-MO, a Snowtex PS-L, a Snowtex PS-LO, etc. which are processed into a special chain shape. .

Two or more kinds of colloidal cerium oxide (Y) can also be used.

As a preferred aspect of the colloidal cerium oxide (Y), an average particle diameter is mentioned Two or more different types of colloidal cerium oxide. If it is in this aspect, the various characteristics of the surface-treated metal material obtained are more excellent. Further, the method of measuring the average particle diameter is a measurement value of a laser diffraction/scattering type particle size distribution measuring apparatus.

Further, in the case of containing two or more kinds of colloidal cerium oxide, colloidal cerium oxide having a particle diameter of 20 nm or less and colloidal cerium having a particle diameter of 50 nm or more are preferably used. If it is in this aspect, the various characteristics of the surface-treated metal material obtained are more excellent.

In the case where the first colloidal ceria having a particle diameter of 20 nm or less and the second colloidal ceria having a particle diameter of 50 nm or more are used, the mass ratio (the mass of the first colloidal ceria / the second colloid 2) The mass of cerium oxide is preferably from 0.25 to 4.0, more preferably from 0.33 to 3.0.

(Lubricant (Z))

The lubricant (Z) is contained in the surface treatment agent for metal materials.

The type of the lubricant (Z) is not particularly limited, and is preferably selected from the group consisting of polyethylene wax, polypropylene wax, carnauba wax, and PTFE in terms of obtaining various characteristics of the surface-treated metal material. At least one of the groups.

(other ingredients)

In the surface treatment agent for a metal material, a solvent may also be contained as needed. For example, water or an organic solvent (for example, a water-soluble organic solvent) or the like may be contained.

Further, in the surface treatment agent for a metal material, an alcohol, a ketone, a cellosolve-based water-soluble solvent, a surfactant, an antifoaming agent, a leveling agent, an antibacterial fungicide, a coloring agent, or the like may be added as needed. By these, the drying property of the treatment agent, the coating appearance, workability, storage property, and design property can be improved. However, it is important to add such a degree to the extent that the quality obtained in the present invention is not impaired, and it is preferably more than several mass% in the treating agent.

(surface treatment agent for metal materials)

The above various components are contained in the surface treatment agent for metal materials.

The content of the bismuth compound dispersion (W) in the surface treatment agent for a metal material is not particularly limited, and it is used for the metal material in terms of various characteristics, particularly conductivity, of the surface-treated metal material obtained. The total solid content of the surface treatment agent is preferably from 35.0 to 85.0% by mass, more preferably from 40.0 to 70.0% by mass.

The content of the resin compound (X) in the surface treatment agent for a metal material is not particularly limited, and the metal surface material obtained has various characteristics, particularly workability and load resistance, in comparison with the metal. The total solid content of the surface treatment agent for the material is preferably 5.0 to 40.0% by mass, more preferably 10.0 to 30.0% by mass.

The content of the colloidal cerium oxide (Y) in the surface treatment agent for a metal material is not particularly limited, and the various properties of the surface-treated metal material obtained, particularly the scratch resistance, are superior to those of the metal material. The solid content of all the surface treatment agents is preferably 2.0 to 20.0% by mass, more preferably 7.0 to 15.0% by mass.

The content of the lubricant (Z) in the surface treatment agent for a metal material is not particularly limited, and is preferably 0.5 to 50% by mass, more preferably 1.0 to 40, based on the total solid content of the surface treatment agent for the metal material. The mass % is further preferably 3.0 to 25.0% by mass, and most preferably 5.0 to 25.0% by mass. When it is in the above range, not only stable and sufficient workability but also properties such as corrosion resistance and electrical conductivity can be obtained.

In the surface treatment agent for a metal material, the mass ratio (X/W) of the mass of the solid content of the bismuth compound dispersion (W) to the mass of the resin compound (X) is not particularly limited, and is preferably 0.20 to 1.00. Good is 0.30~0.65, and the best is 0.35~0.50. If the mass ratio (X/W) In the above range, a composite film having both the properties of the inorganic film and the resin compound (X) as the organic film of the bismuth compound dispersion (W) can be formed, so that the surface-treated metal material can be obtained. It has excellent scratch resistance and processability. Further, since the cerium compound dispersion (W) has excellent film forming properties, a film having extremely small voids and extremely high density is formed, and a dense and thin film formed by filling the voids with the resin compound (X) is formed. When the conductivity is measured, the number of non-conduction points is reduced, so that the film is excellent in conductivity.

Further, the solid component quality of the cerium compound dispersion (W) means a component constituting the film (colloidal cerium oxide (A) or organoalkoxy decane (B), etc.) in the cerium compound dispersion (W), Does not contain alcohol (C) or solvent.

In the surface treatment agent for a metal material, the mass ratio (Y/W) of the mass of the solid content of the cerium compound dispersion (W) to the mass of the colloidal cerium oxide (Y) is not particularly limited, and is preferably 0.10 to 0.60. More preferably, it is 0.10 to 0.50, and further preferably 0.10 to 0.40. In the case where two or more types of colloidal cerium oxide (Y) are used, the total mass of these is calculated as the mass of the colloidal cerium oxide (Y). In the above range, since the colloidal cerium oxide (Y) has a property of imparting hardness to the film and embrittlement of the film on the other hand, a film which is less brittle is formed. Further, the colloidal cerium oxide (Y) does not segregate in the solid content component of the cerium compound dispersion (W) and is uniformly present in the coating film, so that the mechanical properties of the coating film can be more effectively improved. In particular, if colloidal cerium oxide (Y) having a particle diameter of 50 nm or more is used, the surface is exposed on the surface of the film, so that the hardness of only the surface of the film can be remarkably improved.

In the surface treatment agent for a metal material, it is preferred that the zeta potential of the ruthenium compound dispersion (W) is higher than the zeta potential of the colloidal ruthenium dioxide (Y). According to this aspect, the repellency of the ruthenium compound particles is small, and the film formation is easily performed, so that the overall film properties are improved, so that Preferably.

Further, the measurement of the zeta potential was carried out under the conditions of pH 6 using ELSZ-1 (manufactured by MALVERN).

The pH of the surface treatment agent for a metal material is not particularly limited, and is preferably 6 to 11, more preferably 7 to 10. When the pH is within the above range, the surface treatment agent for a metal material is excellent in stability.

The preparation method of the surface treatment agent for metal materials is not specifically limited. For example, the separately prepared cerium compound dispersion (W), the amine ester resin as the resin compound (X), the colloidal cerium oxide (Y), the lubricant (Z), and water can be sufficiently mixed by using a stirrer such as a mixing mixer. And manufacturing.

(surface treatment method)

The surface treatment method using the surface treatment agent for a metal material is not particularly limited, and is preferably a surface treatment method in which the surface treatment agent for the metal material is applied onto the surface of the metal material and dried by heating on the surface of the metal material. The amount of the film formed was 2 to 1000 mg/m ² in terms of Si adhesion.

Hereinafter, the surface treatment method will be described.

The metal material to be used is not particularly limited, and examples thereof include a hot-dip galvanized steel sheet (GI) and an alloyed hot-dip galvanized steel sheet (GA) obtained by alloying the same, and further, a hot-dip galvanized Zn-5% Al. Alloy steel plate (GF), hot-dip galvanized -55% aluminum alloy steel plate (GL), electrogalvanized steel plate (EG), electrogalvanized-Ni alloy steel plate (Zn-Ni), aluminum plated, aluminum plate, aluminum alloy plate. Moreover, it can also be applied to an iron plate which is not plated. Among them, aluminum plates and aluminum alloy plates are preferred.

It is also visible to remove oil or stain on the surface of the metal material before coating. Pretreatment of the metal material is required. In most cases, metal materials are coated with anti-rust oil for the purpose of rust prevention. Moreover, when the rust preventive oil is not applied, there are also oil or stains adhering to the work. By performing pretreatment to clean the surface of the metal material, the surface of the metal material is easily wetted uniformly by the surface treatment agent of the metal material. Further, in the case where there is no oil or stain, and the surface of the material is uniformly wetted by the surface treatment agent with the metal material, the pretreatment process is not particularly necessary. Further, the method of pretreatment is not particularly limited, and examples thereof include hot water washing, solvent washing, and alkaline degreasing cleaning.

As a method of applying a surface treatment agent for a metal material to a metal material, a method of appropriately selecting the shape of the metal material to be treated or the like is preferably a roll coating method, a dipping method, a spray coating method, or the like.

More specifically, in the form of a sheet, a roll coating method may be used, or a treatment agent may be sprayed on a metal material and the gas may be blown by a roll or a high pressure to adjust the coating amount. In the case of a molded article, it is immersed in a treatment agent and pulled, and if necessary, the excess amount of the treatment agent is blown off by the compressed gas to adjust the coating amount and the like.

The heating temperature at the time of drying the coating film formed on the surface of the metal material is preferably 40 to 300 ° C, more preferably 60 to 250 ° C, and particularly preferably 60 to 230 ° C. When it is in the above temperature range, the volatilization of the solvent is promoted, the metal compound is easily fixed, and the film is less likely to cause cracks, and a film excellent in corrosion resistance is obtained.

The heating and drying method is not particularly limited, and the treatment agent may be dried by heating with hot air, an induction heater, infrared rays, near infrared rays or the like. In addition, the heating time is appropriately selected depending on the kind of the compound in the surface treatment agent for the metal material to be used and the like. Among them, in terms of productivity and the like, it is preferably from 0.1 to 60 seconds, more preferably from 1 to 30 seconds.

The amount of the film formed on the surface of the metal material is preferably adjusted to 2 to 1000 mg/m ² , more preferably 10 to 800 mg/m ² , and still more preferably 20 to 500 mg/m ² in terms of Si adhesion. When it is in the above range, a surface-treated metal material which is excellent in corrosion resistance and excellent in various properties can be obtained.

As described above, the surface-treated metal material (the surface-treated metal material having a metal material and a film disposed on the metal material) which has been surface-treated with a surface treatment agent for a metal material can be applied to various uses. For example, materials used in various fields such as construction, electric, and automobiles can be cited. Among them, especially for the electrical field.

[Examples]

Next, the effects of the present invention will be described by way of examples and comparative examples, but the present examples are merely illustrative of the invention and are not intended to limit the invention.

1. Test board production method

(1) Test materials (raw materials)

The following commercially available materials were used as test materials. The details of the test materials used are shown in Table 1.

(2-1) Pretreatment (cleaning)

As a method of producing the test piece of Tables A to E, first, the surface of the above test material was treated with Fine Cleaner 315 manufactured by Nihon Parkerizing to remove oil or stain on the surface. Next, it was confirmed that the surface of the metal material was wetted with water by tap water after washing with tap water, and then rinsed with pure water to remove water in an oven at 100 ° C, and the obtained one was used as a test plate.

(2-2) Pretreatment (chromate phosphate)

As a method of producing the test piece of F to L of Table 1, first, the surface of the test material was washed in the same manner as described above, and then, the phosphate chromate was used to obtain a specific chromium adhesion amount by AM-K702 manufactured by Nihon Parkerizing. Processing, using the winner as a test board.

(3) Processing method

The surface treatment agent for the following metal materials was applied to each test piece by bar coating, and then directly placed in an oven without being washed with water to be dried to form a film having a specific film amount. The drying temperature is adjusted by the ambient temperature in the oven and the time it is placed in the oven. again The drying temperature indicates the temperature at which the surface of the test plate reaches.

Further, as a method of preparing a surface treatment agent for a metal material, first, a specific colloidal ceria and an organoalkoxysilane are mixed to prepare a ruthenium compound dispersion, and then water as a solvent and various other components are added.

Bar coating coating: A metal material was added dropwise to a test plate with a surface treatment agent, and coated by a #3~5 bar coater. The number of the bar coater used and the concentration of the treating agent are adjusted so as to be a specific amount of the film.

Hereinafter, the surface treatment agents of the examples and the comparative examples shown in Table 7 were prepared using the materials shown in Tables 2 to 6, and test pieces for evaluation were prepared under the treatment conditions shown in Table 8 for evaluation. Further, the C _A /C _{B in} Table 7 was measured using a nuclear magnetic resonance analyzer (NMR, model: JNM-ECX400 (manufactured by JEOL Ltd.) using a probe: 5 mm FG/TH tunable probe to measure nuclear species: 1H Using solvent: heavy water, cumulative number of times: 16 times) Calculated by measuring C _A . In the above Table 7, "A/B" represents the mass ratio of the colloidal cerium oxide (A) to the organoalkoxydecane (B). In Table 7, "X/W" represents the mass ratio of the mass of the solid content of the cerium compound dispersion (W) to the mass of the resin compound (X). In Table 7, "Y/W" represents the mass ratio of the mass of the solid content of the cerium compound dispersion (W) to the mass of the colloidal cerium oxide (Y). In Table 7, "the amount of blending" means the content (% by mass) of the lubricant in the surface treating agent for a metal material with respect to all the solid components.

Further, in each of the examples shown in Table 7, the zeta potential of the ruthenium compound dispersion (W) in the surface treatment agent and the surface treatment agent for each comparative example was higher than the zeta potential of the colloidal cerium oxide (Y).

1. Conductivity A method

For the conductivity, a tester was used, and one terminal was connected to the portion where the film was not provided, and the terminal having the needle shape at the tip end was brought into contact with the surface-treated metal material having the film at 20 gf, and evaluated based on the resistance value at this time. The evaluation criteria are described below.

◎: not up to 1.0Ω

○: 1.0 Ω or more and less than 2.0 Ω

△: 2.0 Ω or more and less than 4.0 Ω

×: 4.0 Ω or more

2. Conductivity B method

Conductivity was measured by using an LCR tester (4263B manufactured by HEWLETT PACKARD Co., Ltd.), and the film of one part of the test piece was directly in contact with the aluminum plate exposed by sanding, and the radius of the tip end portion was 10 mm. The measuring portion made of brass in a spherical shape was subjected to measurement by bringing the other terminal into contact with the measurement site under a load of 0.4 N (≒40 gf) from the surface-treated metal material. Further, at the time of measurement, the surface of the terminal was polished by sandpaper in advance, and the zero point correction was performed with the two terminals in contact. The evaluation criteria are described below. The average value of the value is set to 10 Ω or less to pass, and if it exceeds 10 Ω, it is set to fail.

○: 10 Ω or less

×: more than 10 Ω

3. Conductivity C method

Using a resistance measuring device (Loresta GP, ASP probe manufactured by DIA Instruments), the surface electric power of the ASP probe (four probes) in the state where the surface of the test piece was pressed to a load of 200 g was measured. Block 10 and evaluate according to the average value. The evaluation criteria are as follows.

◎: less than 0.1mΩ

○: 0.1 mΩ or more and less than 1.0 mΩ

△: 1.0 mΩ or more and less than 10.0 mΩ

×: 10.0 mΩ or more

4. Processability

A test piece for holding a surface-treated metal material was applied between the mold of the press working machine (Eriksson test machine) and the press plate with a load of 3.5 kN. A hole through which a punch (40 mm square, R: 5 mm) is passed is provided on the mold. Further, the punch is brought into contact with the surface of the test piece opposite to the surface-treated surface, and the punch is pushed up into the hole of the mold, whereby the test piece is protruded in a U-shape with respect to the surface-treated surface (again The surface treatment surface is located on the side of the U-shaped test piece). The processing conditions were set as follows: pressing load: 3.5 kN, processing speed: 120 mm/min, temperature: normal temperature. Highly refined mineral oil is used as a lubricant during processing. The surface of the test piece after press working was visually observed, and the degree of damage was confirmed. The following evaluation criteria are as follows.

In addition, the case of 5 points is set to "◎", the case of 4 points or 3 points is set to "○", the case of 2 points is set to "△", and the case of 1 point is set to "X". The results are shown in Tables 8 and 9.

5 points: no damage was observed in the film of the bending part and the sliding part of the mold

4 points: In the film of the bending portion and the sliding portion of the mold, the damage was found to be less than 0.1 mm in width and less than 0.5 mm in length, but no damage was observed in the width of 0.1 mm or more and the length of 0.5 mm or more.

3 points: A film having a width of 0.1 mm or more and less than 0.2 mm, a length of 0.5 mm or more, and less than 1 mm was observed in the film of the bent portion and the mold sliding portion, but the width was not observed to be 0.2 mm or more. And the damage of the length of 1mm or more

2 points: The film having a width of 0.2 mm or more and less than 0.3 mm and a length of 1 mm or more and less than 2 mm was observed in the film of the bent portion and the mold sliding portion, but no damage of 0.3 mm or more and 2 mm or more in length was observed. situation

1 point: A case where the width of the film is 0.3 mm or more and the length is 2 mm or more in the film of the bent portion and the sliding portion of the mold

5. Load resistance

The load-bearing property was evaluated by using a Bowden tester to test the presence or absence of damage on the test surface when the 10 mm Φ steel ball was slid once, while changing the load with respect to one load. The evaluation criteria are described below.

◎: The load of damage can be visually observed to be 250gf or more.

○: The load of the damage can be visually observed to be 200 gf or more and less than 250 gf.

△: The damage of the damage can be visually observed to be 150 gf or more and less than 200 gf.

×: The load of damage can be visually detected to be less than 150gf

6. Scratch resistance (1)

The scratch resistance (1) was evaluated by the following method. The wrapping film was attached to the front end of the pressing jig of the back and forth friction tester via a double-sided tape through a cushioning material. The cushioning material was obtained by folding "Cotton Ciegal" manufactured by Chiyoda Co., Ltd. into a four-fold shape, and as a wrapping film, a wrapping film #4000 manufactured by Sumitomo 3M Co., Ltd. was used. Then, the test piece was placed on a sample stage of a back and forth friction tester to be fixed. Then, the wound film was brought into contact with the surface-treated surface of the test piece, and a load of 1 kg was applied to the test piece by a pressing jig, and the film was slid 100 times in a horizontal direction at a width of 10 mm and at a speed of 20 mm/s. The sliding portion of the surface-treated surface was read by a scanner under conditions of 24 bit color and 300 dpi, and the degree of damage of the sliding portion was evaluated as described below.

In addition, the case of 5 points is set to "◎", the case of 4 points or 3 points is set to "○", the case of 2 points is set to "△", and the case of 1 point is set to "X". The results are shown in Tables 8 and 9.

(evaluation benchmark)

5 points: no damage at all

4 points: The situation where the sliding part is slightly discolored

3 points: The peeling of the coating film was observed at less than 50% of the sliding portion.

2 points: 50% or more of the sliding portion and less than 75% of the peeling of the coating film

1 point: When the peeling of the coating film is seen at 75% or more of the sliding portion

7. Storage stability

The viscosity of the treatment liquid after the surface treatment agent for metal materials was stored at 40 ° C for 3 months was measured, and evaluated according to the rate of change of the viscosity immediately after preparation.

◎: The rate of change is less than ±5%

○: The rate of change is ±5% or more and less than ±10%

△: The rate of change is ±10% or more and less than ±20%

×: The rate of change is ±20% or more

The evaluation results are shown in Tables 8 and 9.

In Table 8, "film amount" means the film weight. "PMT" indicates the Peak Metal Temperature.

As shown in Table 8, the surface-treated metal material obtained by using the surface treatment agent for a metal material of the present invention is not affected by the surface shape of the raw material, exhibits excellent electrical conductivity, and comprehensively satisfies processability and load resistance. The scratch resistance and the like are opposite to the conductivity in terms of surface coating.

In the comparison of Examples 1 to 6, it was confirmed that a more excellent effect can be obtained by satisfying the range of C _A /C _{B in} the range of 0.1 to 0.8 (more preferably in the range of 0.2 to 0.6).

Further, as is clear from the comparison between Examples 3 and 7 to 12, it was found that if the particle diameter of the colloidal cerium oxide (A) is 20 nm or less, a more excellent effect can be obtained.

Further, as is clear from the comparison of Examples 19 to 27, it was confirmed that the mass ratio (X/W) of the mass of the solid content of the ruthenium compound dispersion (W) to the mass of the resin compound (X) satisfies the range of 0.30 to 0.65. (More preferably in the range of 0.35 to 0.50), a more excellent effect can be obtained.

Further, from the comparison of Examples 39 to 45, it was confirmed that the mass ratio (A/B) of the colloidal cerium oxide (A) to the organoalkoxydecane (B) satisfies the range of 0.05 to 3.00 (more preferably More excellent results can be obtained from the range of 0.10 to 2.50.

Further, as is clear from the comparison of Examples 46 to 50, it was confirmed that the mass ratio (Y/W) of the mass of the solid content of the cerium compound dispersion (W) to the mass of the colloidal cerium oxide (Y) satisfies 0.1 to 0.5. The range (more preferably in the range of 0.1 to 0.4) can achieve better results.

In addition, it is confirmed that the content of the lubricant (Z) in the surface treatment agent for a metal material satisfies the range of 1.0 to 40% by mass (more preferably 3.0 to 25.0% by mass, and further, from the comparison of Examples 51 to 59). It is preferably in the range of 5.0 to 25.0% by mass), and a more excellent effect can be obtained.

On the other hand, as shown in Comparative Examples 1 to 7, when a treatment agent which does not satisfy the requirements of the surface treatment agent for a metal material of the present invention is used, conductivity, workability, load resistance, and abrasion resistance are confirmed. Either the sex or storage stability is poor.

Further, as shown in Comparative Example 8, when the treatment agent of Example 10 shown in Patent Document 1 was used, it was confirmed that the load resistance and the scratch resistance were inferior.

Further, using the test piece of the surface-treated metal material obtained in Examples 31 to 33, the following scratch resistance (2) evaluation was performed.

Furthermore, the following scratch resistance (2) evaluation is different from the above-mentioned scratch resistance (1) evaluation, and The buffer material is used and the evaluation conditions become more severe conditions.

(scratch resistance (2))

The scratch resistance (2) was evaluated by the following method. The wrapping film was attached to the front end of the pressing jig (contact shape: 10 mm × 20 mm, made of stainless steel) of the back and forth friction tester by a double-sided tape. As the wound film, a stretch film # 4000 manufactured by Sumitomo 3M Co., Ltd. was used. Then, the test piece was placed on a sample stage of a back and forth friction tester to be fixed. Then, the wound film was brought into contact with the surface-treated surface of the test piece, and a load of 2 kg was applied to the test piece by a press jig, and the film was slid 100 times at a speed of 20 mm/s in a horizontal direction at a width of 10 mm. The sliding portion of the surface-treated surface was read by a scanner under conditions of 24 bit color and 300 dpi, and the degree of damage of the sliding portion was evaluated as described below. In addition, the case of 5 points is set to "◎", the case of 4 points or 3 points is set to "○", the case of 2 points is set to "△", and the case of 1 point is set to "X". The results are shown in Table 10.

(evaluation benchmark)

5 points: no damage at all

4 points: The situation where the sliding part is slightly discolored

3 points: The peeling of the coating film was observed at less than 50% of the sliding portion.

2 points: 50% or more of the sliding portion and less than 75% of the peeling of the coating film

1 point: When the peeling of the coating film is seen at 75% or more of the sliding portion

The result of the scratch resistance (2) of Example 31 was "○", the result of Example 32 was "◎", and the result of Example 33 was "◎". From these results, it was confirmed that in Examples 32 and 33 in which colloidal cerium oxide having a particle diameter of 20 nm or less and colloidal cerium oxide having a particle diameter of 50 nm or more were used, a more excellent effect was obtained.

Claims (9)

A surface treatment agent for a metal material, comprising: a cerium compound dispersion (W) obtained by mixing colloidal cerium oxide (A) and an organoalkoxy decane (B), and containing the organic alkoxy decane (B) an alcohol (C) produced by hydrolysis; a resin compound (X) selected from at least one selected from the group consisting of an amine ester resin, an acrylic resin, and an epoxy resin; colloidal cerium oxide (Y); And the lubricant (Z); and the molar concentration (mol/L) (C _A ) of the alcohol (C) is generated when the alkoxy group contained in the organoalkoxydecane (B) is hydrolyzed The ratio of molar concentration (mol/L) (C _B ) of the alcohol (C _A /C _B ) is in the range of 0.05 to 0.9; the mass of the solid component of the bismuth compound dispersion (W) and the colloidal cerium oxide ( The mass ratio (Y/W) of the mass of Y) is 0.10 to 0.50. A surface treatment agent for a metal material according to the first aspect of the invention, wherein an aluminum plate or an aluminum alloy plate is used as the metal material. The surface treatment agent for metal materials according to claim 1 or 2, wherein the colloidal cerium oxide (Y) has a particle diameter of 4 to 200 nm. The surface treatment agent for a metal material according to claim 1 or 2, wherein a mass ratio (X/W) of the mass of the solid content of the bismuth compound dispersion (W) to the mass of the resin compound (X) is 0.30~0.65. A surface treatment agent for a metal material according to claim 1 or 2, wherein the deuteration The zeta potential of the dispersion (W) is higher than the zeta potential of the colloidal cerium oxide (Y). The surface treatment agent for a metal material according to the first or second aspect of the invention, wherein the colloidal cerium oxide (Y) contains two or more kinds of colloidal cerium oxide having different average particle diameters. The surface treatment agent for metal materials according to claim 1 or 2, wherein the mass ratio (A/B) of the colloidal cerium oxide (A) to the organoalkoxy decane (B) is 0.50 to 3.00. The surface treatment agent for metal materials according to claim 1 or 2, wherein the lubricant (Z) is at least one selected from the group consisting of polyethylene wax, polypropylene wax, carnauba wax, and PTFE. . The surface treatment agent for metal materials according to claim 1 or 2, wherein the content of the lubricant (Z) is 1.0 to 40% by mass based on the total solid content.