TWI437123B - Aqueous surface-treating agent for metallic materials - Google Patents

Description

Water metal surface treatment agent

The present invention relates to an aqueous metal surface treatment agent which can form a film excellent in storage stability, ultraviolet deterioration resistance, alkali resistance, acid resistance, workability, and film transparency.

In general, it is possible to impart excellent adhesion to the surface of a metal material, and to impart corrosion resistance or processability to the surface of the metal material, by containing an organic resin, with chromic acid, dichromic acid or the like on the surface of the metal material. The method of treating the resin chromate by the treatment liquid of the main component is a general method, and currently, an environment-corresponding non-chromate organic resin film treatment in which another crosslinkable metal is substituted for chromium is actually used.

In the non-chromate organic resin film processing technology, Patent Document 1 discloses that emulsion polymerization is carried out by using a monomer composition containing at least (meth) acrylate and dialkyl (meth) acrylamide and a surfactant. A method for producing a highly weather resistant emulsion characterized by the same.

In the non-chromate organic resin film processing technology, Patent Document 2 discloses that styrene containing at least (meth) acrylate and 0.1 to 20% by mass based on the (meth) acrylate, and an interface are disclosed. A method for producing a fine particle emulsion characterized by emulsion polymerization of a monomer composition of an active agent.

Further, in the non-chromate organic resin film technology, Patent Document 3 discloses a surface treatment agent for a metal plate containing no chromium, which is characterized in that (A) a water-based resin having a carboxyl group and an acid amide bond; (B) One or two or more metal compounds selected from the group consisting of metal compounds of Al, Mg, Ca, Zn, Ni, Co, Fe, Zr, Ti, V, W, Mn, and Ce; and (C) containing a ruthenium compound.

Further, in the non-chromate organic resin film technology, Patent Document 4 discloses an aqueous coating material having a specific nitrogen-containing radical polymerizable unsaturated monomer (a) in an amount of 0.1 to 30% by mass based on the total of the constituent monomers. 1 to 20% by mass of a carboxyl group-containing radical polymerizable unsaturated monomer (b), and 50 to 98.9% by mass of another radical polymerizable unsaturated monomer (c), obtained by radical polymerization of a monomer mixture The resin component (A) and the solid content of the resin component (A) are 100 parts by mass, and the organic acid catalyst (C) is contained in an amount of 0.01 to 10 parts by mass.

Patent Document 1: JP-A-2000-327704

Patent Document 2: JP-A-2000-327722

Patent Document 3: JP-A-2003-201579

Patent Document 4: JP-A-2006-152056

However, any of the above methods and surface treatment agents have properties that can be used as a substitute for the resin chromate film, but are excellent in storage stability, ultraviolet degradation resistance, alkali resistance, acid resistance, and processability. It is still too early to say that the film having excellent transparency of the film is so strong that it is strongly required to satisfy the development of such surface treatment agents and treatment methods.

The present invention can solve the above problems of the prior art, and an object thereof is to provide an aqueous surface treatment agent which can form excellent storage stability, ultraviolet degradation resistance, alkali resistance, acid resistance, processability, and film transparency. Excellent film.

The present inventors have repeatedly studied in order to solve such problems, and as a result, it has been found that a polymer having a polymerization unit derived from a specific structure of (meth) acrylate has a glass transition temperature of 0 to 70 ° C. The aqueous surface treatment agent of a polymer and an emulsifier is excellent in storage stability, and can form a film excellent in ultraviolet deterioration resistance, alkali resistance, acid resistance, workability, and film transparency, and thus completed the present invention.

That is, the present invention relates to a metal surface treatment agent characterized by having a general formula (I) in a molecule.

Wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a general formula (II)

(wherein R3, R4 and R5 represent a polymerization unit of the (meth) acrylate (A) represented by a group represented by an independent hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms] A polymer comprising a polymer (P) having a glass transition temperature of 0 to 70 ° C, an emulsifier, and water, and the polymer (P) is dispersed by the emulsifier.

Further, the "polymerization unit derived from (meth) acrylate (A)" means the polymerization unit formed by opening the carbon-carbon double bond in the (meth) acrylate (A), and this definition is followed by The phrase "polymerization unit derived from ruthenium-containing monomer (B)", "polymerization unit derived from α,β-ethylenically unsaturated carboxylic acid (C)" and "polymerization unit derived from reactive emulsifier" may be the same. Be applicable.

The polymer (P) molecule has a general formula (III)

[wherein, R6, R7 and R8 represent mutually independent hydrogen atoms, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; 1 to 3 alkoxy groups, X represents formula (IV)

Or general formula (V)

The polymerization unit of the ruthenium-containing monomer (B) represented by the formula (wherein R9 represents a hydrogen atom or a methyl group, and R10 represents a alkyl group having 1 to 12 carbon atoms) is preferred.

The polymer (P) is preferably a polymerization unit having an α,β-ethylenically unsaturated carboxylic acid (C) in the molecule.

The ratio of the polymerization unit derived from the (meth) acrylate (A) is preferably 0.1 to 50 parts by mass based on 100 parts by mass of the polymer (P).

The ratio of the polymerization unit derived from the ruthenium-containing monomer (B) is preferably 0.5 to 2.0 parts by mass based on 100 parts by mass of the polymer (P).

The acid value of the polymer (P) is preferably from 5 to 40 mgKOH/g.

The metal surface treatment agent is preferably contained in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the polymer (P).

The plasticizer (Q) preferably has at least one ester bond and/or at least one ether bond in the molecule selected from 2,2,4-trimethyl-1,3pentanediol monoisobutyric acid. At least one of ester, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether, and dipropylene glycol n-butyl ether is more preferred.

By using the aqueous metal surface treatment agent having excellent storage stability of the present invention, it is possible to form a film excellent in ultraviolet deterioration resistance, alkali resistance, acid resistance, workability, and film transparency.

The best form of implementing the invention

The aqueous metal surface treatment agent of the present invention has a molecule derived from the general formula (I)

Wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a general formula (II)

(wherein R3, R4 and R5 represent a polymerization unit of the (meth) acrylate (A) represented by a group represented by an independent hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms] In the polymer, the glass transition temperature is necessarily a polymer (P) of 0 to 70 °C.

The glass transition temperature of the polymer (P) is required to be 0 to 70 ° C, whereby alkali resistance, acid resistance, workability, and film transparency can be favorably maintained. From the above viewpoints, the glass transition temperature is preferably from 10 to 60 ° C, more preferably from 20 to 50 ° C. When the glass transition temperature is less than 0 ° C, the alkali resistance and acid resistance are not significantly lowered, and the necessary film hardness cannot be obtained at the time of processing. Conversely, when it exceeds 70 ° C, storage stability and film compliance necessary for processing are remarkably lowered.

The (meth) acrylate (A) unit imparts an effect of the polymer (P), and the alkali resistance, acid resistance, and processability can be improved as the glass transition temperature increases.

Further, it is necessary that R2 of the (meth) acrylate (A) is formed by only saturation bonding. When an unsaturated bond is present, a radical reaction occurs by ultraviolet rays to form a chromophore or an auxochrome, and the ultraviolet ray deterioration resistance is remarkably lowered.

With respect to the definitions of R3, R4 and R5 in the general formula (II), the alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group, a propyl group and an isopropyl group.

The (meth) acrylate (A) is not particularly limited, and for example, there is acrylic acid. Ester, acrylic acid Ester, methacrylic acid Ester, methacrylic acid Ester and the like.

The polymer (P) contained in the aqueous metal surface treatment agent of the present invention has a general formula (III) in the molecule.

In the formula, R6, R7 and R8 each represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number of 1 to 3 alkoxy groups. 1 to 3 alkoxy groups, X represents formula (IV)

Or general formula (V)

The polymerization unit of the ruthenium-containing monomer (B) represented by the formula (wherein R9 represents a hydrogen atom or a methyl group, and R10 represents a alkyl group having 1 to 12 carbon atoms) is preferred, whereby The adhesion to the metal surface is enhanced to improve processability while improving alkali resistance or acid resistance.

With respect to the definitions of R6, R7 and R8 in the general formula (III), the alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group, a propyl group and an isopropyl group, and the alkoxy group having 1 to 3 carbon atoms contains a group. The oxy group, the ethoxy group, the propoxy group, and the isopropoxy group, and the C 1 to 3 alkoxy group having 1 to 3 alkoxy groups include a methoxyethoxy group.

R10 in the general formula (V) is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms.

With regard to the definition of R10 in the general formula (V), in terms of an alkylene group, there are, for example, a methylene group, an exoethyl group, a 1,3-trimethylene group, a propylene group, a butyl group, and a hexamethyl group. Methylene, octyl, thiol, and twelfth base.

The ruthenium-containing monomer (B) is not particularly limited, and examples thereof include ethylene trimethoxy decane, ethylene triethoxy decane, 3-propylene methoxy propyl trimethoxy decane, and 3-methyl propylene oxime. Propylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropene oxime Oxypropyl triethoxy decane, and the like.

The polymer (P) preferably has a polymerization unit derived from the α,β-ethylenically unsaturated carboxylic acid (C) in the molecule, whereby the adhesion to the surface of the metal to be treated is stronger, and the acid resistance and processing can be improved. Sex.

The α,β-ethylenically unsaturated carboxylic acid (C) is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and crotonic acid.

The ratio of the amount of the (meth) acrylate (A) to the polymer unit derived from the (meth) acrylate (A) is preferably 0.1 to 50 parts by mass based on 100 parts by mass of the polymer (P). It is preferably from 0.5 to 45 parts by mass, more preferably from 3.0 to 35 parts by mass. When the ratio is less than 0.1 part by mass based on 100 parts by mass of the polymer (P), the effect of adding the (meth) acrylate (A) cannot be exhibited, and when it exceeds 50 parts by mass, it is difficult to maintain storage stability.

The ratio of the amount of the ruthenium-containing monomer (B) to the polymer unit containing the ruthenium monomer (B) is preferably 0.5 to 2.0 parts by mass, and 0.7 to ≤ 100 parts by mass of the polymer (P). 2.0 parts by mass is more preferable, and 1.0 to 2.0 parts by mass is more preferable. When the ratio is less than 0.5 part by mass based on 100 parts by mass of the polymer (P), it is difficult to exhibit the effect of adding the fluorene-containing monomer (B), and when it exceeds 2.0 parts by mass, the storage stability tends to be lowered.

With respect to the compounding amount of the α,β-ethylenically unsaturated carboxylic acid (C), the acid value of the polymer (P) derived from the polymer unit of (C) is preferably 5 to 40 mg KOH/g, and 10 to 35. Preferably, the mg KOH/gram is more preferably 15 to 30 mg KOH/g. When the acid value is less than 5 mgKOH/g, it is difficult to exhibit the effect of adding the α,β-ethylenically unsaturated carboxylic acid (C). On the other hand, when it exceeds 40 mgKOH/g, the water solubility of the polymer (P) becomes strong, which not only lowers the storage stability, but also tends to lower the alkali resistance and acid resistance.

In the case where the emulsifier used in the production of the polymer (P) is a reactive emulsifier, the polymer unit derived from the reactive emulsifier also becomes a constituent component of the polymer (P). In the case where only a reactive emulsifier is used, the ratio of the polymer unit derived from the reactive emulsifier is preferably 0.5 to 5 parts by mass, more preferably 1 to 3 parts by mass, per 100 parts by mass of the polymer (P). . When the ratio is less than 0.5 part by mass based on 100 parts by mass of the polymer (P), it is difficult to obtain the storage stability of the aqueous metal surface treatment agent of the present invention, and when it exceeds 5 parts by mass, the water resistance of the obtained film is lowered. The tendency. The emulsifier will be described later.

The polymer (P) is as described above, and contains a polymerization unit derived from (meth) acrylate (A) as an essential constituent unit, and contains a polymerization unit derived from a ruthenium-containing monomer (B) derived from α,β-ethylenic unsaturation. The polymerization unit of the carboxylic acid (C) and/or the reactive emulsifier is obtained as an arbitrary constituent unit. However, all of them are residual constituent units other than the polymerization units, and all of them are derived from an alkyl group selected from the group not containing an aromatic ring. A polymerization unit of at least one (meth) acrylate of (meth) acrylate and hydroxyalkyl (meth) acrylate.

The carbon number of the above alkyl group is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 4. Further, the number of carbon atoms of the hydroxyalkyl group is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 4.

Specifically, the (meth) acrylate may, for example, be methacrylate, ethacrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate or secondary butyl. Acrylate, tertiary butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, methacrylate, 2-hydroxyethyl Acrylate, 3-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate , secondary butyl methacrylate, tertiary butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl Acrylate, mercapto methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and the like.

The method for producing the polymer (P) is not particularly limited, and the polymer (P) is produced by a known method. For example, a polymer (P)-based polymerization initiator, water, an emulsifier, and a monomer are collectively mixed and polymerized, a monomer dropping method, a pre-emulsion method, or the like. Further, it is possible to perform heterogeneous structure of particles by multistage polymerization such as seed polymerization, core-shell polymerization, and 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 polymerization initiator is not particularly limited, and for example, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxybenzoate, and lauryl peroxide can be used. , tertiary butyl hydroperoxide, and the like.

In the aqueous metal surface treatment agent of the present invention, the polymer (P) can be dispersed in water by an emulsifier.

As the emulsifier, at least one selected from the group consisting of a reactive emulsifier and a non-reactive emulsifier can be used. The reactive emulsifier is not particularly limited, and examples thereof include a vinyl phthalate, a styrene citrate, a sulfoethyl methacrylate, an alkylallyl sulfosuccinate, and an alkene sulfonate. Acid salt, polyoxyalkylene alkene ether sulfate, polyoxyalkylene alkene ether, polyoxyethylene alkyl propenyl phenyl ether, polyoxyethylene alkyl propylene phenyl ether sulfate salt, polyoxyethylene-1- (allyloxymethyl)alkyl ether sulfate, α-[1-{(allyloxy)methyl}-2-(nonylphenoxy)ethyl]-ω-hydroxypolyoxyethylene And α-sulfo-ω-(1-(alkoxy)methyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl) salt and the like. The non-reactive emulsifier is not particularly limited, and examples thereof include a higher fatty acid salt (sodium laurate, sodium oleate, etc.), a higher alcohol sulfate salt (sodium lauryl sulfate, sodium oleate, etc.), and a higher alkyl aryl group. Sulfate (sodium dodecyl benzoate, sodium dodecyl diphenyl ether diacetate, etc.), polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl sulfhydryl Ether, polyoxyethylene oleyl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, and the like. The above salts are sodium salts, potassium salts, ammonium salts and the like.

As the emulsifier, only a reactive emulsifier or only a non-reactive emulsifier may be used, or these may be used in combination. Since the amount of the emulsifier used can be reduced, it is preferred to use a reactive emulsifier.

The amount of use in the case where only a reactive emulsifier is used as an emulsifier is as described above. In terms of the amount of use of the non-reactive emulsifier, it is preferably 3 to 10 parts by mass, more preferably 5 to 8 parts by weight, per 100 parts by mass of the polymer (P). When the amount is less than 3 parts by mass, it is difficult to obtain the storage stability of the aqueous metal surface treatment agent of the present invention, and when it exceeds 10 parts by mass, the water resistance of the obtained film tends to decrease. In the case where the reactive emulsifier and the non-reactive emulsifier are used in combination, the amount of use in the case of using only one may be considered. As described above, the amount of the emulsifier used is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, per 100 parts by mass of the polymer (P).

The polymer dispersion (emulsion or suspension) or the polymer solution obtained by the above polymerization can be used as it is or adjusted as a solid surface treatment agent or the like as a metal surface treatment agent.

The metal surface treatment agent of the present invention may contain a plasticizer (Q).

The plasticizer (Q) is preferably one having at least one ester bond and/or at least one ether bond in the molecule, and is selected from 2,2,4-trimethyl-1,3pentanediol. At least one of butyrate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether, and dipropylene glycol n-butyl ether is preferably 2,2,4-trimethyl-1. 3 pentylene glycol monoisobutyrate and/or diethylene glycol monobutyl ether acetate are more preferred. When the plasticizer (Q) has no ester bond or ether bond, it is not preferable because it cannot function as a plasticizer of the polymer (P).

The compounding amount of the plasticizer (Q) is preferably 0.5 to 50 parts by mass, more preferably 2 to 45 parts by mass, even more preferably 5 to 40 parts by mass, per 100 parts by mass of the polymer (P). When the amount is less than 0.5 part by mass, it is difficult to exhibit the effect of adding the plasticizer (Q). As a result, it is difficult to obtain good film-forming property, and it is difficult to obtain good transparency of the film. Moreover, when it exceeds 50 mass parts, storage stability will fall.

Further, the film formation means the film formation, and the microscopic means the form in which the particles of the polymer (P) are melted after drying. In the film forming stage, the plasticizer (Q) acts as a plasticizer for the polymer (P) to promote melting of the particles. As a result, the diffusion of the incident light can be suppressed, the transparency of the film can be improved, and the alkali resistance and the acid resistance can be improved, and the workability can be improved in order to improve the cohesive force of the film.

The water-based metal surface treatment agent of the present invention may contain a substance having no C=C double bond in the resin other than the polymer (P) for the purpose of improving chemical resistance and/or corrosion resistance. Examples of such other resins include an acrylic resin, an epoxy resin, an urethane resin, and the like which do not have a C=C double bond. The other resin is not particularly limited, and a commonly used one can be used in the aqueous metal surface treatment agent. For the acrylic resin, for example, poly(methyl) methacrylate, poly(meth) acrylate, polyacrylic acid 2 can be used. -ethylhexyl ester or the like, for the epoxy resin, for example, a hydrogenated bisphenol A type epoxy resin or the like can be used, and for the urethane resin, for example, hexamethylene diisocyanate or diisocyanate can be used. An aliphatic diisocyanate such as a crotonone ester and a polyether polyol (polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) or a polyester polyol (a condensate of adipic acid and ethylene glycol) Polycondensate.

The amount of the other resin is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the polymer (P), more preferably 50 parts by mass or less; In the case of 90 parts by mass or less, preferably 80 parts by mass or less is more preferably 70 parts by mass or less, and in the case of the urethane resin, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less. It is more preferably 70 parts by mass or less. When the range exceeding the respective preference is used, it is difficult to obtain ultraviolet degradation resistance, alkali resistance, acid resistance, workability, and film permeability from the polymer (P).

The medium of the aqueous metal surface treatment agent of the present invention is water.

The aqueous metal surface treatment agent of the present invention may contain a leveling agent for improving film coating properties, a water-soluble solvent for improving film drying property, a rust preventive pigment, a coloring pigment, and a film for improving the effect of the present invention. A filler for liquid or gas phase cerium oxide for density and film hardness; a wax for improving lubricity; and the like.

As the leveling agent, a nonionic or cationic surfactant may be used, such as a polyoxyethylene propylene group or a polypropylene oxide adduct or an acetylene diol compound, for example, in terms of a water-soluble solvent. Examples include alcohols such as ethanol, isopropanol, tertiary butanol, and propylene glycol; esters such as ethyl acetate and butyl acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

The amount of addition of these additives is generally less than 20% by mass based on the solid content of the surface treatment agent.

The ratio of the solid component to the polymer (P) in the aqueous metal surface treatment agent of the present invention, that is, the ratio of the polymer (P) in the dried film is preferably from 10 to 100% by mass, more preferably from 20 to 100 parts by mass. It is preferably 30 to 100% by mass. When the ratio of the polymer (P) is less than 5% by mass, it is difficult to obtain ultraviolet resistance, alkali resistance, acid resistance, workability, and film transparency from the polymer (P).

Further, it is considered that in the present invention, the plasticizer evaporates in the drying step after coating, so that it is considered that a part of the remaining material is obtained, and it is not contained in the solid component.

The minimum film forming temperature at which the aqueous metal surface treatment agent of the present invention is applied to a metal material is preferably -5 to 40 ° C, more preferably 0 to 20 ° C. When the minimum film forming temperature is less than -5 ° C, there is a tendency that storage stability is difficult to obtain. When the minimum film forming temperature exceeds 40 ° C, the film formation is insufficient, and it is difficult to obtain transparency of the film, and it is also difficult to obtain alkali resistance and acid resistance.

The pH of the aqueous metal surface treatment agent of the present invention is preferably from 3 to 12, more preferably from 5 to 10. When the pH is less than 3 or exceeds 12, it is difficult to obtain dispersion stability of the polymer (P).

The solid content concentration in the aqueous metal surface treatment agent of the present invention is not particularly limited, and is preferably from 3 to 50% by mass, more preferably from 5 to 35% by mass. When it is less than 3% by mass, there is a problem in coating properties, and the cost of the treating agent is increased. When it exceeds 50% by mass, the storage stability tends to decrease.

The metal material to which the aqueous metal surface treatment agent of the present invention is applied is not particularly limited, and for example, iron, an alloy mainly composed of iron, aluminum, an alloy mainly composed of aluminum, copper, an alloy mainly composed of copper, or the like may be used. As the plated metal material plated on any metal material, for example, a zinc-based plated steel sheet can be used. The most suitable material for the adaptation of the aqueous metal surface treatment agent of the present invention is a zinc-based plated steel sheet. Examples of the zinc-based plated steel sheet include a zinc-plated steel sheet, a zinc-nickel plated steel sheet, a zinc-iron plated steel sheet, a zinc-chromium plated steel sheet, a zinc-aluminum plated steel sheet, and a zinc-titanium plated steel sheet. Zinc-magnesium plated steel plate, zinc-manganese plated steel plate, zinc-aluminum-magnesium plated steel plate, zinc-aluminum-magnesium-bismuth plated steel plate, etc., and further, in such a plating layer, a small amount of dissimilar metal elements or impurities Containing cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, antimony, bismuth, tin, copper, cadmium, arsenic, etc., may also use dispersed cerium oxide, aluminum oxide, It is obtained from inorganic substances such as titanium dioxide. Further, the above plating and other types of plating, for example, multi-layer plating combined with iron plating, iron-phosphorus plating, nickel plating, cobalt plating, or the like can also be applied. The plating method is not particularly limited, and any of known methods such as a plating method, a hot plating method, a vapor deposition method, a dispersion plating method, and a vacuum plating method can be used.

The aqueous metal surface treatment agent of the present invention is applied to a metal material, preferably at 50 to 250 ° C, more preferably 70 to 150 ° C, and more preferably at a temperature of 100 to 140 ° C (to reach the temperature of the metal material). Dry and suitable for metal materials. When the reaching temperature is less than 50 ° C, the solvent of the aqueous metal surface treating agent is completely non-volatile, and when it is higher than 250 ° C, a part of the film formed by using the aqueous metal surface treating agent tends to be decomposed. The film quality after drying is preferably 0.05 to 5.0 g/m ^{2 , more} preferably 0.2 to 3.0 g/m ^{2 , still more} preferably 0.5 to 2.5 g/m ² . When the film quality is less than 0.05 g/m ² , the properties of the metal material cannot be covered, so that the respective properties cannot be exhibited. When the film thickness is larger than 5.0 g/m ² , scale is generated during processing, and workability is lowered. The tendency.

In the following, the invention will be specifically described by way of examples and comparative examples of the invention, but the invention is not limited thereto.

Manufacture of polymer dispersion (1) Composition of the polymer

The (meth) acrylate (A) used is as follows. Styrene (St) was used as a control for the (meth) acrylate (A).

A1: Acrylic ester

A2: methacrylic acid ester

St: styrene (control)

The ruthenium containing monomer (B) used is as follows.

B1; ethylene tris(methoxyethoxy)decane

B2: 3-propenyloxypropyltrimethoxydecane

B3; 3-methacryloxypropylmethyldimethoxydecane

The α,β-ethylenically unsaturated carboxylic acid (C) used is as follows.

C1: Acrylic

C2: methacrylic acid

The emulsifier used is as follows.

S1: eleminol IS-2 as a reactive emulsifier (manufactured by Sanyo Chemical Co., Ltd.; alkylallyl sulfosuccinate)

S2: LN2025D (manufactured by Teika Co., Ltd.; sodium dodecyl benzoate) as a non-reactive emulsifier

Other single systems used were methyl methacrylate (MMA), 2-ethylhexyl acrylate (2EHA) and butyl acrylate (BA).

(2) Production example of polymer dispersion

After installing a stirrer, a reflux condenser, a dropping funnel, and a thermometer in a four-necked flask, the internal air was replaced with nitrogen, and then 150 parts by mass of ion-exchanged water and eleminol JS-23 parts by mass were charged. Loading the methacrylic acid in the dropping funnel 10 parts by mass of the ester, 44.5 parts by mass of MMA, 37.0 parts by mass of BA, 1 part by mass of ethylene tris(methoxyethoxy)decane, and 4.5 parts by mass of acrylic acid were mixed and used as a mixed monomer. After the temperature of the flask was raised to 70 ° C, 10% by mass of the mixed monomer was placed in a flask, and then 0.3 parts by mass of ammonium persulfate was added. After the completion of the reaction, 90% by mass of the residual mixed monomer was dropped over 3 hours.

After the completion of the dropwise addition, the temperature of the flask was maintained at 75 ° C for 1 hour to obtain a polymer dispersion.

Surface treatment liquid manufacturing (1) Components other than the polymer (P)

The plasticizer used is as follows.

Q1: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate

Q2: Diethylene glycol monobutyl ether acetate

Q3: ethylene glycol monobutyl ether

Q4: Dipropylene glycol mono-n-butyl ether

Q5: N-methyl-2-pyrrolidone (control)

Other resins used are as follows.

R1: hexaethylene glycol type polyether polyurethane resin

R2: bisphenol A type polyether polyurethane resin

(2) Manufacturing example of surface treatment liquid

The polymer dispersion obtained above was cooled to 40 ° C, adjusted to pH 7 with aqueous ammonia, and 30 parts by mass of diethylene glycol monobutyl ether acetate was added to the plasticizer to prepare a surface treatment liquid of Example 25.

(3) Manufacturing of surface treatment liquid

The surface treatment liquid of the example was produced as shown in Table 1, and the surface treatment liquid which is a comparative example is shown in Table 2. Further, the solid content concentration of the surface treatment liquid was adjusted to 30% by mass.

Modulation of test plates (1) Materials

The commercially available materials shown below were used.

Molten zinc plated steel sheet (GI): plate thickness = 0.8 mm, mass per unit area = 60/60 (g/m ² )

Molten zinc-55% aluminum alloy plated steel sheet (GL): sheet thickness = 0.8 mm, mass per unit area = 150/150 (g/m ² )

(2) Degreasing treatment

A fine cleaner-4336 (registered trademark: manufactured by Nippon Parkerizing Co., Ltd.) which is a bismuth hydride alkali degreaser is dissolved in water at a concentration of 20 g/liter, and the resulting solution is sprayed at a temperature of 60 ° C for 2 minutes. It was washed with pure water after 30 seconds of water washing.

(3) The surface treatment liquid of the Example shown in Table 1 and the surface treatment liquid of the comparative example shown in Table 2 were used, and the amount of the film after drying was 1.5 g/m ² by using a bar coater. The material applied to the degreased treatment was dried at a maximum plate temperature of 80 ° C to form a test plate. Evaluation method (1) Storage stability

In the case where each of the surface treatment liquids prepared as described above was allowed to stand in the atmosphere at 40 ° C, the storage stability was evaluated during the gelation period.

(evaluation benchmark)

◎: 6 months or more

○: 3 months or more, less than 6 months

△: 1 month or more, less than 3 months

×: less than 1 month

The performance of each test plate was evaluated by the following evaluation method.

(2) UV degradation resistance

The ultraviolet ray humidifier (UVCON fluorescent lamp ultraviolet wet exposure tester) was irradiated with ultraviolet rays of 365 nm for 4 hours, and then left to stand at an atmospheric temperature of 50 ° C and a humidity of 60% Rh for 2 hours, and 30 cycles were performed. The ultraviolet ray deterioration resistance was evaluated by the color tone change (ΔE) before and after the test.

Tone measurement was performed using a color meter ZE2000 (manufactured by NIPPON DENSHOKU Co., Ltd., light source: halogen lamp 12V/2A). The color tone measurement was also the same in the evaluation of the following alkali resistance and acid resistance.

(evaluation benchmark)

◎: △E<1

○: 1≦△E<3

△: 3≦△E<7

×: 7≦△E

(3) Alkali resistance

The mixture was immersed in a 3 mass% aqueous sodium hydroxide solution at 25 ° C for 1 hour, and the alkali resistance was evaluated by the color change (ΔE) before and after the test.

(evaluation benchmark)

◎: △E<1

○: 1≦△E<3

△: 3≦△E<7

×: 7≦△E

(4) Acid resistance

The 3% by mass of hydrochloric acid at 25 ° C was immersed for 1 hour, and the acid resistance was evaluated by the change in color tone (ΔE) before and after the test.

(evaluation benchmark)

◎: △E<1

○: 1≦△E<3

△: 3≦△E<7

×: 7≦△E

(5) Processability

The workability was evaluated by evaluating the damage morphology of the surface after the draw bead test by the universal testing machine. The drawing conditions were a pressing load of 0.5 ton, a bead front end radius of 5 mm, a bead height of 5 mm, and a drawing speed of 5 cm/sec.

(evaluation benchmark)

◎: no damage

○: There is a slight damage

△: Part of the burnt

×: Fully generated charred

(6) Film transparency

The transparency of the film was evaluated by the change in brightness (ΔL) before and after the surface treatment. The brightness measurement was performed using a color meter ZE2000 (manufactured by NIPPON DENSHOKU Co., Ltd., light source: halogen lamp 12V/2A).

(evaluation benchmark)

◎: -1<△L<1

○: -5<ΔL≦-1, or 1≦△L<5

△: -10<ΔL≦-5, or 5≦△L<10

×: ΔL≦-10, or 10≦△L

The evaluation results are shown in Tables 3 to 6. In Tables 3 to 6, the ultraviolet ray resistance is intended to be resistant to ultraviolet ray deterioration, and it is understood from the comparison between the corresponding examples and the comparative examples that the storage stability and the ultraviolet ray resistance are deteriorated in the case where the necessity is within the scope of the present invention. Compared with those with excellent resistance to alkali, acid, process, and film transparency, when the Tg is too low, alkali resistance, acid resistance, and processability are deteriorated. In the case where the Tg is too high, storage stability and alkali resistance are high. Properties, acid resistance, workability, and film transparency are deteriorated; in addition, when styrene is used instead of (meth) acrylate (A), or as another resin, a substance having a C=C double bond is used, The ultraviolet ray deterioration property is deteriorated. Further, when another (meth) acrylate is used instead of the (meth) acrylate (A), it is understood that alkali resistance, acid resistance, and processability are deteriorated.

Moreover, it is understood from the comparison between the examples that when the ruthenium-containing monomer (B) is used, although the storage stability is lowered, the ultraviolet ray deterioration resistance is increased, and the α,β-ethylenically unsaturated carboxylic acid (C) is used. In this case, there is a tendency to improve ultraviolet ray deterioration resistance, acid resistance, and film transparency. When a reactive emulsifier is used as an emulsifier, it is possible to reduce the same effect as in the case of using a non-reactive emulsifier. The amount of the emulsifier used; in the case of using a suitable plasticizer, it is found that the transparency of the film is excellent as compared with the case of using a plasticizer which is not suitable.

Claims (8)

A metal surface treatment agent comprising a polymer (P), a plasticizer (Q), an emulsifier, and water, wherein the polymer (P) has a (meth)acrylic acid in the molecule a polymerization unit of the ester (A) and a polymerization unit derived from the α,β-ethylenically unsaturated carboxylic acid (C) and having a glass transition temperature of 0 to 70 ° C; the plasticizer (Q) is selected from the group consisting of 2, 2, and 4 At least one of methyl-1,3 pentanediol monoisobutyrate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether, and dipropylene glycol n-butyl ether; P) is dispersed by the emulsifier, and contains 0.5 to 50 parts by mass of the plasticizer (Q) with respect to 100 parts by mass of the polymer (P). The treatment agent according to claim 1, wherein the polymer (P) molecule has a polymerization unit derived from the ruthenium-containing monomer (B) represented by the general formula (III). Wherein R6, R7 and R8 represent mutually independent hydrogen atoms, hydroxyl groups, alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms or alkoxy carbon numbers having 1 to 3 carbon atoms; 1 to 3 alkoxy groups, X represents a group represented by formula (IV) or general formula (V): (wherein R9 represents a hydrogen atom or a methyl group, and R10 represents an alkylene group having 1 to 12 carbon atoms)]. The treating agent of claim 1, wherein the emulsifier is a reactive emulsifier, and is present in the polymer (P) as a polymer unit derived from the reactive emulsifier. Such as the treatment agent of the scope of claim 1, in addition to (meth)acrylic acid In addition to the polymerization unit of the ester (A), the residual constituent units of the polymer (P) are all selected from alkyl (meth) acrylate and hydroxyalkyl (methyl) which do not contain an aromatic ring. A (meth) acrylate of at least one type of hydroxyalkyl (meth) acrylate which is a polymerization unit derived from an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms. Such as the treatment agent of claim 3, in addition to (meth)acrylic acid In addition to the polymerization unit of the ester (A) and the polymerization unit derived from the reactive emulsifier, all of the residual constituent units of the polymer (P) are selected from alkyl (meth) acrylates and hydroxyalkyl groups which do not contain an aromatic ring ( A (meth) acrylate of at least one type of methyl acrylate, which is a polymerization unit derived from an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms. The treating agent according to any one of claims 1 to 5, wherein the (meth)acrylic acid is different from 100 parts by mass of the polymer (P) The ratio of the polymerization unit of the ester (A) is from 0.1 to 50 parts by mass. The treatment agent according to the second aspect of the invention, wherein the ratio of the polymerization unit derived from the ruthenium-containing monomer (B) is from 0.5 to 2.0 parts by mass based on 100 parts by mass of the polymer (P). For example, in the treatment agent of claim 1, wherein the acid value of the polymer (P) is 15 to 30 mg KOH/g.