JPH1136079A - Metal surface treating composition and galvanized steel sheet formed with film treated with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal surface treating comps. having excellent workability, corrosion resistance and finish coating property without the conventional chromium treatment process and a surface treated galvanized steel sheet which is coated with the compsn. and is utilized particularly in the field of household electrical appliances, building materials, automobiles, etc. SOLUTION: This metal surface treating comps. contains, per (A) 100 pts.wt. water-dispersible or water-soluble resin, (B) 10 to 50 pts.wt., by solid content, silica particles, (C) 0.5 to 5.0 pts.wt., by solid content, aminoalkylene phosphonic acid and/or alkyl methane-1-hydroxy-1,1-diphosphonic acid, (D) 1 to 8 pts.wt. lithium silicate and (E) 0.2 to 1.0 wt.% ammonium metavanadate. The film is formed on the galvanized steel sheet by applying the compsn. thereon in such a manner that the dry film weight of 0.5 to 5.0 g/m<2> is attained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal surface treatment composition which is excellent in workability, corrosion resistance and top coatability without a conventional chromium treatment step, and in which this composition is applied, particularly for home appliances, building materials and automobiles. The present invention relates to a surface-treated galvanized steel sheet used in fields such as:

[0002]

2. Description of the Related Art Conventionally, chromate treatment and phosphate treatment have been generally performed to improve the corrosion resistance of metal surfaces. However, chromium toxicity has recently become a social problem. The surface treatment method using chromate involves problems such as scattering of chromate fume in the treatment process, high costs for wastewater treatment equipment, and problems due to elution of chromate from the chemical conversion coating. There is. Hexavalent chromium compounds are available from IARC (International Agency
For example, many public organizations have designated it as a carcinogen for the human body, and it is extremely harmful.

[0003] In the phosphate treatment, zinc phosphate or iron phosphate surface treatment is usually performed. However, for the purpose of imparting corrosion resistance, rinsing treatment with chromic acid is usually performed after phosphoric acid treatment. Therefore, there are problems of chromium treatment, sludge treatment due to reaction accelerator in the phosphating agent, treatment of waste water such as metal ions, and elution of metal ions from the metal to be treated.

[0004] As a surface treatment other than chromate and phosphate treatment, for example, sodium nitrite, sodium borate, imidazole, aromatic carboxylic acid, surfactant and the like are used alone or on a cold-rolled steel sheet or galvanized steel sheet. Although treatment is performed using these in combination, they all have a rust-preventing effect in cold water or in the air, but have poor rust-preventing power when exposed to a high-temperature, high-humidity atmosphere, When it is applied to a galvanized steel sheet, its effect is inferior.

Hitherto, pyrazole compounds have been known as rust preventives (JP-B-43-11531, JP-B-44-143).
25446). In addition, a vaporizable rust inhibitor,
For example, a water-soluble rust inhibitor to which an organic nitrite such as cyclohexylammonium nitrite or diisopropylammonium nitrite is added is known (Japanese Patent Publication No. Sho 44).
-33132). Furthermore, pyrazole compounds and suberic acid, azelaic acid, adipic acid, sebacic acid,
An aqueous solution of a mixture with one or more aliphatic dicarboxylic acids such as brassic acid or the like is adjusted to pH 7 to 7 with aqueous ammonia and an amine.
It is also known that after adjusting to 8, a water-soluble resin and a surfactant are added thereto and used (Japanese Patent Publication No. 61-44592).
Reference).

[0006] These known rust preventives have excellent rust preventive power when exposed to a high-temperature and high-humidity atmosphere, but are exposed to corrosive environments such as salt water or salt water spray specified in JIS Z-2371. Inferior rust resistance in case.

[0007]

The present inventors have conducted intensive studies to develop a pollution-free surface treatment composition which does not use a chromium compound and which solves the disadvantages of the prior art. A coating solution containing silica particles, a specific phosphonic acid, lithium silicate, and ammonium metavanadate is applied to a metal plate and dried, and the coating is a conventional surface treatment agent comprising chromic anhydride and sulfuric acid or nitric acid and fluoride. Chromate obtained by spraying or dipping
The present invention was found to exhibit the same corrosion resistance and topcoating properties as those of a chromic film (chromic chromate), and completed the present invention.

That is, the present invention relates to (A) 100 parts by weight (solid content) of a water-dispersible or water-soluble resin, (B) 10 to 50 parts by weight of silica particles in solid content, (C) aminoalkylenephosphone. Acid and / or alkylmethane-1-hydroxy-1,1-diphosphonic acid in a solid content of 0.5-5.
0 part by weight, (D) 1 to 8 parts by weight of lithium silicate, and (E) 0.2 to 1.0 part by weight of ammonium metavanadate, a metal surface treatment composition,
And coating the composition on a galvanized steel sheet so as to have a dry film weight of 0.5 to 5.0 g / m ² to form a film to provide a surface-treated galvanized steel sheet having excellent corrosion resistance. To provide.

[0009]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the water-dispersible or water-soluble resin (A) can be used without any particular limitation as long as it has a film-forming ability. For example, a water-dispersible or water-soluble acrylic resin , A polyurethane resin, an ethylene / acrylic copolymer, etc., and these can be used alone or in combination.

Among them, as the water-dispersible or water-soluble acrylic resin, a vinyl monomer mixture containing at least one of an acrylate ester and a methacrylate ester is subjected to emulsion polymerization, suspension polymerization or solution polymerization, If necessary, the resin may be a neutralized or aqueous resin or a resin obtained by modifying the resin. Representative examples include the following.

(1) An emulsion obtained by emulsion polymerization of a vinyl monomer mixture in water in the presence of an emulsifier or a high molecular weight resin dispersion stabilizer.

(2) A vinyl monomer mixture containing a carboxyl group-containing monomer or an amino group-containing monomer is solution-polymerized in an organic solvent and neutralized with a neutralizing agent which is a base or an acid. Aqueous one.

The acrylic resin may have a normal temperature crosslinking property. For example, a method of providing a carbonyl group in the acrylic resin and adding a polyhydrazide compound for crosslinking (US Pat. No. 3,345,336) JP-A-63-1
No. 79910) can be used.

The monomer components of the vinyl monomer mixture used for preparing the acrylic resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate (n
-, I-, t-), hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, (meth)
Lauryl acrylate, stearyl (meth) acrylate,
Alkyl or cycloalkyl esters of acrylic acid or methacrylic acid having 1 to 18 (1 to 24) carbon atoms, such as cyclohexyl (meth) acrylate; methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ) C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid, such as ethoxybutyl acrylate; acrylic acid, methacrylic acid, crotonic acid,
Carboxyl group-containing unsaturated monomers such as itaconic acid, maleic acid and fumaric acid; 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth)
C2-8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as acrylates; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and the like; Nitrogen alkyl (meth) acrylate; acrylamide, methacrylamide, N-butoxymethyl (meth) acrylamide,
Polymerizable amides such as N, N-dimethylaminopropyl (meth) acrylamide and N, N-dimethylaminoethyl (meth) acrylamide; epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether Monomer: vinyl acetate, styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, acrylonitrile and the like.

The water-dispersible or water-soluble polyurethane resin includes polyester polyols and polyethers.
Polyurethane consisting of a polyol such as terpolyol and diisocyanate is optionally subjected to a chain in the presence of a chain extender which is a low molecular weight compound having two or more active hydrogens such as diol and diamine. It is elongated and stably dispersed or dissolved in water, and known ones can be widely used (for example, JP-B-42-24192, JP-B-42-2).
No. 4194, JP-B-42-5118, JP-B-49-9
No. 86, Japanese Patent Publication No. 49-33104, Japanese Patent Publication No. 50-15
027, JP-B-53-29175). As a method for stably dispersing or dissolving the polyurethane resin in water, for example, the following method can be used.

(1) A method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, amino group or carboxyl group into a side chain or a terminal of a polyurethane polymer, and dispersing or dissolving in water by self-emulsification.

(2) The reaction-completed polyurethane polymer or terminal isocyanate group is replaced with an oxime, an alcohol,
A method in which a polyurethane polymer blocked with a blocking agent such as phenol, mercaptan, amine, and sodium bisulfite is forcibly dispersed in water using an emulsifier and mechanical shearing force. Further, a method in which a urethane polymer having a terminal isocyanate group is mixed with water / emulsifier / chain extender, and dispersion and high molecular weight are simultaneously performed using mechanical shearing force.

(3) A method in which a water-soluble polyol such as polyethylene glycol is used as a polyol as a main raw material of polyurethane, and is dispersed or dissolved in water as a water-soluble polyurethane.

The above-mentioned dispersion or dissolution method for the polyurethane resin is not limited to a single method, and a mixture obtained by each method can also be used.

Examples of the diisocyanate that can be used for synthesizing the polyurethane resin include aromatic, alicyclic and aliphatic diisocyanates, and specifically, hexamethylene diisocyanate and tetramethylene diisocyanate. Isocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, p-xylylene diisocyanate,
m-xylylene diisocyanate, 1,3- (diisocyanatomethyl) cyclohexanone, 1,4- (diisocyanatomethyl) cyclohexanone, 4,4'-diisocyanatocyclohexanone, 4,4'-methylenebis ( Cyclohexyl isocyanate), isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-naphthalenedi isocyanate, 3,3'-dimethyl- 4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate and the like can be mentioned. Of these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate
, Hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred.

Commercially available polyurethane resins include Hydran HW-330, HW-340 and HW-340.
-350 (all manufactured by Dainippon Ink and Chemicals, Incorporated),
Super Flex 100, 150, F-3438
D (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

Further, the water-dispersible or water-soluble ethylene-acrylic copolymer includes a copolymer of ethylene and a polymerizable unsaturated carboxylic acid, and a polymerizable unsaturated compound in a dispersion of the copolymer. In addition, at least one kind of water-dispersible or water-soluble resin selected from two kinds of resins obtained by emulsion polymerization and further cross-linking within particles can be used.

The above copolymer is a copolymer of ethylene and one or more of unsaturated carboxylic acids such as (meth) acrylic acid and maleic acid. In the copolymer, the content of the unsaturated carboxylic acid is suitably in the range of 3 to 60% by weight, preferably 5 to 40% by weight. When the content is less than 3% by weight, it is difficult to disperse the copolymer in water. On the other hand, when the content is more than 60% by weight, the resulting film becomes insufficient in corrosion resistance and chemical resistance.

The above copolymer can be dispersed in water by neutralizing an acid group in the copolymer with a basic substance. Examples of the basic substance include alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; ammonia, morpholine, triethylamine, and dimethylethanolamine. Particularly, ammonia and lower amines are preferable. .

The aqueous dispersion of the above copolymer is, for example, a mixture of ethylene, a polymerizable unsaturated carboxylic acid, a polymerization initiator and a basic substance used for neutralization in hot water generally at about 60 to 200 ° C. And reacting for about 1 to 8 hours.

The above resin is added to an aqueous dispersion of a copolymer,
It is a crosslinked resin formed by adding a polymerizable unsaturated compound, performing emulsion polymerization, and further performing intra-particle crosslinking. Examples of the polymerizable unsaturated compound include the vinyl monomers listed in the description of the water-dispersible or water-soluble acrylic resin.
The species or two or more species can be appropriately selected and used.

In the above resin, the weight ratio of the solid content of the aqueous dispersion of the copolymer to the polymerizable unsaturated compound is 90/10 to 1%.
Suitably, it is in the range of 0/90.

In the above resin, entanglement and grafting of molecules occur during emulsion polymerization, and further, as a polymerizable unsaturated compound, a reactive group (for example, carboxyl group-epoxy group, amino group-epoxy group) or When di (meth) acrylates or the like are contained, intraparticle crosslinking can be advanced.

After the emulsion polymerization, a crosslinking agent such as methylol melamines, epoxy compounds, imines and aziridines is added to the carboxyl group 1 in the resin solid of the emulsion polymer.
You may add the quantity used as 0.01-1.4 equivalents with respect to equivalents, and may carry out intraparticle crosslinking reaction. The resin can be obtained as described above.

These water-dispersible or water-soluble ethylene
A commercially available acrylic copolymer is Hitec S-3
121, S-3123, S-3125, S-31
27, S-8721 (all manufactured by Toho Chemical Co., Ltd.), Nipporan 3202 and 3203 (all manufactured by Polyurethane Co.), and the like.

In the present invention, the silica particles (B) contribute to improvement in adhesion and corrosion resistance, and have a particle size of 5 to 1
The silica particles have a diameter of 00 nm, preferably 5 to 50 nm, and may be any of silica particles such as fumed silica, pulverized silica, and water-dispersible colloidal silica. Commercial products of water-dispersible colloidal silica include, for example,
Notetex N, Snowtex C, and Snowtex O (all manufactured by Nissan Chemical Industries, Ltd.). Other commercially available silica particles include, for example, AEROSIL 2
00V, R-811 (manufactured by Nippon Aerosil Co., Ltd.) and the like.

In the present invention, aminoalkylenephosphonic acid and / or alkylmethane-1-hydroxy-1,1
Diphosphonic acid (C) contributes to the improvement of corrosion resistance because it captures eluted metal ions to form a strong chelate compound. Examples of aminoalkylenephosphonic acids include nitrilotrismethylenephosphonic acid, Examples include nitrilotrispropylene phosphonic acid, nitrilodiethylmethylenephosphonic acid, and nitrilopropylbismethylenephosphonic acid. Examples of the alkylmethane-1-hydroxy-1,1-diphosphonic acid include methane-1
-Hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, propane-1-hydroxy-1,1-diphosphonic acid and the like.

In the present invention, lithium silicate (D) particularly contributes to the improvement of the corrosion resistance of the end face and the corrosion resistance after processing, and is one of the basic alkali metal salts represented by Li ₂ O.xSiO ₂ . Specifically, the x value is 3.5 (lithium silicate 35), 4.5 (lithium silicate 45), 7.5
(Lithium silicate 75). When the lithium silicate is added, the composition of the present invention generally has a pH of 7.5 to 7.5.
It shows an alkalinity of 10.

In the present invention, ammonium metavanadate (E) serves to passivate the metal surface to improve corrosion resistance and is one type of oxyacid salt.

In the composition of the present invention, (B), (C),
The mixing ratio of the components (D) and (E) is 100 parts by weight (solid content) of the water-dispersible or water-soluble resin (A), respectively.
It is as follows.

Component (B): 10 to 50 parts by weight, preferably 20 to 40 parts by weight (solid content) Component (C): 0.5 to 5 parts by weight, preferably 1.5 to 3 parts by weight (〃) Component (D): 1 to 8 parts by weight, preferably 2 to 5 parts by weight (〃) Component (E): 0.2 to 1 part by weight, preferably 0.3 to 0.5 part by weight (〃) (B When the mixing ratio of the silica particles as the component) is less than 10 parts by weight, the hardness of the obtained film is reduced and the film shows tackiness,
On the other hand, if it exceeds 50 parts by weight, the elongation at break of the obtained film is lowered, and the adhesion to the material and the corrosion resistance are insufficient, which is not preferable. If the blending ratio of component (C) is less than 0.5 parts by weight, the resulting coatings are inferior in corrosion resistance. On the other hand, if it exceeds 50 parts by weight, the pH values of the coatings themselves are as low as 1.8 or less. Is not preferred because the pH decreases and the corrosion resistance decreases.

If the proportion of lithium silicate as the component (D) is less than 1 part by weight, the corrosion resistance of the obtained film is inferior, while if it exceeds 8 parts by weight, adhesion to the material, corrosion resistance,
It is not preferable because the suitability for overcoating is insufficient. When the compounding ratio of the component (E) is less than 0.2 part by weight, the corrosion resistance of the obtained film is poor. Absent.

The composition of the present invention may further comprise, if necessary,
Chelating agents such as titanium chelate; crosslinking agents such as 1,2,4-triazole, 2-allylthiourea, melamine resin, urea resin, blocked polyisocyanate compound; neutralization of amine compound and the like Agent: A reaction accelerator, a thickener, an antifoaming agent, an organic solvent and the like can be appropriately contained.

The composition of the present invention can be applied to a metal plate, and in particular, can be applied to a galvanized steel sheet to form a film, whereby a surface-treated galvanized steel sheet having excellent corrosion resistance and overcoating properties can be obtained. it can.

The galvanized steel sheet includes a hot-dip galvanized steel sheet, an electro-galvanized steel sheet, an iron-zinc alloy-coated steel sheet, a nickel-zinc alloy-plated steel sheet, and an aluminum-coated steel sheet.
Zinc alloy-plated steel sheets (eg, galvanized steel sheets and galvanized steel sheets) and chemical conversion-treated zinc obtained by subjecting these zinc-based coated steel sheets to a chemical conversion treatment such as zinc phosphate treatment or chromate treatment. System-plated steel sheet.

The coating amount of the composition of the present invention to zinc-plated steel sheet, dry film weight at 0.5 to 5 g / m ^2, preferably in a range of 0.7 to 2.5 g / m ² Appropriate. When the dry film weight is less than 0.5 g / m ² , the corrosion resistance is not sufficient. On the other hand, even if the coating weight exceeds 5 g / m ² , further improvement in the performance corresponding thereto cannot be seen.

When the composition of the present invention is applied to a galvanized steel sheet to form a film, the viscosity of the composition of the present invention with a diluent such as water is adjusted to, for example, 5 to 20 centipoise (c) depending on the amount of application.
ps), and after coating by a known method such as roll coating, spray coating, dipping coating, brush coating or the like so as to have a predetermined film weight, the ambient temperature is usually 150 to 330. What is necessary is just to dry at 10 degreeC for 10 to 100 seconds. The ultimate temperature of the steel sheet at this time (PMT, Pe
ak Metal Temperature) is preferably in the range of 100 to 150 ° C.

An upper layer film can be further formed on the zinc-coated steel sheet formed as described above. The upper layer film-forming composition may be appropriately selected depending on the purpose, and various film-forming compositions can be used. Examples of the film-forming composition include conventionally known film-forming compositions used for rust-proof steel sheets, fingerprint-resistant steel sheets, lubricating steel sheets, and colored coatings.

[0044]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. In the following description, “part” and “%”
Represents "parts by weight" and "% by weight" unless otherwise specified.

Production of water-dispersible resin Production Example 1 "Primacol 5983" (Ethylene-α, β-unsaturated carboxylic acid copolymer, manufactured by Dow Chemical Company) was placed in a reaction vessel.
400 g, 36 g of 28% ammonia water, 1,200 water
g, and the inside of the container was purged with nitrogen, and then the temperature was increased.
After maintaining at 150 ° C. for 3 hours, the mixture was cooled to obtain an ethylene-acrylic copolymer dispersion.

To this dispersion, 4 g of potassium persulfate was added
A solution dissolved in 20 g was added, and the temperature was raised to 80 ° C. Into this, a mixture of 40 g of methyl methacrylate, 36 g of butyl methacrylate, 8 g of methacrylic acid, and a solution of 4 g of potassium persulfate in 100 g of water were added dropwise over 1 hour. 30 minutes after the completion of the dropwise addition, the crosslinking agent “Epicoat 2”
56 "(epoxy compound, manufactured by Yuka Shell Co., Ltd.) was added, and the mixture was aged at 80 ° C for 3 hours. The obtained emulsion is crosslinked in the particles, and has a nonvolatile content of 25% and a pH of 25%.
9.2.

Production Example 1 of Metal Surface Treatment Composition Emulsion 200 having a solid content of 25% obtained in Production Example 1 above.
Parts (solid content 50 parts), "Yodosol AD-57" (Note 1) 50 parts (solid content 25 parts), "Snow-Tex N"
(Note 3) 125 parts (solid content 25 parts), nitrilotrismethylene phosphonic acid 2 parts, “lithium silicate 35” (Note 1)
0) 2 parts and 0.5 part of ammonium metavanadate were blended and uniformly mixed, and then the solid content was reduced to 20 with deionized water.
% To obtain a metal surface treatment composition.

Examples 2 to 11 and Comparative Examples 1 to 10 In Example 1, the solid content composition (parts by weight) of the metal surface treatment composition was as shown in Table 1 below, and the solid content was adjusted with deionized water. Was performed in the same manner as in Example 1 to obtain a metal surface treatment composition. Table 1 shows the solid content. (Note) in Table 1 is as follows.

(Note 1) Iodosol AD-57: an acrylic emulsion having a solid content of 50%, manufactured by Kanebo NSC, T
g 60 ° C., MFT 60 ° C. (Note 2) Superflex 150: a non-yellowing type polyurethane emulsion of 30% solid content, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Tg 55 ° C. (Note 3) Snowtex N: Nissan Chemical Co., solid content 20
% Colloidal silica aqueous dispersion (ammonia neutralized), particle size 10 to 20 nm (Note 4) NTMP: Nitrilotrismethylene phosphonic acid (Note 5) NTPP: Nitrilotris propylene phosphonic acid (Note 6) NDEMP: Nitrilo diethyl methylene phosphone Acid (Note 7) M-1-H-1,1-DP: methane-1-hydroxy-1,1-diphosphonic acid (Note 8) E-1-H-1,1-DP: ethane-1-hydroxy -1,1-diphosphonic acid (Note 9) P-1-H-1,1-DP: propane-1-hydroxy-1,1-diphosphonic acid (Note 10) Lithium silicate 35: Nihon Kagaku Kogyo Co., Ltd., Li
_{2 O.3.5} SiO ₂ (Note 11) Lithium silicate 45: Nihon Kagaku Kogyo, Li
₂ O · _4.5 SiO ₂ (Note 12) Lithium silicate 75: manufactured by Nippon Chemical Industry Co., Ltd.
₂ O ・_7.5 SiO ₂

[0050]

[Table 1]

[0051]

[Table 2]

Coating Process Examples 12 to 41 and Comparative Examples 1 to 28 Using the metal surface treatment compositions obtained in the above Examples and Comparative Examples, forming a treated film on a galvanized steel sheet according to the following procedure as shown in Table 2. And an upper layer film was formed on the treated film according to the following procedure as shown in Table 3 to obtain each surface-treated galvanized steel sheet. The obtained steel plate was subjected to a performance test as a test plate. Table 2 shows the results.

Types of galvanized steel sheet ・ Electro galvanized steel sheet (hereinafter abbreviated as “EG”) Plate thickness 0.6 mm Coating weight 20 g / m ²・ Hot-dip galvanized steel sheet (hereinafter abbreviated as “HDG”) Plate thickness 0.6 mm Plating weight 120 g / m ² Degreasing Alkali degreasing agent “CC-” manufactured by Nippon CV Chemicals
561B "(sodium silicate No. 3 equivalent) as an aqueous dispersion having a concentration of 2%, sprayed at a liquid temperature of 65 ° C for 60 seconds, degreased the surface of the galvanized steel sheet, and then heated with hot water at a liquid temperature of 50 ° C for 20 seconds. It was sprayed and washed with hot water.

Application of Metal Surface Treatment Composition The degreased galvanized steel sheet is subjected to electrolytic chromate treatment, if necessary, and the metal surface treatment composition obtained in the above Examples and Comparative Examples is applied to the surface of the galvanized steel sheet. Was applied at the dry film weight shown in Table 2 below, and dried at an ambient temperature of 290 ° C. for 10 seconds (the maximum temperature of the steel sheet was 110 ° C.) to form a treated film.

Formation of Upper Layer Film An upper layer film was formed on the galvanized steel sheet on which the above-mentioned treated film had been formed by one of the following methods A and B as required.

A. "Amirac # 1000 White" (manufactured by Kansai Paint Co., Ltd., thermosetting alkyd resin paint, white) was applied on the galvanized steel sheet on which the treated film was formed so as to have a dry film thickness of 30 μm. Bake for a minute.

B. "Magiclon # 1000 White" (Kansai Paint Co., Ltd., thermosetting acrylic resin paint, white) was applied on the galvanized steel sheet on which the treated film was formed so as to have a dry film thickness of 30 [mu] m. Bake for a minute.

Test method Corrosion resistance: The end face and the back face of the test plate were sealed and subjected to salt spray test (JIS Z-2371) at 48, 72, 12
After 0, 240 and 360 hours, the state of white rust on the test plate surface was evaluated.

：: No white rust generated ○: White rust generated 5% △: White rust generated 5 to 10% ×: White rust generated 10% or more XX: White rust generated on the entire surface Topcoat adhesion: test The adhesion of the upper layer coating of the plate was evaluated by performing a Goban-like cellophane test.

◎: No peeling of upper film was observed. ○: Peeling of one or two upper films was observed. Δ: Peeling of three to ten upper films was observed. ×: Ten or more upper films were observed. Peeling is observed

[0061]

The film obtained from the composition of the present invention has excellent adhesion to galvanized steel sheets and excellent corrosion resistance even without containing a hexavalent chromium compound. Therefore, it can be sufficiently used as a non-chromium surface treatment agent containing no hexavalent chromium compound which is harmful to the working environment and hygiene.
Further, when the composition of the present invention is applied to a conventional electrolytic chromate-treated plate, the corrosion resistance can be further improved.

Further, by coating the composition for forming an upper layer film according to various purposes on the film of the zinc-plated steel sheet on which a film obtained from the composition of the present invention has been formed to form an upper layer film, corrosion resistance, It is possible to obtain a multi-layer surface-treated galvanized steel sheet having excellent adhesion and the above purpose.

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

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[Procedure amendment]

[Submission date] October 6, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

In the present invention, the silica particles (B) contribute to improvement in adhesion and corrosion resistance, and have a particle size of 5 to 1
The silica particles have a diameter of 00 nm, preferably 5 to 50 nm, and may be any of silica particles such as fumed silica, pulverized silica, and water-dispersible colloidal silica. Commercial products of water-dispersible colloidal silica include, for example,
Tex N, Sno-Tex C, Sno-Tex O (all manufactured by Nissan Chemical Industries, Ltd.) and the like. Other commercially available silica particles include, for example, AEROSIL 2
00V, R-811 (manufactured by Nippon Aerosil Co., Ltd.) and the like.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

Component (B): 10 to 50 parts by weight, preferably 20 to 40 parts by weight (solid content) Component (C): 0.5 to 5 parts by weight, preferably 1.5 to 3 parts by weight (〃) Component (D): 1 to 8 parts by weight, preferably 2 to 5 parts by weight (〃) Component (E): 0.2 to 1 part by weight, preferably 0.3 to 0.5 part by weight (〃) (B When the mixing ratio of the silica particles as the component) is less than 10 parts by weight, the hardness of the obtained film is reduced and the film shows tackiness,
On the other hand, if it exceeds 50 parts by weight, the elongation at break of the obtained film is lowered, and the adhesion to the material and the corrosion resistance are insufficient, which is not preferable. If the compounding ratio of the component (C) is less than 0.5 parts by weight, the resulting coatings have poor corrosion resistance. On the other hand, if it exceeds 5 parts by weight, the pH value of the coatings themselves is as low as 1.8 or less. Is not preferred because the pH decreases and the corrosion resistance decreases.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction contents]

Coating Process Examples 12 to 41 and Comparative Examples 11 to 28 Using the metal surface treatment compositions obtained in the above Examples and Comparative Examples, forming a treated film on a galvanized steel sheet according to the following procedure as shown in Table 2. And an upper layer film was formed on the treated film according to the following procedure as shown in Table 3 to obtain each surface-treated galvanized steel sheet. The obtained steel plate was subjected to a performance test as a test plate. The results are shown in Tables 2 and 3.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction contents]

◎: No white rust generated ○: Less than 5% of white rust generated △: 5 to 10% of white rust generated ×: 10% or more of white rust generated Overcoat adhesion: Adhesion of upper layer coating on test plate Was evaluated by performing a Goban order serothepe test.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction contents]

◎: No peeling of the upper film was observed. ○: Peeling of one or two upper films was observed. Δ: Peeling of 3 to 9 upper films was observed. ×: 10 or more upper films were observed. Peeling is observed

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/5317 C08K 5/5317 C08L 101/14 C08L 101/14 C09D 5/00 C09D 5/00 D 5/08 5/08 7 / 12 7/12 Z 201/00 201/00 C23C 22/48 C23C 22/48

Claims (3)

[Claims] 1. A method according to claim 1, wherein 100 parts by weight (solid content) of the water-dispersible or water-soluble resin (A) is 10 to 50 parts by weight of (B) silica particles in solid content, (C) aminoalkylenephosphonic acid and / or Or alkylmethane-1-hydroxy-1,1
-0.5 to 5.0 parts by weight of diphosphonic acid in solid content;
A metal surface treatment composition comprising (D) 1 to 8 parts by weight of lithium silicate and (E) 0.2 to 1.0 part by weight of ammonium metavanadate. 2. On a zinc-based galvanized steel sheet, based on 100 parts by weight (solid content) of (A) a water-dispersible or water-soluble resin,
(B) 10 to 50 parts by weight of silica particles in solid content,
(C) 0.5 to 5.0 parts by weight of solid content of aminoalkylenephosphonic acid and / or alkylmethane-1-hydroxy-1,1-diphosphonic acid, and (D) 1 part of lithium silicate
The metal surface treatment composition comprising ８8 parts by weight and (E) 0.2-1.0 parts by weight of ammonium metavanadate has a dry film weight of 0.5-5.0 g / m ^2. Surface-treated galvanized steel sheet with excellent corrosion resistance, formed by applying a coating. 3. A multi-layer surface-treated galvanized steel sheet, further comprising an upper film formed on the metal film treated film according to claim 2.