JP2000248380A - Production of non-chromium type treated galvanized steel sheet - Google Patents

Production of non-chromium type treated galvanized steel sheet

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Publication number
JP2000248380A
JP2000248380A JP11375602A JP37560299A JP2000248380A JP 2000248380 A JP2000248380 A JP 2000248380A JP 11375602 A JP11375602 A JP 11375602A JP 37560299 A JP37560299 A JP 37560299A JP 2000248380 A JP2000248380 A JP 2000248380A
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JP
Japan
Prior art keywords
steel sheet
coating film
compound
film
containing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP11375602A
Other languages
Japanese (ja)
Inventor
Toshinobu Akagawa
Takeshi Miyake
Toshiaki Shimakura
Toshiaki Takamatsu
Koji Tanimura
Katsuyoshi Yamazoe
豪 三宅
勝芳 山添
俊明 島倉
宏治 谷村
敏伸 赤川
利明 高松
Original Assignee
Nippon Paint Co Ltd
Nippon Steel Corp
新日本製鐵株式会社
日本ペイント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP37705098 priority Critical
Priority to JP10-377050 priority
Application filed by Nippon Paint Co Ltd, Nippon Steel Corp, 新日本製鐵株式会社, 日本ペイント株式会社 filed Critical Nippon Paint Co Ltd
Priority to JP11375602A priority patent/JP2000248380A/en
Publication of JP2000248380A publication Critical patent/JP2000248380A/en
Application status is Pending legal-status Critical

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Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a non-chromium type treated galvanized steel sheet excellent in corrosion resistance without being incorporated with harmful hexavalent chromium. SOLUTION: On the surface of a galvanized steel sheet or a galvannealed steel sheet as a substrate, (a) a coating film contg. a water based resin and at least one kind among a thiocarbonyl group, a vanadic acid and a phosphoric acid compd. or (b) a coating film contg. a water based resin, a thiocarbonyl group-contg. compd. and particulate silica is formed, and this coating film is dried and baked in such a manner that the arrival temp. is controlled to 50 to 250 deg.C to form a non-chromium type rust preventive film. The coating film in the (a) may optionally be mixed with particulate silica.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to home appliances, construction materials,
The present invention relates to a method for producing a non-chromium-type treated galvanized steel sheet which does not contain hexavalent chromium and has excellent corrosion resistance, which is used for automobiles and the like.

[0002]

2. Description of the Related Art A galvanized steel sheet or a zinc alloy-coated steel sheet, in an atmosphere containing salt such as seawater or a high-temperature and high-humidity atmosphere, has white rust on its surface and significantly impairs its appearance.
The rust-preventive force on the base iron surface is reduced.

In order to prevent white rust, a chromate-based rust preventive agent has conventionally been used.
No. 370 describes a resin-based treating agent comprising a water-dispersible chromium compound and water-dispersible silica in an olefin-α, β-ethylenically unsaturated carboxylic acid copolymer resin dispersion.

[0004] Such a film made of a chromate-based treating agent is recognized as having the best corrosion resistance among known treating agents. Nevertheless, the film formed by the chromate treatment contains hexavalent chromium, which is known to be a harmful element. Therefore, there is a need for a non-toxic or low-toxic rust-resistant zinc-based galvanized steel sheet that does not contain hexavalent chromium. Is growing.

[0005] Non-chromium rust preventive agents containing no harmful chromium are disclosed in JP-A-8-239776 and JP-A-8-6.
Patent No. 7834 discloses a method in which sulfide or sulfur is used as a rust preventive component. However, not only sulfur but also some sulfides give off a peculiar odor, and handling of these treating agents was not always easy.

[0006] A treating agent using a triazine thiol compound containing a sulfur atom but having no odor or toxicity has also been proposed. For example, Japanese Patent Application Laid-Open No. 31737/1983 discloses an aqueous solution containing a dithiol-S-triazine derivative. An anticorrosive paint is disclosed. However, this water-soluble anticorrosive paint
It is intended to prevent corrosion of mild steel, copper, brass, etc., and is particularly prepared so that the base material is more easily adhered to copper or brass. Therefore, it is not sufficient as a rust inhibitor for metal surfaces such as zinc.

JP-A-61-223062 describes a reactive emulsion of a compound obtained by mixing a thiocarbonyl group-containing compound with an organic compound which is hardly soluble or insoluble in water. However, this emulsion also
It reacts with copper, nickel, tin, cobalt, aluminum and the like and their alloys, and is still insufficient as a rust inhibitor for metal surfaces such as zinc.

The applicants of the present application have disclosed in Japanese Patent Application No. 9-2557 a triazinethiol-containing rust-preventive coating agent which is also effective for rust-prevention of galvanized steel sheets. However, triazine thiol is an expensive compound, so it would be beneficial to have a less expensive rust inhibitor.

As a surface treatment method for zinc or zinc alloy which does not contain chromium and does not use triazine thiol,
JP-A-54-71734 and JP-A-3-2265.
No. 84 is disclosed. JP-A-54-
No. 71734 discloses a treatment method comprising preparing 2 to 6 bonded phosphate esters of myo-inositol or a salt thereof in 0.5.
And at least one of titanium fluoride and zirconium fluoride is 0.5 to 30 g in terms of metal.
/ L and an aqueous solution containing 1 to 50 g / l of thiourea or a derivative thereof for surface-treating zinc or a zinc alloy. This method requires titanium fluoride or zirconium fluoride to form a passivation film as a protective layer on the zinc surface. JP-A-3-226584 discloses that one or both of Ni 2+ and Co 2+ is 0.02 g / l.
A surface treatment agent that is an aqueous solution having a pH of 5 to 10 containing the above and at least one of the compounds having ammonia and a primary amine group is used. This treatment agent requires one or both of Ni 2+ and Co 2+ to impart coating adhesion and corrosion resistance after coating by depositing cobalt or nickel. The treating agents containing these metal ions have disadvantages such as an increase in load during wastewater treatment.

[0010]

As described above, conventional rust inhibitors containing no chromium are inferior to chromium-containing rust inhibitors in terms of corrosion resistance, and have other disadvantages as described above. Was. So, instead of chromium-containing rust inhibitor,
Moreover, as a new rust preventive agent free from the above-mentioned inconveniences, the applicants have heretofore described (1) a rust preventive coating agent containing an aqueous resin, a thiocarbonyl group-containing compound and a phosphate ion, and optionally containing finely divided silica ( Japanese Patent Application No. 10-36264
), (2) an aqueous resin, a rust-preventive coating agent containing a thiocarbonyl group-containing compound and finely divided silica and containing no phosphate ion (Japanese Patent Application No. 10-36265), (3) an aqueous resin and a vanadate compound And, optionally, a rust-preventive coating (Japanese Patent Application No. 10-36267) further comprising at least one of a thiocarbonyl group-containing compound, a phosphate ion and finely divided silica.

These new rust preventive coating agents do not contain chromium and have excellent corrosion resistance, so that they can be used as rust preventive agents for galvanized or zinc alloy plated steel sheets in place of conventional toxic chromate treatment agents. There is expected.

Generally, a galvanized or zinc alloy-plated steel sheet which has been subjected to a rust-proof treatment is manufactured by applying a rust-preventive coating agent to a zinc-plated or zinc-alloy-plated steel sheet as a base, and then drying and baking the coating film. . In order to obtain the desired excellent corrosion resistance of a zinc-coated steel sheet treated with the above-mentioned new rust-preventive coating agent, it is necessary to optimize the conditions relating to the production.

Accordingly, an object of the present invention is to provide a manufacturing method for a galvanized or zinc alloy-coated steel sheet provided with these new rust-proof coatings.

[0014]

According to the present invention, there is provided a method for producing a non-chromium treated zinc-coated steel sheet, comprising: a zinc-coated steel sheet or a zinc-alloy-coated steel sheet as a base; Forming a coating containing at least one of a group-containing compound, a vanadate compound and a phosphate compound, or (b) a coating containing an aqueous resin, a thiocarbonyl group-containing compound and finely divided silica; The coating is dried and baked at a temperature of 50 to 250 ° C. to form a chromium-free rust preventive film.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the manufacturing method of the present invention, a steel sheet whose surface is subjected to zinc plating or zinc alloy plating is used as a base. Specifically, zinc plating or one or two of zinc and iron, nickel, cobalt, chromium, magnesium, aluminum, silicon, manganese, etc.
It refers to a cold-rolled steel sheet or a hot-rolled steel sheet that has been subjected to alloy plating consisting of at least one kind, and the plating method is not particularly limited, and may be any of an electroplating method, a hot-dip plating method, and a vacuum plating method. Here, zinc plating and zinc alloy plating are collectively referred to as “zinc-based plating”.

Before forming a rust preventive film on this steel sheet,
For example, any surface treatment such as degreasing may be performed.

The coating film formed on the underlying zinc-coated steel sheet is (a) a coating film containing an aqueous resin and at least one of a thiocarbonyl group-containing compound, a vanadate compound and a phosphate compound; Or (b) a coating film containing an aqueous resin, a thiocarbonyl group-containing compound and fine silica. Among these, the coating film of (a) is (1) a coating agent containing an aqueous resin, a thiocarbonyl group-containing compound and a phosphate compound in water, and (2) a coating agent containing an aqueous resin and a vanadate compound in water. (3) a coating agent containing an aqueous resin, a thiocarbonyl group-containing compound, a vanadate compound and a phosphate compound in water, or (4) a coating agent containing an aqueous resin and a phosphate compound in water. Optionally, each coating can optionally include finely divided silica.

The composition of each component in each coating agent is preferably such that the composition in the rust preventive film obtained after drying and baking is as follows.

When a coating agent containing an aqueous resin, a thiocarbonyl group-containing compound and a phosphoric acid compound (the coating agent of the above (1)) is used in water, the film obtained after drying and baking has a solid content of an aqueous resin. Based on 100 parts by weight of the organic resin obtained by curing or crosslinking the resin, 0.1 to 50 parts by weight of the thiocarbonyl group-containing compound and 0.01 to 20 parts by weight of the phosphoric acid compound (as PO4) (more preferably 0 to 4 parts by weight). .5~5 parts including (as PO 4)).

Coating agent containing aqueous resin and vanadate compound in water (coating agent of (2) above)
When using, the film obtained after drying and baking,
The solid content contains 0.1 to 20 parts by weight of a vanadate compound based on 100 parts by weight of an organic resin obtained by curing or crosslinking an aqueous resin.

When a coating agent containing the aqueous resin, the thiocarbonyl group-containing compound, the vanadate compound and the phosphate compound (the coating agent of the above (3)) is used in water, the film obtained after drying and baking is a solid. For example, 0.1 to 50 parts by weight of a thiocarbonyl group-containing compound and 0.1 to 20 parts by weight of a vanadate compound per 100 parts by weight of an organic resin obtained by curing or crosslinking an aqueous resin.
Parts by weight and 0.01 to 20 parts by weight of a phosphate compound (PO 4
As) (more preferably 0.5 to 5 parts by weight (as PO 4) containing).

When a coating agent containing an aqueous resin and a phosphate compound (the coating agent of the above (4)) is used in water, the film obtained after drying and baking is converted into a solid content by curing or crosslinking of the aqueous resin. Phosphoric acid compound 0.01 to 2 parts per 100 parts by weight of obtained organic resin
0 parts by weight (as PO 4 ) (more preferably 0.5 to 5
Parts by weight (as PO 4 ).

When the above-mentioned film contains fine silica as an optional component, its content is determined by the organic resin 10 as a solid content.
1 to 500 parts by weight, preferably 10 to 1 parts by weight per 0 parts by weight
It may be 00 parts by weight.

In the case of a coating film containing the aqueous resin, the thiocarbonyl group-containing compound and the fine silica (the coating film (b)),
That is, based on 100 parts by weight of an organic resin obtained by curing or drying an aqueous resin, 0.1 to 50 parts by weight of a thioiocarbonyl group-containing compound and 1 to 5 parts by weight of fine silica are used.
00 parts by weight, preferably 10 to 100 parts by weight.

As described above, the rust-preventive film is based on an organic resin, and the organic resin is dried and dried after applying a composition containing an aqueous resin and other components of the rust-preventive film in water to the underlying plated steel sheet. It is obtained by curing or crosslinking the aqueous resin by baking. The term “aqueous resin” used herein refers to a water-soluble resin, as well as a water-insoluble resin that is originally water-insoluble but can be in a finely dispersed state in water, such as an emulsion or a suspension. Include it.

Examples of the resin which can be used as the aqueous resin in the present invention include polyolefin resins, acrylic olefin resins, polyurethane resins, acrylic resins, polycarbonate resins, epoxy resins, polyester resins, alkyd resins, Phenolic resin,
Other heat-curable resins can be exemplified, and a crosslinkable resin is more preferable. Particularly preferred resins are
An acrylic olefin resin, a polyurethane resin, and a mixed resin of both. The aqueous resin may be used as a mixture of two or more types or by copolymerization.

The thiocarbonyl group-containing compound in the present invention is a thiocarbonyl group represented by the following formula:

[0028]

Embedded image

A compound having the following formula: Typically,

Embedded image

Thiourea and its derivatives, for example, methylthiourea, dimethylthiourea, ethylthiourea, diethylthiourea, diphenylthiourea, thiopental, thiocarbazide, thiocarbazones, thiocyanuric acids, thiohydantoin, 2-thiouramil,
Such as thiourazole,

[0031]

Embedded image

A thioamide compound represented by the formula:
Is, for example, H, CH 3 , C 2 H 5 , C 6 H 5 , C
8 H 5 , C 5 H 3 SO, etc.), for example, thioformamide, thioacetamide, thiopropionamide,
Thiobenzamide, thiocarbostyril, thiosaccharin, etc.

[0033]

Embedded image

(Wherein R represents, for example, H or CH 3 ), for example, thioformaldehyde, thioacetaldehyde, etc.

[0035]

Embedded image

Carbothioic acids represented by the formula (R in the formula:
For example, CH 3 , C 6 H 5, etc.), for example, thioacetic acid, thiobenzoic acid, dithioacetic acid and the like,

[0037]

Embedded image

Thiocarbonates represented by the following formulas and other compounds having the structure of the formula (1), for example, thiocoumazone,
Thiocmotiazone, thionin blue J, thiopyrone, thiopyrine, thiobenzophenone and the like are exemplified.

As the vanadate compound, for example, ammonium vanadate, sodium vanadate, potassium vanadate and the like can be used.

As the phosphate compound, any compound containing phosphate ions may be used. For example, ammonium phosphate, sodium phosphate, potassium phosphate and the like can be used.

The fine silica used in the present invention is:
Silica having such characteristics that it can maintain a stable water-dispersed state when dispersed in water because it has a fine particle size, and has a property such that sedimentation is not recognized semipermanently.
The finely divided silica is not particularly limited as long as it has a small amount of impurities such as sodium and is weakly alkaline. For example, "Snowtex N" (manufactured by Nissan Chemical Industries, Ltd.) and "Adelite AT-20N" (manufactured by Asahi Denka Kogyo).
And commercially available silica sol, or commercially available aerosil powdered silica. The smaller the particle size of silica, the better the corrosion resistance.

The rust preventive film of the present invention may contain components other than the above components. For example, pigments, surfactants and the like can be mentioned. Further, in order to improve the affinity between the organic resin and the silica particles and the pigment, and further to improve the adhesion between the organic resin and the base zinc-coated steel sheet, a silane coupling agent or a hydrolysis condensate thereof or both of them. May be blended. Here, the “hydrolysis condensate of a silane coupling agent” refers to an oligomer of a silane coupling agent obtained by subjecting a silane coupling agent to a raw material and hydrolyzing and polymerizing the same.

As the pigment, for example, titanium oxide (Ti
O 2 ), zinc oxide (ZnO), zirconium oxide (Zr
O 2 ), calcium carbide (CaCO 3 ), barium sulfate (BaSO 4 ), alumina (Al 2 O 3 ), kaolin clay, carbon black, iron oxide (Fe 2 O 3 , Fe 3
Inorganic pigments such as O 4 ) and various coloring pigments such as organic pigments can be used.

The silane coupling agent which can be used in the present invention is not particularly limited, but preferred examples include the following: vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, Vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) ) -3-
(Triethoxysilyl) -1-propanamine, N,
N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,
N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane.

Particularly preferred silane coupling agents are vinyltrimethoxysilane, vinylethoxysilane, 3-
Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)
-3- (triethoxysilyl) -1-propanamine,
N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine. One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

In the present invention, the silane compound is added in an amount of 0.1 to 1 liter of a composition containing an aqueous resin and water as main components.
It is used at a concentration of from 02 to 20 g, preferably from 0.1 to 2.5 g. If the addition amount of the silane compound is less than 0.02 g, the effect of the addition is reduced, and the effect of improving the corrosion resistance and the adhesion of the top coat is insufficient. If it exceeds 20 g, the storage stability is lowered, which is not preferable.

In order to form a coating film from a coating agent based on an aqueous resin, first, a coating agent composition containing predetermined components in water is applied to a galvanized steel sheet. The method of applying the rust preventive coating agent is not particularly limited, and generally used air knives, curtain coats, roll coats, air sprays, airless sprays, immersion and the like can be employed.

The coating composition for forming a coating film can be prepared at any concentration. Generally, a coating composition containing 1 to 80 parts by weight of a solid content (a component other than water) and 99 to 20 parts by weight of water is preferable from the viewpoint of application and subsequent heating and drying.

Next, the coating film thus formed was placed in an open furnace,
Known heating furnaces such as hot blast stoves, induction heating furnaces, near-infrared furnaces,
Alternatively, drying and baking are performed by heating using a combination thereof. By heating the coating film, moisture is removed from the coating film, and when the aqueous resin is a curable resin, it is cured, and when the aqueous resin is a crosslinkable resin, it is crosslinked to form an organic resin for a rust-preventive film. I do. Depending on the type of the aqueous resin used, curing or cross-linking with energy rays such as ultraviolet rays or electron beams may be used in combination.

When the coating film is dried and baked in a direct-fired furnace, the corrosion resistance and solvent resistance of the non-chromium treated galvanized steel sheet of the obtained product are the same as those using the same rust preventive coating agent. It was confirmed that the heating method was improved as compared with the case where the heating method was adopted. Therefore, for applications where better corrosion resistance and solvent resistance are required for the product steel sheet, it is advantageous to perform drying and baking in a direct fire furnace.

When forming a rust-preventive film by drying and baking a coating film of a coating agent, the ultimate temperature (final heating temperature) of the underlying zinc-based plated steel sheet must be 50 to 250 ° C. If the temperature is lower than 50 ° C., the water in the paint is not sufficiently evaporated, and the cured and cross-linked state of the resin is insufficient, and the properties required for the product, particularly the film adhesion and corrosion resistance, are inferior. I will. On the other hand, if the temperature exceeds 250 ° C., thermal decomposition of the organic resin occurs, so that the SST
Not only the corrosion resistance typified by water resistance and water resistance is lowered, but also the resin itself may be discolored to impair the appearance. The ultimate temperature is more preferably from 70 to 200C.

The temperature rise rate for drying and baking to form a rustproof film is preferably 40 ° C./sec or less. If the temperature is raised faster than 40 ° C./sec, a phenomenon that only the surface of the coating film is dried occurs, and a coating film defect called armpit blocking may occur. On the other hand, if the temperature is 40 ° C./sec or less, a good product can be produced without affecting the product performance at a heating rate. An increase in the length of the drying furnace, which is not preferable in terms of equipment, or a reduction in the production speed, results in a decrease in productivity, which is also not preferable. Therefore, in practical operation, the temperature is preferably 5 ° C./sec or more.

It is preferable that the dry film thickness of the rust preventive film is 0.2 μm or more. If it is less than 0.2 μm, the rust prevention (corrosion resistance) is insufficient. On the other hand, when the film thickness exceeds 5 μm,
Further improvement in rust prevention (corrosion resistance) is not recognized so much, which is uneconomical. Therefore, the upper limit of the film thickness is suitably 5 μm. The more preferable dry film thickness of the rust preventive film is 0.5 to 3 μm.

The chromium-free treated zinc-coated steel sheet produced by the method of the present invention may be used in addition to the above-mentioned rust-preventive film, for example, in order to enhance the adhesion of the rust-preventive film to the base steel sheet. An undercoating layer disposed between the film and a topcoat layer on a rustproof coating or the like can be optionally included. These undercoat layers and topcoat layers can be formed using known materials and formation methods.

[0055]

Next, the present invention will be further described with reference to examples.

A cold rolled steel sheet having a thickness of 0.8 mm and a width of 1200 mm was used as an original plate for plating. For electroplating, after annealing in an annealing line, degreased and pickled in an electroplating line, the amount of plating (alloy) for plating adjust its total amount) on one side 20 g / m 2, melt plating, after annealing at hot-dip plating line, by adjusting the coating weight on one side 50 / m 2, to prepare a coated steel sheet, the It was used as a base material in Examples of the invention. Neither base material was subjected to post-treatment such as chemical treatment after plating.

On the product surface after electroplating and hot-dip plating, the following coating material was dried with a roll coater to have a film thickness of 0.
The coating was performed so as to have a thickness of 5 to 5.0 μm (evaluation center: 1.0 μm), followed by dry baking in various baking furnaces, and performance evaluation was performed after cooling. The paint used was a polyolefin-based resin ("Hi-Tech S-7024", manufactured by Toho Chemical Co., Ltd.) added to pure water so that the resin solid content concentration became 20% by weight, and thiourea was further added at 5.0 g / l. Ammonium phosphate was dissolved to a phosphate ion concentration of 1.25 g / l, and 0.2 g / l of 3-methacryloxypropyltrimethoxysilane was added as a silane coupling agent. Finally, 300 g / l of water-dispersible silica ("Snowtex N", manufactured by Nissan Chemical Industries, Ltd.) was added, and the mixture was stirred and dispersed with a disper for 30 minutes to adjust the pH to 8.0.

As the type of the baking furnace, a direct fire furnace, a hot blast furnace, an induction heating furnace, and a near infrared furnace were used. The drying conditions are as shown in Table 1. By changing the line speed and changing the furnace time, the temperature of the baked plate reached 4 ° C.
The heating rate was changed in the range of 5 to 50 ° C./sec by changing the current value in the range of 0 to 300 ° C. and changing the current value in the induction heating furnace and the atmosphere temperature in the other furnaces. Cooling was performed by using a water spray cooling device immediately after the furnace to room temperature.

The evaluation of the performance was carried out according to the methods shown in Table 2 on the film adhesion, corrosion resistance, conductivity and solvent resistance. The performance evaluation results were as shown in Tables 3 to 5.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

In the case of electro-Zn plating, as shown in Examples 1 to 20, when the ultimate temperature after baking is in the range of 50 to 250 ° C., regardless of the type of baking furnace, as shown in Examples 1 to 20, Shows good performance. In addition, the corrosion resistance and the solvent resistance showed good performance irrespective of the type of the baking furnace, and it was found that a good result was obtained particularly in the direct fire furnace as compared with other baking furnace types. This is thought to be the result of the film-forming reaction on the outermost layer being sufficiently performed and the film being denser in the case of a direct-fired furnace because the surface layer of the coating film is exposed to a higher temperature than in other dry baking furnace types. . Good product performance was obtained when the temperature was raised during baking at a rate of 5 to 40 ° C./sec.

On the other hand, as shown in Comparative Examples 1 to 9, when the temperature reached was low, the appearance was good, but the film was not formed sufficiently, and the film adhesion and corrosion resistance were poor. . If the temperature reached is too high, the resin will be discolored.
This is remarkable in the case of a hot blast stove and a near-infrared stove, and the corrosion resistance is deteriorated due to the deterioration of the resin. Further, at a heating rate of 50 ° C./sec, surface coating defects were generated, and the corrosion resistance was deteriorated due to the defects. This tendency was also noticeable in a furnace having a high ambient temperature.

Next, electric Zn--Ni alloy plating, hot-dip Zn
Plating and hot-dip Zn-Fe alloy plating (Examples 21 to 5)
Although the same evaluation was performed for 0), it was confirmed that the present invention had the same product performance regardless of the plating base material.

[0068]

As described above, according to the present invention,
It is possible to manufacture a non-chromium-type treated galvanized steel sheet which does not contain harmful hexavalent chromium and has excellent corrosion resistance, and can greatly contribute to promoting the use thereof.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor, Go Miyake 1 Kimitsu, Kimitsu City, Chiba Prefecture Inside Nippon Steel Corporation (72) Inventor Koji Tanimura 1 Kimitsu, Kimitsu City, Chiba Prefecture Nippon Steel Corporation (72) Inventor Toshinobu Akakawa 1 Kimitsu, Kimitsu-shi, Chiba Nippon Steel Co., Ltd. (72) Inventor Toshiaki Shimakura 4-1-1-15 Minamishinagawa, Shinagawa-ku, Tokyo Japan Paint Inside (72) Inventor Katsuyoshi Yamazoe 4-1-1-15 Minamishinagawa, Shinagawa-ku, Tokyo Japan Paint Co., Ltd.

Claims (4)

[Claims]
1. A zinc-plated steel sheet or a zinc-alloy-plated steel sheet as a base, on which an aqueous resin and at least one of a thiocarbonyl group-containing compound, a vanadate compound and a phosphate compound are contained. Forming a coating film or (b) a coating film containing an aqueous resin, a thiocarbonyl group-containing compound and finely divided silica, and then reaching a plate temperature of 50 to 250 ° C.
Forming a non-chromium type rust-preventive film by drying and baking this coating film.
2. The drying and baking of the coating film is carried out at 40 ° C. /
The method according to claim 1, wherein the heating is performed at a heating rate of not more than sec.
3. The drying and baking of the coating film is performed in a direct fire furnace,
The method according to claim 1 or 2, wherein the method is performed in a hot blast furnace, an induction heating furnace, a near infrared furnace, or a combination thereof.
4. The method according to claim 3, wherein the coating is dried and baked in an open fire furnace.
JP11375602A 1998-12-29 1999-12-28 Production of non-chromium type treated galvanized steel sheet Pending JP2000248380A (en)

Priority Applications (3)

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JP37705098 1998-12-29
JP10-377050 1998-12-29
JP11375602A JP2000248380A (en) 1998-12-29 1999-12-28 Production of non-chromium type treated galvanized steel sheet

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WO2005010235A1 (en) 2003-07-29 2005-02-03 Jfe Steel Corporation Surface-treated steel sheet and method for producing same
US7291402B2 (en) 2002-07-23 2007-11-06 Jfe Steel Corporation Surface-treated steel sheets of good white rust resistance, and method for producing them
JP2008229428A (en) * 2007-03-19 2008-10-02 Nippon Steel Corp Manufacturing method of plated steel sheet excellent in corrosion resistance and coating material adhesion
US7517591B2 (en) 2003-06-16 2009-04-14 Jfe Steel Corporation Highly corrosion-resistant surface-treated steel sheet and method for producing same
US8304092B2 (en) * 2006-12-13 2012-11-06 Jfe Steel Corporation Surface-treated galvanized steel sheet with superior flat-portion corrosion resistance, blackening resistance, and appearance and corrosion resistance after press forming and aqueous surface-treatment liquid for galvanized steel sheet

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US7291402B2 (en) 2002-07-23 2007-11-06 Jfe Steel Corporation Surface-treated steel sheets of good white rust resistance, and method for producing them
US7517591B2 (en) 2003-06-16 2009-04-14 Jfe Steel Corporation Highly corrosion-resistant surface-treated steel sheet and method for producing same
US8012599B2 (en) 2003-06-16 2011-09-06 Jfe Steel Corporation Surface-treated steel sheet with excellent corrosion resistance and method for manufacturing same
WO2005010235A1 (en) 2003-07-29 2005-02-03 Jfe Steel Corporation Surface-treated steel sheet and method for producing same
US7842400B2 (en) 2003-07-29 2010-11-30 Jfe Steel Corporation Surface-treated steel sheet and method for manufacturing the same
US8304092B2 (en) * 2006-12-13 2012-11-06 Jfe Steel Corporation Surface-treated galvanized steel sheet with superior flat-portion corrosion resistance, blackening resistance, and appearance and corrosion resistance after press forming and aqueous surface-treatment liquid for galvanized steel sheet
JP2008229428A (en) * 2007-03-19 2008-10-02 Nippon Steel Corp Manufacturing method of plated steel sheet excellent in corrosion resistance and coating material adhesion

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