WO1999042639A1

WO1999042639A1 - Anticorrosive coating material and method of rust prevention

Info

Publication number: WO1999042639A1
Application number: PCT/JP1999/000664
Authority: WO
Inventors: Hiroshi Kanai; Atsushi Morishita; Yujiro Miyauchi; Toshiaki Shimakura; Motoo Kabeya
Original assignee: Nippon Steel Corporation; Nippon Paint Co., Ltd.
Priority date: 1998-02-18
Filing date: 1999-02-16
Publication date: 1999-08-26
Also published as: AU2546799A; TW555824B

Abstract

An inexpensive chromium-free anticorrosive coating material which imparts higher corrosion resistance to metallic materials than rust preventives containing chromium. The coating material comprises a composition consisting mainly of a water-compatible resin and water and, per liter of the composition, 0.2 to 50 g of a compound having a thiocarbonyl group and 0.1 to 20 g of a vanadic acid compound, and optionally contains 0.1 to 5 g of phosphate ions and/or 50 to 500 g of water-dispersible silica.

Description

Specification

Technical Field

The present invention relates to a surface treatment composition and a surface treatment method for a metal material, particularly steel coated with a metal (hereinafter referred to as coated steel) or uncoated steel which is not coated or the like. Provide a protective agent that imparts sufficient corrosion resistance to steel.

Background art

In an atmosphere containing salt such as seawater or a high-temperature and high-humidity atmosphere, the coated steel has a surface that causes rust and significantly impairs the appearance, and has a reduced resistance to the steel surface. Conventionally, chromate-based anti-oxidants have been frequently used to prevent the generation of gas. For example, Japanese Patent Application Laid-Open No. 3-131370 describes that “Olefin Ichi,] 3-ethylenically unsaturated A resin-based treating agent comprising a water-dispersible chromium compound and water-dispersible silica in a carboxylic acid copolymer resin dispersion is disclosed.

However, even the chromium-containing resin-based treating agent as described above does not always have sufficient corrosion resistance, and causes a problem when exposed to a salt water or high-temperature and high-humidity atmosphere for a long time. In recent years, there has been an increasing demand for non-chromium anti-oxidants.

The inventors have found that sulfide ion reacts with zinc to form a stable ZnS film, and has already disclosed in JP-A-8-239776, JP-A-8-679384. Publication No. 1 discloses a non-chromium antioxidant using sulfide and sulfur.

However, some of the sulfides had a characteristic odor, and handling was not always easy.

In addition, a fireproofing agent using a triazinethiol compound containing a zeo atom and having no odor or toxicity has been proposed. For example, “water-soluble anticorrosion paint” in JP-A-53-31737 discloses a water-soluble anticorrosion paint to which a dithiol-S-triazine derivative is added.

In addition, the “reactive emulsion with metal” in JP-A-61-223062 includes a metal obtained by mixing a thiocarbonyl group-containing compound and a water-insoluble or insoluble organic compound in water. A reactive emulsion with is disclosed. However, the water-soluble anticorrosion paint disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 53-31737 is intended for anticorrosion of mild steel, copper, machinyu, copper wire and the like. Is prepared so as to be more easily adhered to copper or copper. Therefore, it was insufficient as a protective agent for metal surfaces such as aluminum and aluminum. In addition, the reactive emulsion disclosed in the above-mentioned Japanese Patent Application Laid-Open No. Sho 61-223203 is also an emulsion which reacts with copper, nickel, tin, cobalt, aluminum and the like and alloys thereof. It was insufficient as a protective agent for metal surfaces such as ships.

The present inventors have studied a triazinethiol-containing anti-corrosion coating agent which is also effective in preventing zinc-based steel sheets, and have developed a triazine thiol-containing anti-corrosion coating agent described in Japanese Patent Application No. 9-25557. Disclosed. However, triazine thiol is an expensive compound, and a cheaper antioxidant has been desired.

As a surface treatment method of zinc or a zinc alloy containing no chromium and not using triazine thiol, JP-A-54-71734 and JP-A-3-222684 are mentioned. . Japanese Unexamined Patent Publication No. Sho 54-7117734 discloses the use of myo-inositol.

0.5 to 100 _§ // 1 of 2 to 6 bonded phosphate esters or salts thereof, and one or more selected from the group consisting of titanium fluoride and zirconium fluoride in terms of metal. A zinc or zinc alloy surface treatment method characterized in that zinc or a zinc alloy is surface-treated with an aqueous solution containing 5 to 30 g / l and thiourea or a derivative thereof 1 to 50 g Zl. is there. This technique requires titanium fluoride or zirconium fluoride to form a passivation film as a protective layer on the zinc surface. Also JP-A 3 - 2 2 6 5 8 4 JP is of N i ² + and C o ^{2 +} 1 or 2 or 0 0 and on 2 g or more, a compound having an ammonia and primary amine groups. Disclosed is a surface treating agent that is an aqueous solution of pH 5 to 10 having one or two kinds. This requires Ni ^{2 +} and / or Co ^{2 +} to provide paint adhesion and post-paint corrosion resistance by depositing cobalt or nickel. As described above, the treating agent containing metal ions has disadvantages such as an increase in the load during wastewater treatment.

Disclosure of the invention

The present invention has been made in view of the above-mentioned conventional problems, and has as its object to prevent chromium-containing protection. An object of the present invention is to provide an inexpensive and effective anti-corrosion coating agent and anti-corrosion treatment method for non-metallic metal materials having corrosion resistance higher than that of anti-corrosion agents. Another object of the present invention is to provide a metal material which is non-chromium-resistant and has excellent corrosion resistance.

In order to achieve the above-mentioned object, a water-proof coating composition according to the present invention comprises a water-based resin and water as main components, a so-called ordinary water-proof coating composition, and more preferably 0.2 to 50 g. The compound containing a thiocarbinole group-containing compound and 0:! To 20 g of a vanadium diacid conjugate.

In another embodiment, the anti-corrosion coating agent according to the present invention further comprises 0.1 to 5 g of phosphate ions and phosphorus or 50 to 500 g (mainly an aqueous resin and water). (Per composition 11) water-dispersible silica.

Further, the method for preventing corrosion according to the present invention is a treatment method for coating any one of the above-described coatings on a metal material.

In the present invention, the metal material refers to a plate material such as steel, titanium, aluminum, or copper, or a formed material, and includes a metal material coated by plating, thermal spraying, or the like. Copper includes cold-rolled steel sheets, hot-rolled steel sheets, and stainless steel sheets.

In the present invention, coated steel refers to metals such as Zn-based, A1-based, Ni-based, Cr-based, Sn-based, Pb-based, and Fe-based, or one of these metals and other metals. Or steel coated with an alloy with a higher alloy. Other metals include, for example, Co, Ni, Fe, Cr, Al, Mg, Sn, Mn, Zn, Ti, and the like. After these coatings are applied, alloys formed by heat treatment or the like are also included. Co, Mo, W, Ni, Ti, Cr, Al, Mn, Fe, Mg, Pb, Sb, Sn , Cu, Cd, As, etc., or a dispersion of Z and an inorganic substance such as silica, alumina, titania, or plating containing a component other than metal such as Fe-P. Furthermore, the above-mentioned plating may be combined in multiple layers.

Coating methods include electroplating, fusion plating, vapor deposition plating, and thermal spraying. Further, the metal material treated for protection according to the present invention is a metal material coated with any one of the above-described coating materials for preventing corrosion.

In general, in order to be effective as a coating for preventing corrosion, it is necessary to (1) prevent the penetration of corrosive liquid, (2) have adhesion to the metal substrate of the protection film, and (3) prevent ion (4) It is necessary to satisfy the requirements such as passivation of the metal surface by (4) water resistance, acid resistance, and alkali resistance of the protection film. If any of these is insufficient, the protection cannot be exerted. The conventional chromium compound as a fire retardant mainly excels in (3) passivation. Here, passivation refers to a state in which a metal or an alloy retains inertness despite being in an environment that is chemically or electrochemically active.

Sulfides, like chromic acid, are easily adsorbed on metal surfaces and have excellent oxidizing ability, so they can passivate metal surfaces. Therefore, a thiocarbonyl-containing compound, which is one of the sulfides, has a metal material-preventing effect.

When a vanadium compound is added to such a protective agent, the following protective effect of vanadium ion is added, and the protective effect is further promoted.

The vanadate compound is dissolved in the protective agent as an ion, and depending on the conjugate and the amount added, the dissolution amount as an ion is saturated and dispersed as a solid in the protective agent.がある May be pigment. In any case, the vanadate ion forms a passivation film on the surface of a metal such as zinc or aluminum in the same manner as chromate at the time of application. This is the reason why the vanadate compound exhibits a protective effect. In addition, when water, which is a corrosion factor, penetrates into the anti-corrosion film and a corrosion site is formed on the surface of zinc or aluminum, it is eluted from the vanadate compound by vanadate ions present in the film or permeated water. It is considered that the vanadate ion acts on the corrosion site and suppresses the corrosion reaction.

When the vanadate ion coexists with the thiocarbonyl group-containing compound or the phosphate ion, a synergistic action with them is developed. The reason for this synergism is not clear, but vanadate ions form a passive film at sites where phosphate-containing compounds cannot be adsorbed, or vice versa. Ion-dithiocarbonyl phosphate at the defect of the active film It is considered that the adsorption of the water supplements the action of the vanadate ion and provides a synergistic effect of the anti-dust effect.

Furthermore, when a thiocarbonyl group-containing compound is added together with phosphate ions to a water-resistant coating agent containing an aqueous resin, its protection effect is significantly improved, and is superior to conventional chrome-containing resin-based protection agents. A protective coating agent is obtained. This is presumed to be because the synergistic action of the thiocarbonyl group-containing compound and the ion phosphate exerts a protective effect. That is, it is presumed that (1) the ion of the thiol group in the thiocarbonyl group-containing compound is adsorbed to the site on the surface of the active zinc alloy during the application of the protective coating, and exerts the protective effect. Naturally, a sulfur atom easily forms a coordination bond with zinc or aluminum, but a thiocarbon group (formula I)

\

c = s (I)

The compound having / has the formula (Π) = N-1 0

\ \

Those having both a nitrogen atom and an oxygen atom, such as c = s and c = s (II), are preferable. In these compounds, nitrogen atoms and oxygen atoms can also form coordinate bonds with metals such as zinc and aluminum, so especially in the case of thiocarbonyl compounds having these atoms simultaneously, a chelate bond is formed on the zinc or aluminum surface. It is easy to form, and the thiocarbon compound can be strongly adsorbed on the surface of a metal such as zinc or aluminum. No thiocarbonyl group-containing compound is adsorbed on sites on metal surfaces such as inactive zinc or aluminum (for example, on the surface of oxides), but phosphate ions act on such inactive surfaces. Then, a phosphate compound such as zinc phosphate or aluminum phosphate is formed to form an active surface. Since the compound containing a thiocarbonyl group is adsorbed on the activated surface in this way, zinc, aluminum, etc. It is presumed that the metal has a protective effect on the entire surface of the metal. In addition, (2) the thiocarbonyl group-containing compound and the phosphate ion also act as a crosslinking accelerator for the resin film. It is presumed that the synergistic action of the two reduces the number of micropores in the resin film and efficiently blocks harmful ions such as water and chloride ions.

It should be noted that, in addition to the excellent protection effect due to the coexistence of the above-mentioned thiocarbonyl group-containing compound and phosphate ion, it was discovered that the addition of water-dispersible silica further promoted the protection effect. Was done.

Water-dispersible silica adsorbs protective ions and molecules such as phosphate ion-thiocarbonyl group-containing compounds and vanadate ions onto the surface of the silica particles, and causes a corrosion reaction to occur on a metal-coated surface such as zinc or aluminum. It is thought that the protective action is enhanced by releasing the protective ions and molecules to the site as appropriate.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

First, the thiocarbonyl group-containing compound-based protective coating agent according to the present invention will be described in detail.

In the present invention, the thiocarbon group-containing compound is a thiocarbonyl group (I)

\

c = s (I)

The term “compound” means that the compound can release a thiocarbonyl group-containing compound in an aqueous solution or in the presence of an acid or an alkali.

A typical example of the thiocarbonyl group-containing compound is represented by the formula (III)

=: f j

\

C = S (ill)

/

= N Such as methylthiourea, dimethylthiourea, ethylthiourea, dimethylthiourea, diphenylthiourea, thiopental, thiocarbazide, thiocarbazone, thiocyanoic acid, thiohydantoin, 2-thioperamyl, and 3-thiourea; Thioperazole, etc .; Formula (IV)

NH ₂

\

C = S (IV)

/

A compound having a thioamide group represented by, for example, thioformamide, thioacetamide, thiopropionamide, thiobenzamide, thiocarbostyril, thiosaccharin and the like; Formula (V)

H

\

C = S (V)

/

A compound having a thioaldehyde group represented by, for example, thioformaldehyde, thioacetaldehyde, etc .;

c = s or c = s (VI)

Z /

A thiocarboxylic acid having a thiocarboxy group or a dithioloxyloxy group represented by OH SH, for example, thioacetic acid, thiobenzoic acid, dithioacetic acid, etc .; OH OH SH

\ \ \

^{C == S} C = S or _{C = S} (vii

^/ · / /

OH SH SH thiocarbonates represented by SH; and other compounds having the structure of formula (I), such as thiokumazon, thiomomotiazone, thionin blue J, thiopyrone, thiopyrine, thiobenzophenone, and the like.

Among the above, those that do not directly dissolve in water are dissolved in an alkaline solution and then incorporated into a protective coating agent.

The thiocarbonyl-containing compound is preferably contained in an amount of 2 g to 50 gZ1 per 11 of a composition containing water-soluble resin and water as a main component, and more preferably 0.5 to 201. If it is less than 0.2 _g l is corrosion resistance becomes insufficient, whereas when it exceeds 50 g Bruno 1, the corrosion resistance not only uneconomical saturated, connexion by the aqueous resin to be used, the resin is gelled Coating becomes impossible.

The vanadate compound is added in a concentration of 0.1 to 20 g, preferably 0.5 to 10 g, per liter of a composition containing a water-soluble resin and water as a main component. If the concentration of the vanadium acid compound is less than 0.1 g, the protection is reduced, and if it is more than 20 g, the protection is saturated and uneconomical.

The vanadate compound is vanadate, typically metavanadate, orthovanadate, for example, vanadate such as ammonium vanadate, sodium vanadate, potassium vanadate, strontium vanadate, sodium hydrogen vanadate, and the like. Further, it can be supplied in the form of a phosphovanadate such as phosphovanadate or ammonium phosphovanadate.

Phosphate ions form a phosphate layer on the surface of the metal substrate, passivate it, promote the crosslinking reaction of the resin film derived from the aqueous resin, and form a dense water-proof film. Strength is further improved. The content of phosphate ions is 0.1 lg to 5 g, more preferably 0.5 g to 3 g, and preferably less than 0.1 g / 1, per composition containing water-soluble resin and water as main components. In the case of, the protection effect is not fully exhibited, On the other hand, if the content exceeds 5 g Zl, the 1 "life of the protection is reduced, and the resin is gelled, so that the storage stability of the protection coating as a product is deteriorated.

The water-proof coating agent according to the present invention further comprises 50 to 500 g, more preferably 100 to 400 g of water dispersed in 1 liter of the total composition containing an aqueous resin and water as main components. Corrosion resistance is further improved by adding the functional silica. Moreover, in addition to the corrosion resistance, the drying property, the scratch resistance, and the coating property can be improved.

In the present invention, the water-dispersible silica is a generic name for a silica force having characteristics such that, when dispersed in water, it has a fine particle size, can maintain a stable water-dispersed state, and does not semi-permanently settle. That's what they say. The water-dispersible silica is not particularly limited as long as it has a small amount of impurities such as sodium and is weakly alkaline. For example, commercially available silica gels such as "Snowtex N" (manufactured by Nissan Chemical Industries, Ltd.) and "Adelite AT-20N" (manufactured by Asahi Denka Kogyo Co., Ltd.), or commercially available aerosil powder silica particles are used. be able to.

The content of the water-dispersible silica is preferably 50 to 500 g per liter of the above-mentioned water-proof coating agent. If the content is less than 50 g, the effect of improving the corrosion resistance is not sufficient. On the other hand, if it exceeds 500 g, the corrosion resistance is saturated and uneconomical.

The water-resistant resin is contained in the anti-corrosion coating agent of the present invention. In the present invention, the term “aqueous resin” includes not only a water-soluble resin but also a water-insoluble resin, such as an emulsion or a suspension, in which the insoluble resin is finely dispersed in water. Examples of the resin that can be used as such an aqueous resin include polyolefin resin, polyurethane resin, acrylic resin, polycarbonate resin, epoxy resin, polyester resin, alkyd resin, phenol resin, and others. Heat-curable resin and the like can be exemplified, and a crosslinkable resin is more preferable. Particularly preferred resins are polyolefin-based resins, polyurethane-based resins, and mixed resin-based resins of both. The aqueous resin may be used as a mixture of two or more kinds. The water-proof coating agent according to the present invention is preferably composed of an aqueous resin (including a water-soluble resin and a water-dispersible resin) in a solid content of 1 to 80 parts by weight and water of 99 to 20 parts by weight, more preferably 5 to 90 parts by weight, respectively. 50 parts by weight and 95 to 50 parts by weight as a main component. You. The composition may further include a viscosity modifier, a pigment, a dye, a surfactant, an organic solvent, and the like.

Further, the heat-resistant coating agent according to the present invention may further contain other components. For example, pigments, surfactants and the like can be mentioned. In addition, a silane coupling agent may be added to improve the affinity between the aqueous resin and the silica particles and the pigment, and further improve the adhesion between the aqueous resin and the surface of zinc, aluminum or iron. ,.

As the pigment, such as titanium oxide (T i 0 _2), zinc oxide (Z nO), oxide Jill Koniumu (Z and rO), calcium carbonate (CaC 0 _3), barium sulfate (B a SO _4), alumina ( A1 ₂ 0 _3), kaolin clay, carbon black, iron oxide _{_{(F e 2 0 3, F}} e 3 0

Inorganic pigments such as J and various coloring pigments such as organic pigments can be used.

Examples of the above silane coupling agent include —aminopropyl trimethoxysilane, γ-aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, Ν- [2- (vinyl Benzylamino) ethyl] -3-aminopropyl trimethoxysilane.

A solvent may be used in the water-proof coating agent according to the present invention in order to improve the film forming property of the aqueous resin and form a more uniform and smooth coating film. The solvent is not particularly limited as long as it is generally used for coatings, and examples thereof include alcohol-based, ketone-based, ester-based, and ether-based solvents.

In the present invention, a metal material can be subjected to a heat-proof treatment by using the above-mentioned heat-proof coating agent as a metal material-proof coating agent.

In the above-mentioned heat-proofing treatment, the above-mentioned mackerel-barrier coating agent of the present invention is applied to an object to be coated, and after the application, the object to be coated is dried and hardened. Methods of drying and curing include hot air heating, induction heating, electric heating, near-infrared heating, far-infrared heating, etc., or a combination of these methods to heat and dry the object to be coated. The method can be selected according to the type of aqueous resin to be used, such as a method of irradiating and curing a coating film, or a method of combining a method of heating and a method of applying energy rays. When drying and curing by heat, the object to be coated is heated in advance and then A method may be used in which the heat-resistant coating agent of the present invention is hot-applied, and the remaining heat is used, or a necessary hot energy is further added and dried.

In the case of curing by heating, the heating temperature is not particularly limited, but the ultimate plate temperature is desirably 40 to 250 ° C. If the temperature is lower than 40 ° C., the evaporation rate of water is slow, and sufficient film-forming properties may not be obtained, resulting in insufficient protection. On the other hand, when the temperature exceeds 250 ° C., thermal decomposition of the aqueous resin occurs, so that the corrosion resistance is reduced and the appearance may be changed. More preferably, it is 60 to 200 ° C. The drying time when the object is heated and dried after application is not particularly limited, but is about 1 second to 5 minutes.

In the above-mentioned heat-proof treatment, it is preferable that the dry film thickness of the above-mentioned heat-proof coating agent of the present invention is 0.1 // m or more. If it is less than 0.1 // m, the protection is insufficient. On the other hand, if the dry film thickness is too thick, it is uneconomical as a coating base treatment and inconvenient for coating, so that the thickness is more preferably 0.1 to 2 ° μπι. More preferably, it is 0.1 to 10 / m.

However, when used as a water-based waterproof coating, the film thickness may be 0.1 / m or more.

In the above-mentioned heat-proofing treatment, the method of applying the above-mentioned fire-proofing coating agent of the present invention is not particularly limited, and it can be applied by generally used roll coating, air spray, airless spray, immersion or the like.

The material coated with the anti-corrosion coating agent of the present invention is a metal material as described above.

Further, the anti-corrosion coating agent of the present invention can be used as a coating base treatment agent and a water-based anti-corrosion paint as described above, and can also be applied as a so-called primary anti-corrosion agent. Furthermore, it can be used not only for the undercoat treatment of a lubricating film on a metal plate and the undercoat treatment in the field of coil coating, but also as a lubricating inhibitor for lubricated steel sheets by adding a wax to the present agent.

Example

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples and comparative examples, the concentration expression (gZl) refers to an anti-adhesion coating mainly composed of an aqueous resin and water. Means the weight (g) of each component contained in 1 liter of the agent composition.

In the following Examples, the corrosion resistance was evaluated by the following method.

〔Evaluation method〕

(A) Protection

a) Preparation of specimen

The anti-corrosion coating agent of the present invention (solid content: 20 wt./.) Was applied to a commercially available galvanized zinc-coated steel sheet EG—MO material and a molten A 1-10% Si plated steel sheet (plated adhesion amount 30 g / m ² ). After coating with a bar coat # 3 so as to have a dry film thickness of 1 / zm, it was dried to a PMT of 150 ° C.

b) Salt spray test (S ST resistance)

A 5% saline solution was sprayed on the coated surface of the object to be coated at 35 ° C., and the degree of whitening after 240 hours was evaluated on a scale of 10 out of 10. The evaluation was performed for both the flat part and the Erichsen 7 mm extruded part.

The evaluation criteria were as follows.

0 points No abnormality

9 points Between 10 points and 8 points

8 points slightly white

7 6 points Between 8 points and 5 points

5 white spots on half of the area

4 Between 2 points 5 points and 1 point

1 point White color is generated on the entire surface

(B) Topcoat adhesion

a) Preparation of specimen

The anti-corrosion coating agent of the present invention (solid content: 20% by weight) is bar-coated on a commercially available electroplated zinc-coated steel sheet EG—MO material and molten A 1-10% Si plated steel sheet (plated adhesion amount 30 g / m ² ). After coating in # 3 so that the dry film thickness was 1 μηι, it was dried to PMT 150 ° C. After drying, Super Lac 100 (manufactured by Paint Co., Ltd .; acrylic melamine paint) was applied in a dry coat to a dry film thickness of 20 / m. After drying at 150 ° C for 20 minutes, the top coat adhesion test plate Make Was.

b) Primary adhesion test

Crosscut: The tape-peeling property of the portion where a 1-mm cut was cut was evaluated, and it was evaluated on a scale of 10 out of the following criteria.

Erichsen (Er) 7 mm: Tape was applied to the part extruded with Erichsen to 7 mm, and the tape peelability was similarly evaluated.

Crosscut + Erichsen (E r) 7 mm: A tape with a 1 mm cut was extruded with Ericksen to a thickness of 7 _mm , and the tape peelability was similarly evaluated.

The evaluation criteria were as follows.

10 points: No abnormalities

9 points: The percentage of peeling out of the measured grids is 10% or less.

8 points: 20% or less.

7 points 30% or less.

6 points II 40% or less.

5 points n 50% or less.

4 points a 60% or less.

3 points 1170% or less.

2 points 〃 80% or less.

1 point 90% or less.

0 points Greater than 90%. c) Secondary adhesion test

After immersing the test plate in boiling water for 30 minutes, the same tests and evaluations as the primary test were performed.

Example 1

In pure water, polyolefin resin “Hitech S_7042” (trade name; manufactured by Toho Chemical Co., Ltd.) and polyurethane resin “BonTiter HU X-320” (trade name; manufactured by Asahi Denka Co., Ltd.) Is added at a ratio of 1: 1 (weight ratio) in terms of solids so that the total concentration of the resin solids is 20% by weight, and ammonium vanadate is further added. 3 g / l, thiourea at 5.0 _{g /} l, and ammonium phosphate dissolved at a phosphate ion concentration of 2.5 _{g /} 1, and finally water-dispersible silica "Snowtex N"

(Trade name; manufactured by Nissan Chemical Industry Co., Ltd.) was added in an amount of 300 gZl, and the mixture was stirred and dispersed with a disperser for 30 minutes to adjust the pH to 8.0, thereby obtaining an anti-coating agent. To evaluate the obtained water-proof coating agent for the water-proof property and the topcoat adhesion, as described in the above evaluation method, a commercially available electric zinc plated steel sheet was used.

"EP-MO" (Nippon Test Panel Co., Ltd., 70 x 150 x 0.8) was applied and dried. Electric zinc plating steel plate was degreased with an alkaline degreasing agent "Surf Cleaner 53", manufactured by Nippon Paint Co., Ltd. After water washing and drying, the above evaluation was performed.

Table 1 shows the evaluation results.

Examples 2 to 6

In the same manner as in Example 1, except that the mixing ratio of the polyolefin resin and the polyurethane resin, the type of the compound containing a thiopropyl group and the type and the amount of the vanadic acid compound were changed as described in Table 1, respectively. Thus, a galvanized steel sheet having been subjected to a water-proof treatment was obtained. Table 1 shows the evaluation results.

Comparative Example 1

Reduce the amount of thiourea to 0.1 gZ and the amount of ammonium vanadate to 0.1 gZ.

A commercially available electroplated zinc-plated steel sheet was treated in the same manner as in Example 1 except that the amount of phosphate ions and “Snowtex N” were changed as shown in Table 1 and the amount was set to 05 gZ 1. This was polished, degreased, washed with water, dried and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2

Commercially available electric power was obtained in the same manner as in Comparative Example 1 except that 0.1 _{g of} potassium vanadate was added as a vanadate compound, and the amounts of phosphate ions and `` Snowtex N '' were changed as shown in Table 1. The zinc plating steel plate was processed. This was polished, degreased, washed with water, dried and evaluated in the same manner as in Example 1. Table 1 shows the results.

Note: PO: Polyolefin resin, PU: Polyurethane resin Examples 7 to 9

In Example 1, the prevention treatment was carried out in the same manner as in Example 1 except that the added amount of ammonium vanadate and the added amounts of phosphate ions and “Snowtex N” were changed as shown in Table 2. An electro-zinc plated steel sheet was obtained, and evaluation of the anti-corrosion property and the adhesion of the top coat was performed in the same manner. Table 2 shows the evaluation results.

Table 2

Note: PO: Polyolefin resin, PU: Polyurethane resin

Example 10

In pure water, the polyolefin resin “HI-TECH S-7024” (trade name; manufactured by Toho Chemical Co., Ltd.) and the polyurethane resin “Bon Titer HUX-320” (trade name; manufactured by Asahi Denka Co., Ltd.) Mix and add 1: 1 (weight ratio) solids so that the concentration is 20% by weight. Add 3 g / 1 ammonium vanadate, 5.0 g / l thiourea, and ammonium phosphate. Dissolve so that the phosphate ion concentration becomes 2.5 gZl, and finally add 300 gZl of water-dispersible silica "Snowtex N" (trade name; manufactured by Sansan Chemical Industry Co., Ltd.) and then disperse for 30 minutes with a disperser. The mixture was stirred and dispersed for a while, and adjusted to pH 8.0 to obtain an anti-coating agent. In order to evaluate the obtained anti-saba coating agent for anti-scratch property and top coat adhesion, as described in the above evaluation method, a commercially available molten A 1-10% S 1 steel sheet (metal adhesion amount 30) was used. g / m ² ) and dried. The above evaluation was performed after the molten A1-10% Si steel plate was degreased with an alkaline degreasing agent ("Surf Cleaner 53", manufactured by Nippon Paint Co., Ltd.), washed with water, and dried.

Table 3 shows the evaluation results.

Examples 11 to 15

The same as Example 10 except that the mixing ratio of the polyolefin resin and the polyurethane resin, the type of the thiocarbonyl group-containing compound, and the type and the amount of the vanadic acid compound were changed as shown in Table 3 in Example 10. A 1-10% Si plated steel sheet (plated adhesion amount: 30 g / m ² ) treated in this manner was subjected to the same treatment as described above. Table 3 shows the evaluation results. Comparative Example 3

Except that the addition amount of thiourea was 0.1 g / 1, the addition amount of ammonium vanadate was 0.05 g / 1, and the amounts of phosphate ions and `` Snowtex N '' were changed as shown in Table 3. In the same manner as in Example 1, a molten A 1-10% Si plating steel plate (plate adhesion amount 30 gZm ² ) was treated. This was polished, degreased, washed with water and dried in the same manner as in Example 10, and then evaluated. Table 3 shows the results.

Comparative Example 4

Potassium vanadate is added as a vanadate compound with 0.1 g / 1 Melting A 1-10% Si plated steel sheet (plated adhesion amount 30 g / m ^{2) in the same} manner as in Comparative Example 3 except that the amounts of acid ions and “Snowtex N” were changed as described in Table 1. ) Was processed. This was polished, degreased, washed with water, dried and evaluated in the same manner as in Example 10. Table 3 shows the results.

Table 3

Note: PO: Polyolefin resin, PU: Polyurethane resin Example 16 to: 18

In Example 10, protection was performed in the same manner as in Example 10 except that the addition amount of ammonium vanadate and the addition amounts of ion phosphate and “Snowtex N” were changed as shown in Table 4. A treated electric zinc plated steel sheet was obtained, and similarly, the heat resistance and the topcoat adhesion were evaluated. Table 4 shows the evaluation results.

Table 4

Note: PO: Polyolefin resin, PU: Polyurethane resin

Industrial applicability

ADVANTAGE OF THE INVENTION According to the water-proof coating agent which concerns on this invention, and the water-proofing processing method using this water-proof coating agent, the water-proofing agent superior to the conventional chromate-containing aqueous resin-based protective agent is exhibited, In addition, all of the components used have low toxicity, and thus can provide a non-chromium protective coating agent having low pollution and excellent protective properties.

Claims

The scope of the claims

1. One liter of a composition mainly composed of an aqueous resin and water contains 0.2 to 50 g of a thiocarbonyl group-containing compound and 0.1 to 20 g of a vanadate compound. Anti-corrosion coating agent.

2. Composition containing water-based resin and water as main components 0.2 to 50 g of thiocarbonyl group-containing compound, 0.1 to 5 g of phosphate ion and 0.1 to 20 g of vanadate in 1 liter An anti-coating agent comprising a compound.

3. In one liter of a composition mainly composed of an aqueous resin and water, 0.2 to 50 g of a thiocarbonyl group-containing compound, 50 to 500 g of water-dispersible silica, and 0.1 to 20 g of vanadium An anti-coating agent characterized by containing an acid compound.

4. In a liter of a composition mainly composed of an aqueous resin and water, 0.2 to 50 g of a thiocarbonyl group-containing compound, 0.1 to 5 g of phosphate ions, 50 to 500 g of water A water-resistant coating agent comprising dispersible silica and 0.1 to 20 g of a vanadate compound.

5. A method for preventing fire, comprising coating the fireproof coating agent according to claim 1 on a metal material.

6. A metal material which is coated with the coating agent according to claim 1.