WO2003085171A1

WO2003085171A1 - Heat-resistant metal plate excellent in marring resistance and corrosion resistance

Info

Publication number: WO2003085171A1
Application number: PCT/JP2003/004402
Authority: WO
Inventors: Kengo Yoshida; Toshikazu Amemiya; Atsushi Morishita; Akira Takahashi
Original assignee: Nippon Steel Corporation
Priority date: 2002-04-08
Filing date: 2003-04-07
Publication date: 2003-10-16
Also published as: JPWO2003085171A1; AU2003221041A1; TW593751B; TW200306362A

Abstract

A heat-resistant metal plate excellent in marring resistance and corrosion resistance; a water-based silicate coating material with which the heat-resistant metal plate can be obtained; and a process for producing the heat-resistant metal plate. The water-based silicate coating material, which comprises an alkali metal silicate, colloidal silica, a silane coupling agent, a polyolefin wax dispersion, and water and has an alkali metal content of 10 to 20 wt.% on a solid basis, is applied to a surface of a metal or plated metal plate in an amount of 0.1 to 3.0 g/m2 on a dry basis and dried to form a silicate coating film.

Description

Description Heat-resistant metal sheet with excellent scratch resistance and corrosion resistance

The present invention relates to a heat-treated metal sheet excellent in scratch resistance and corrosion resistance, a water-based silicate paint capable of obtaining the heat-treated metal sheet, and a production method. Background art

To date, surface-treated steel sheets, such as electro-zinc coated steel sheets and hot-dip zinc-coated steel sheets, have been developed and widely used in applications such as home appliances, building materials, and automotive parts. Many of these steel sheets are subjected to chromate-treated phosphate treatment for the purpose of improving corrosion resistance and paint adhesion.

In recent years, in particular, in the home appliance industry, applications that are applied uncoated from the viewpoint of saving processes and costs are increasing. Not only corrosion resistance and paint adhesion, but also galling resistance, fingerprint resistance, and unevenness of condensation The required level of various performances for the surface appearance and quality of steel sheets, such as properties, is increasing.

In order to meet the performance demands of such customers, a painted metal sheet was developed, in which an organic composite film based on a special resin was formed on a steel sheet with a chromate treatment. For example, Japanese Patent Publication No. 4-141191 discloses the formation of an organic composite film in which a colloid sol of a specific fine particle size is added to a water-based organic resin on a steel plate coated with chromate, and the corrosion resistance is improved. A method of manufacturing a surface-treated steel sheet with improved performance such as fingerprint resistance is disclosed.

Japanese Unexamined Patent Publication No. Hei 3-3 9485 discloses that a zinc-based plated steel plate is After the mouth mate treatment, a paint in which silica and a glass transition point (T g point) having a glass transition point (T g point) of 40 ° C. or more are dispersed in an aqueous resin is 0.3 to 3.0 g / m 2 as a dry weight. ^Two coatings are disclosed. Japanese Patent Application Laid-Open No. 3-28380 discloses that after a chromate treatment is applied to an electro-zinc-plated steel sheet, a lipoxylated polyethylene resin and a Teflon (trademark) lubricant are used. A lubricated steel sheet coated with a paint of 0.5 to 4.0 g / m ² as a dry weight is disclosed. Furthermore, in order to meet the demands of customers who require severe galling resistance, such as deep drawing workability, surface-treated steel sheets with improved lubricity by adding a solid lubricant to the organic film have been developed. . For example, Japanese Patent Application Laid-Open No. 6-173,037 discloses a steel sheet having a lubricating film in which silica and polyolefin are added to an ether-ester type urethane resin and an epoxy resin.

The technology disclosed in Japanese Patent Publication No. 4 _ 1 4 1 9 1 is excellent in performance balance such as corrosion resistance, paint adhesion, fingerprint resistance and dew condensation resistance, and is currently one of the main products for home appliances. It is used as one. However, even with a surface-treated steel sheet coated with such an organic film, scratches at the time of soldering, galling at the time of press working, and abrasion at the time of product transportation may occur. is there.

On the other hand, the techniques disclosed in JP-A-3-39485 and JP-A-3-28380 are less likely to cause the above-described press galling or abrasion. In addition, the technology disclosed in Japanese Patent Application Laid-Open No. 6-173,037 has excellent press galling resistance even in severe processing such as deep drawing.

However, the resin films used for these steel sheets have a heat resistance of only about 150 to 250 ° C, and it cannot be said that they have a sufficient function for the heat resistance. Specifically, for example, used for CRT In a heat shrink pan, a heat treatment at about 600 ° C. is performed, and in a stove or the like, it is used at about 200 to 400 ° C. for a long time. Therefore, there has been a demand for the development of a surface-treated steel sheet having not only a heat resistance function but also excellent scratch resistance and corrosion resistance. Disclosure of the invention

An object of the present invention is to provide a heat-treated metal plate having excellent scratch resistance and corrosion resistance, an aqueous silicate paint capable of obtaining the heat-treated metal plate, and a production method.

As a result of various studies to solve the above-mentioned problems, the present inventors have found that an alkali metal silicate, a colloidal silica, a silane coupling agent, A water-based silicate paint composed of a dispersion of a polyethylene resin and water and having an aluminum metal content of 10 to 20% by mass in terms of solid content is defined as a dry mass of 0%. It has been found that a heat-treated metal sheet having excellent scratch resistance and corrosion resistance can be obtained by applying and drying from 1 to 3.0 g / m ² .

That is, the gist of the present invention is as follows.

(1) 0 in the upper layer of the metal or plated metal sheet. 1~ 3. O g Z m has a ^second Kei salt coating, said Kei salt coating Kei acid alkali metal salts, copolymers Roidarushirika, Shirankatsupuri ring A heat-treated metal sheet having excellent scratch resistance and corrosion resistance, characterized by comprising an agent and a polyolefin resin and having an alkali metal content of 10 to 20% by mass.

(2) 0.1 to 3.0 Og / m ² silicate coating on the metal or plated metal plate, wherein the silicate coating is alkali metal silicate, colloidal silica, phosphoric acid Salts, silane coupling agents and polyoles It must be composed of filtus and have a Si / P mass ratio of 30 to 150 in the silicate film and a metal content of 10 to 20 mass%. A heat-treated metal plate with excellent scratch and corrosion resistance.

(3) It is composed of alkali metal silicate, colloidal silica, silane coupling agent, polyrefin wax dispersion and water, and has an alkali metal content of 10 to 20% by mass in terms of solid content. Aqueous caked acid capable of producing a heat-resistant metal plate according to the above (1), which is coated and dried on an upper layer of a metal or plated metal plate and has excellent scratch resistance and corrosion resistance. Salt paint.

(4) It is composed of alkali metal silicate, colloidal silica, phosphate, silane coupling agent, polyolefin wax dispersion and water, and has a Si / P mass ratio of 3 0 to 150, and the content of aluminum alloy is 10 to 20% by mass in terms of solid content, applied to the upper layer of a metal or plated metal plate, and dried. A water-based silicate paint capable of producing the heat-treated metal sheet according to the above (2), which is excellent in scratch resistance and corrosion resistance.

(5) Consisting of alkali metal silicate, colloidal silica, silane coupling agent, polyolefin wax dispersion and water, and having an alkali metal content of 10 to 20 mass in terms of solid content. % Of a water-based silicate paint on a metal or plated metal plate in a dry mass of 0.1 to 3.0 g Zm ² and dried to form a silicate film. With excellent scratch resistance and corrosion resistance

The method for producing a heat-resistant metal sheet according to (1).

(6) It is composed of alkali metal silicate, colloidal silica, phosphate, silane coupling agent, polyolefin wax dispersion, and water, and has a Si / P mass ratio. Between 30 and 150 In addition, an aqueous silicate paint having an alkali metal content of 10 to 20% by mass in terms of solid content is used as a dry mass of 0.1 to 3.0 on the upper layer of a metal or a metal plate. The method for producing a heat-resistant metal sheet according to the above (2), wherein the metal sheet is coated with g / m ² and dried to form a silicate film, which is excellent in scratch resistance and corrosion resistance. BEST MODE FOR CARRYING OUT THE INVENTION

As the water-based silicate coating in the present invention, a coating obtained by adding an alkali metal silicate, colloidal silica, a silane coupling agent, and a polyolefin resin, or a coating obtained by further adding a phosphate in addition to these is used. I do. Although alkali metal silicate and colloidal silica alone are inferior in film forming properties, water resistance and scratch resistance, the addition of a silane coupling agent and the optimization of the content of aluminum metal in the film This improves the film forming properties and water resistance. The synergistic effect of these additives improves not only the corrosion resistance of the flat and processed parts before heating, but also the corrosion resistance after heating. On the other hand, scratch resistance can be improved by adding an appropriate amount of polyolefin as a lubricant. Also, by adding an appropriate amount of phosphate, the water resistance and the barrier property of the silicate film are improved, and the corrosion resistance can be further improved. By combining these technologies, we have succeeded in developing a heat-treated metal sheet with unprecedented excellent scratch resistance and corrosion resistance.

Hereinafter, a method for producing a heat-treated metal sheet having excellent scratch resistance and corrosion resistance according to the present invention will be described in detail.

Examples of the metal or plated metal plate to which the present invention can be applied include a steel plate and a zinc-plated metal plate having a plated upper layer, a zinc-nickel plated metal plate, a zinc-iron plated metal plate, and zinc. Chrome-plated metal plate, zinc-aluminum-plated metal plate, zinc-titanium-plated metal plate, Zinc-based electrical plating and melting of zinc-magnesium plated metal plate, zinc-manganese plated metal plate, zinc-aluminum magnesium plated metal plate, zinc-aluminum magnesium-silicon plated metal plate, etc. Plating, vapor-deposited steel plate, aluminum or aluminum alloy-plated metal plate, lead or lead alloy-plated metal plate, tin or tin alloy-plated metal plate, and a small amount of dissimilar metals in these plating layers Contains elements such as coparte, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, antimony, tin, copper, cadmium, silicon, arsenic, etc. And / or those in which inorganic substances such as silica, alumina, and titania are dispersed. Further, the present invention is applicable to a multi-layer plating in which the above plating is combined with another type of plating, for example, iron plating, iron-iron plating, or the like. However, when exposed to temperatures above 500 ° C, it is desirable to use an alloy plating such as zinc-nickel with a high melting point.

The plating adhesion amount on each plated metal plate is preferably 1 g Zm ² or more on one side, and if it is less than this, the corrosion resistance decreases.

The heat-treated metal sheet of the present invention is formed by forming a silicate film directly on a base metal or a plated metal sheet, or by forming a chromate film as a first layer from the lower layer and then forming a second layer. To form a silicate film. It is also possible to use a chromate free film as the first layer. As a means for forming a chromate film before forming a silicate film, for example, chromic anhydride, chromic acid, etc. Immersion in an aqueous solution containing salt or bichromate as the main component (reaction type) Chromate treatment, electrolytic type chromate treatment, and further, applying a treatment solution obtained by mixing the above aqueous solution with colloidal sily force etc. Coating-type mouth mate treatment method to dry without washing with water And the like.

Similarly, immersion (reaction-type) treatment, electrolytic treatment, and application after drying without washing with water are used as means for forming a close-mate free film before forming a silicate film. In general, the silicate compound used in the present invention is M ₂₀ n SiO ₂ (where M is an alkali metal of sodium, potassium, and lithium, and n is an arbitrary value. ) Means at least one mixture selected from sodium silicate, potassium silicate, and lithium silicate. N, which is the molar ratio between M ₂ O and S i O ₂ , is preferably in the range of 1 to 10. If the value of n is less than 1, the resulting film tends to absorb moisture, and the water resistance and the adhesion of the film become insufficient, and the corrosion resistance deteriorates. On the other hand, if it exceeds 10, the obtained film becomes brittle and the corrosion resistance of the processed portion deteriorates, which is not preferable.

The content of alkali metal contained in these silicate compounds is in the range of 10 to 20% by mass in terms of solid content as the content in the silicate coating. When the amount is less than 10% by mass, the film-forming property is poor and the corrosion resistance is poor. When the amount is more than 20% by mass, the water resistance is undesirably deteriorated.

As the colloidal silica used in the present invention, any of spherical, linear, or branched colloidal silica having a spherical coidal sily force bonded thereto may be used. In the case of spherical silica, the particle diameter is 5 to 50 nm, and in the case of linear silica, the diameter is 5 to 50 nm and the length Z thickness is chemically bonded to 1 to 5 In the case of having a bead-like force, it is preferable that the ratio of [the average particle diameter of the spherical force Z length of the bonded body] is 4 or more and has one or more branches.

Examples of the silane coupling agent used in the present invention include V— (2-aminoethyl) aminopropyltrimethoxysilane, y- (2 Aminoethyl) aminopropylmethyldimethoxysilane, 0 / — (

2 —aminoethyl) aminopropyl pyrethoxysilane, γ_ (2-aminoethyl) aminopropylmethylethoxysilane, γ —methacryloxypropyl trimethoxysilane, γ —methacrylate mouth xylmethylpymethyethoxysilane, γ —Metacryloxypropyl pyrrhetoxysilane, γ —Metharyloxypropyl methyl methyl ethoxysilane, Ν— / 3— (Ν-bierbenzilaminoethyl) _ γ—Aminoprovirtrimethoxysilane, Ν—] 3 — (N-Burbenyl diaminoethyl) — γ —Aminopropylmethyldimethoxysilane, Ν-J3 (N-vinylbenzylaminoethyl) — γ —Aminopropyl triethoxysilane, Ν-] 3-(Ν— Vininolebenzinoreami nochinore) i γ-amino propyl Tilgetoxysilane, γ-glycidoxy lip mouth Bitrimethoxysilane, y—Glycidoxypropylmethyldimethoxysilane, γ—Glycidoxypropyl methylethoxysilane, y—Glycidoxypropylmethyl methoxysilane, γ—Mercaptopropyl methylethoxysilane, y—mercaptopropylmethyldimethoxysilane, γ—mercaptopropylmethylethoxysilane, y—mercaptopropylmethylethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyl / reethoxyethoxysilane, butyltriethoxysilane, T / click b Ropuro Piruto Li main Tokishishiran, _gamma - click port opening pro Pirumechirujime Tokishishiran, gamma - click throat propyl Liethoxysilane, γ—Cross-mouth propylmethylethoxysilane, hexamethoxydisilazane. Pill methyl ethoxy silane, Burt trimethoxy silane, Bier methyl dimethoxy silane, Vinyl triethoxy Sisilane, Burmethyl ethoxysilane, Octadecyl dimethyl

[3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3_ (triethoxysilyl) propyl] Ammonium chloride, octadecyl dimethyl [3- (methylethoxysilyl) propyl] ammonium chloride, methinoletrichlorosilane, dimethinoresichlorosilane, trimethylclosilane, etc. The use of _v -glycidoxypropyl trimethoxysilane having a silyether ether group or γ-glycidoxyprovirtriethoxysilane further improves the corrosion resistance of the silicate film.

The silane coupling agent is incorporated in the silicate film in a range of 1% by mass or more and 20% by mass or less in terms of solid content. If it is less than 1% by mass, the corrosion resistance is inferior. If it exceeds 20% by mass, the stability and the corrosion resistance of the processing solution are undesirably deteriorated.

As the polyolefin wax used in the present invention, a polyethylene wax, a polypropylene wax, a polybutylene wax, or a modified polyolefin wax having a polar group added to these waxes may have an emulsifier concentration of 5% or less. Preferably, those dispersed in water or an aqueous solution without using an emulsifier are used. The polar group can be obtained by oxidizing the polyolefin with an oxidizing agent such as oxygen, ozone, or nitric acid in the presence of a catalyst, or oxidized polyolefin wax, or acrylic acid, metaacrylic acid, or the like. Ethylene unsaturated carboxylic acid monomers such as crotonic acid, maleic acid, fumaric acid, and itaconic acid and polyolefin wax are dissolved with benzol and the like, and a polymerization initiator (peroxide, redox, heavy metal, etc.) is dissolved. (Catalyst, etc.) and heated in a nitrogen stream to obtain a graph. The mass average particle size of the polyolefin wax purge ion is preferably from 0.1 to 5. 5. μιη, more preferably from 0.3 to 1. 1. μππι. If the mass average particle size is less than 0.1 m, it is not preferable because the coagulation and the stability are poor. On the other hand, when the mass average particle diameter exceeds 5.0 μιη, the dispersion stability is poor, which is not preferable. Further, the ratio of the mass average particle diameter to the number average particle diameter is preferably in the range of mass average particle diameter / number average particle diameter, that is, approximately 3. The polyolefin wax is preferably incorporated into the silicate film in a range of 35% by mass or less in terms of solid content. If it exceeds 35% by mass, the corrosion resistance after heating deteriorates, which is not preferable.

The as-phosphate salt used in the present invention, Seiri phosphate (H ₃ P 0 _4), TsugiAri phosphate (Η ₃ Ρ Ο _2), there phosphate (Η _₃ Ρ Ο _3), pyro -phosphate _{_{_{(Η 4 Ρ 2 Ο 7)}}} , preparative Ripori-phosphate of _{_{_{(Η 5 Ρ 3 Ο 1 (}}} )) and chemical formula _{_{Η Χ + 2 Ρ X 0 3Χ}} + ι ( where X is an integer of 3 or more) All condensed phosphoric acids and their salts are included. In particular, orthophosphate, phosphite, hypophosphite, and pyrophosphate are preferred because they are economical.

The Si mass ratio in the silicate film and the aqueous silicate solution is preferably in the range of 30 to 150. Further, the mass ratio of S i / P is preferably 35 to 80. If the Si ZP mass ratio is less than 30, bath stability and corrosion resistance will deteriorate. On the other hand, if the Si / P mass ratio exceeds 150, the effect of improving corrosion resistance and adhesion cannot be obtained.

The range of the coating amount of the kaic acid film is 0.1 to 3. O g Zm ² as dry weight. Preferably 0. 3~ 1. O g Zm ² to al of. The amount of adhered poor scratch resistance and corrosion resistance of interest is less than 0. lg Zm ^2, or 3. O g / m ² and more than that the order to form the undesirable Kei salt coating for difficult weldability Spray, spray, Any method such as a curtain, a flow coater, a rono coater, a no coater, a brush J, a dipping and an air knife squeezing may be used. The baking temperature is desirably 80 to 250 ° C. . Although there is no particular limitation on the drying equipment, a method using hot air blowing, a method using indirect heating with a heater, a method using infrared rays, a method using induction heating, and a method using these in combination can be adopted. Example

The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

(1) Type of drug

Table 1 shows a list of drugs used in the examples.

Drug

(2) Kind of metal plate

The metal plates shown in Table 2 were used.

Table 2 Types of metal plates and coating weight (plate thickness 2 mm)

(3) Chromate treatment

The EG and ZN shown in Table 2, chromic acid 5 0 gZ l, the electrolytic click Lome preparative process by energizing a predetermined quantity of electricity at a current density of 1 O AZD m ² in a bath of sulfuric acid 0. 3 g / 1 After washing with water, it was dried at a plate temperature of 80 ° C using a hot air drying oven.

For GI shown in Table 2, reduced chromic acid with a reduction rate of 40% was used. After silica coated with chromate treatment solution was blended so that 3 at a ratio of _{S i 0 2 / C r 0} 3, and dried without washing. The amount of the chromate film adhered was quantified in terms of Cr by X-ray fluorescence analysis.

(4) Preparation of water-based silicate paint

An aqueous silicate coating was prepared by mixing the silicate, colloidal silica, silane coupling agent, phosphate, and polyolefin wax shown in Table 1 in the ratios shown in Tables 4-7.

(5) Application and drying method of water-based silicate paint

Apply the water-based silicate paint prepared in (4) to the untreated plated metal plate and the chromated metal plate shown in (3) to the values shown in Tables 4 to 7 in terms of dry weight. The sample was baked and dried at an ultimate plate temperature of 140 to produce a sample for evaluation. The amount of the silicate coating was calculated by measuring the amount of the liquid film at the time of coating by a gravimetric method.

(6) Performance evaluation items

1) Flat plate corrosion resistance

The sample for evaluation prepared in (5) was sprayed with a 5% NaCl aqueous solution on the coated steel plate sample at an ambient temperature of 35 ° C according to the salt spray test method described in JIS Z 2371 for 72 hours. The subsequent whitening rate was measured and evaluated. In the following evaluations, ◎ and Δ were determined to be good.

◎: White 鲭 No occurrence

〇: Whiteness occurrence rate <10%

△: White △ Occurrence rate of 10% or more and less than 50%

X: White 鲭 incidence rate 50% or more

2) Corrosion resistance of processed part

The test specimen of the evaluation sample prepared in (5) was subjected to 6 mm Erichsen processing, and a 5% aqueous NaCl solution was applied at an ambient temperature of 35 ° C and a salt water spray test method described in JIS Z 2371. Sprayed on painted steel sheet sample After 48 hours, the incidence of white spots in the processed part was measured. In the following evaluations, ◎ and Δ were judged to be good.

◎: White 鲭 No occurrence

〇: Whiteness occurrence rate <10%

△: White △ Occurrence rate of 10% or more and less than 50%

X: White 鲭 incidence rate 50% or more

3) Corrosion resistance after heating

The sample prepared in (5) was subjected to a heating treatment to 600 ° C by an induction heating method, and 5% NaCl at an ambient temperature of 35 ° C and a temperature of 35% according to the salt spray test method described in JIS Z 2371. The aqueous solution was sprayed on the coated steel sheet sample, and the reddish emission rate in the processed portion 48 hours later was measured. In the following evaluations, ◎ and Δ were judged to be good. '

◎: Red 鲭 No occurrence

〇: Red 鲭 incidence rate less than 10%

△: Red 鲭 Occurrence rate 10% or more, less than 50%

X: Red 鲭 incidence rate 50% or more

4) Scratch resistance

A square tube crank press test was performed on the sample prepared in (5). The conditions of the square cylinder crank press test were as follows: a blank (0.8 x 220 x l80 mm) was molded to 65 x ll 5 mm and a height of 5 omm with a wrinkle pressure of 6 tons. The sliding surface after molding was visually evaluated. In the following evaluations, ◎ and Δ were judged to be good.

◎: No blackening

〇: The area less than 50% of the sliding part is blackened and there is a sliding flaw. △: The area of 50% or more of the sliding part is blackened and there is a sliding flaw.

X: Base metal is exposed and galling

5) Continuous weldability A continuous spot welding test was performed on the sample prepared in (5) under the conditions shown in Table 3, and the number of spots at which a nugget diameter of 3 mm or more could be formed stably was determined.

Table 3 Welding conditions

In the following evaluations, ◎ and Δ were determined to be good.

◎: Number of hit points 5 0 0 0 or more

〇: Number of hit points 2 5 0 0 or more and less than 5 0 0 0

△: Number of hits 1 0 0 0 or more and less than 2 500

X: Number of hits less than 100

Tables 4 to 7 show the above evaluation results. From Tables 4 to 7, it is clear that the heat-treated metal sheet of the present invention is excellent not only in flat plate corrosion resistance, corrosion resistance in the processed portion, and corrosion resistance after heating, but also in scratch resistance and weldability.

撇嗨; i ¾

Table 4

(1) Type and mass% of silanecaline in icy silicate paint and silicate film (solid content) (2) Type and mass% of wax in icy silicate paint and silicate film (solid content)

Table 4 (continued)

Table 5

1) In water-based silicate paints and silicate coatings ί: Type and quality of silane coupling agent in%: (solid content)

2) Water type and mass% (solid content conversion) in water-based silicate paint and silicate coating

5 (continued)

Performance

No.Plate processed part After heating Scratch resistance Weldability Remarks Corrosion resistance Corrosion resistance Corrosion resistance

29 〇〇〇 ◎ © Date

30 ◎ ◎ ◎ ◎ ◎ The present invention

31 ◎ ◎ ◎ ◎ ◎ Invention

32 ◎ ◎ ◎ ◎ ◎

33 ◎ 〇 ◎ ◎ ◎ Date of departure

34 △ X 〇 X ◎ Ratio

35 ◎ 〇 ◎ ◎ ◎ Date of departure

36 ◎ ◎ ◎ ◎ ◎ The present invention

37 ◎ ◎ ◎ ◎ ◎ Date of departure

38 ◎ 〇 ◎ ◎ ◎ The present invention

39 〇〇〇〇 ◎ The present invention

40 ◎ ◎ ◎ ◎ ◎ Main departure 0

41 ◎ ◎ ◎ ◎ 〇 The present invention

42 ◎ ◎ ◎ ◎ ◎

43 ◎ ◎-© ◎ ◎

44 ◎ ◎ ◎ ◎ ◎

45 ◎ ◎ ◎ 〇 ◎ The present invention

# Separation λ

Table 6

Table 6 (continued)

, ντ mi performance

Zinc flat plate Processing part After heating Scratch resistance Weldability Remarks Corrosion resistance Corrosion resistance Corrosion resistance

45 〇〇 ◎ ◎ ◎ The present invention

46 ◎ ◎ o ◎ ◎ The present invention

47 ◎ ◎ 〇 ◎ ◎ The present invention

48 ◎ ◎ 〇 ◎ ◎ The present invention

49 ◎ 〇〇 ◎. ◎ The present invention

50 〇〇〇〇 ◎ The present invention

5 1 〇〇〇〇 ◎ The present invention

52 ◎ ◎ 〇 ◎ ◎ The present invention

53 ◎ ◎ o ◎ 〇 Date of departure

54 ◎ ◎ ◎ ◎ ◎

55 ◎ ◎ 〇〇 ◎ Date of departure

56 〇〇 ◎ ◎ ◎ The present invention

57 ◎ ◎ o ◎ ◎ The present invention

58 ◎ ◎ 〇 ◎ ◎ The present invention

59 ◎ ◎ 〇 ◎ ◎ The present invention

60 ◎ 〇 ◎ ◎ ◎

6 1 m X 〇 X ◎ Comparative example

62 ◎ 〇〇 ◎ ◎ The present invention

63 ◎ ◎ 〇 ◎ ◎ The present invention

64 ◎ ◎ ◎ ◎ ◎ Date of departure

65 ◎ 〇 ◎ ◎ ◎ The present invention

66 〇〇〇 ◎ ◎ The present invention

67 ◎ ◎ 〇 ◎ ◎ The present invention

68 ◎ ◎ 〇 ◎ 〇 The present invention

69 ◎ ◎ 〇 ◎ ◎ The present invention

70 ◎ ◎ ◎ ◎ ◎

7 1 ◎ ◎ o ◎ ◎ The present invention

72 ◎ ◎ 〇 ◎ ◎ The present invention

Nen * ¾

Table 7

撇 fin ^^ ¾

Table 7 (continued) 1—j Performance

Plate processing part After heating Scratch resistance Weldability Remarks Corrosion resistance Corrosion resistance Corrosion resistance

73 o 〇 ◎ ◎ ◎ Uninvented

74 ◎ ◎ ◎ ◎ Invention

75 ® ◎ ◎ ◎ ◎ Departure ^

◎ ◎ ◎ ◎ ◎ Uninvented

7 1 ◎ 〇 ◎ ◎ ◎ Departure s

78 〇〇〇 ◎ ◎ The present invention

79 〇〇〇〇 ◎ The present invention

80 ◎ ◎ ◎ ◎ ◎ The present invention

81 ◎ ◎ ◎ ◎ 〇 The present invention

82 ◎ ◎ ◎ ◎ ◎ The present invention

83 ◎ ◎ ◎ o ◎ The present invention

84 〇〇 ◎ ◎ ◎ The present invention

85 ◎ ◎ ◎ ◎ ◎ Primary s month

86 ◎ ◎ ◎

87 ◎ ◎ ◎ The present invention

◎ ◎ ◎ ◎ The present invention

88 ◎ 〇 ◎ ◎ ◎

89 Δ X ◎ X ◎ Comparative example

90 ◎ 〇 ◎ ◎ ◎ 3 Explanation

91 ◎ ◎ ◎ ◎ ◎ The present invention

92 ◎ ◎ ◎ ◎ ◎ The present invention

93 ◎ 〇 ◎ ◎ ◎ The present invention

94 〇〇〇 O ◎ The present invention

95 ◎ ◎ ◎ ◎ ◎ Date of departure

96 ◎ ◎ ◎ ◎ 発明 The present invention

97 ◎ ◎ ◎ ◎ ◎ The present invention

98 ◎ ◎ ◎ ◎ ◎ The present invention

99 ◎ ◎ ◎ ◎ ◎ The present invention

1 00 ◎ ◎ ◎ 〇 ◎ The present invention

Industrial applicability

Since the heat-resistant metal plate of the present invention is a heat-resistant metal plate having good scratch resistance and corrosion resistance, it is suitable as a heat-resistant material in the fields of home appliances, building materials and automobiles. Further, the heat-treated metal plate having good scratch resistance and corrosion resistance can be provided to the market by the aqueous silicate coating and the production method according to the present invention.

20

Claims

The scope of the claims

1. A 0.1 to 3. Og / m ² silicate coating on the metal or plated metal plate, and the silicate coating is an alkali metal silicate, colloidal silica, silane coupling agent A heat-treated metal sheet having excellent scratch resistance and corrosion resistance, characterized in that the heat-treated metal sheet is made of polyolefin and has an alkali metal content of 10 to 20% by mass.

2. A 0.1 to 3 Og / m ² silicate coating on the top layer of the metal or plated metal plate, the silicate coating being an alkali metal silicate, colloidal silica, or phosphorus It is composed of a silicate, a silane coupling agent and a polyolefin resin, and has a Si / P mass ratio of 30 to 150 in the silicate film and an alkali metal content of 10 A heat-treated metal sheet having excellent scratch resistance and corrosion resistance, characterized in that the content of the metal sheet is from 20 to 20% by mass.

3. It is composed of alkali metal silicate, colloidal silica, silane coupling agent, polyolefin dispersion and water, and has an alkali metal content of 10 to 20% by mass in terms of solid content. The aqueous silicate which can be applied to the upper layer of a metal or plated metal plate and dried to produce the heat-resistant metal plate according to claim 1, which is excellent in scratch resistance and corrosion resistance. paint.

4. It is composed of alkali metal silicate, colloidal silica, phosphate, silane coupling agent, polyolefin wax dispersion and water, and has a Si / P mass ratio of 30. Applied to the upper layer of a metal or plated metal plate, characterized in that the content of alkali metal is from 10 to 20% by mass in terms of solid content, dried and scratch resistant The heat-treated metal sheet according to claim 2, which has excellent heat resistance and corrosion resistance.

twenty one Aqueous silicate paints that can be made.

5. Aqueous solution composed of alkali metal silicate, colloidal silica, silane coupling agent, polyolefin wax dispensing ion and water and having an alkali metal content of 10 to 20% by mass in terms of solid content. the Kei salt paint, metal, or a dry mass in the upper layer of the plated metal plate 0. 1~ 3. O g Zm ² coating, scratch resistance, characterized in that dried to form a Kei salt coating 2. The method for producing a heat-treated metal sheet according to claim 1, which is excellent in corrosion resistance.

6. It is composed of alkali metal silicate, colloidal silica, phosphate, silane coupling agent, polyolefin wax dispersion and water, and has a Si / P mass ratio of 30 to 1 The water-based silicate paint having an alkali metal content of 10 to 20% by mass in terms of solid content of 50 or more is used as a dry mass on the upper layer of the metal or plated metal plate. 3. The method for producing a heat-treated metal sheet according to claim 2, wherein the metal sheet is coated with 1 to 3.0 g / m ² and dried to form a silicate film, and has excellent scratch resistance and corrosion resistance.

twenty two