WO2003093533A1

WO2003093533A1 - Thermostabilized metal plate of high corrosion resistance, metal plate with organic coating and phosphated galvanized metal plate

Info

Publication number: WO2003093533A1
Application number: PCT/JP2003/004688
Authority: WO
Inventors: Kengo Yoshida; Toshikazu Amemiya; Atsushi Morishita; Akira Takahashi; Shigeyuki Meguro; Katsuyoshi Yamasoe
Original assignee: Nippon Steel Corporation; Nippon Paint Co., Ltd.
Priority date: 2002-04-16
Filing date: 2003-04-14
Publication date: 2003-11-13
Also published as: JPWO2003093533A1; TW200307056A; AU2003236248A1; JP4416645B2; AU2003236248A8

Abstract

A thermostabilized metal plate of high corrosion resistance; a metal plate with organic coating; and a phosphated galvanized metal plate. The thermostabilized metal plate comprises a metal plate or plated metal plate and, superimposed on a surface thereof, a precoating composed of a titanium compound and/or a zirconium compound (a), a phosphate compound (b) and a guanidine compound (c), the precoating overlaid with a silicate coating. In the metal plate with organic coating, the precoating is overlaid with an organic/inorganic composite coating containing colloidal silica. The phosphated galvanized metal plate comprises a zinc or zinc alloy plated metal plate having a zinc phosphate coating at its surface, the zinc phosphate coating overlaid with a sealing coating composed of a titanium compound and/or a zirconium compound (a), a phosphate compound (b) and a guanidine compound (c).

Description

Description Heat-resistant metal plate, organic coated metal plate, and phosphate-treated zinc-plated metal plate with excellent corrosion resistance

The present invention relates to a heat-treated metal sheet having excellent corrosion resistance, which can be suitably used for applications such as automobiles, home appliances, and building materials, and an organic-coated metal sheet having excellent flat plate corrosion resistance, processed part corrosion resistance, paint adhesion, and weldability. And a phosphate-treated zinc-based metal plate having excellent corrosion resistance and adhesion. 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 have been treated with lip mouth treatment and phosphate for the purpose of improving corrosion resistance and paint adhesion.

Furthermore, in recent years, in particular, in the home appliance industry, those that have been applied without coating have been increasing from the viewpoint of saving processes and costs. Not only corrosion resistance and paint adhesion, but also galling resistance, fingerprint resistance, and Demand for various performance requirements for steel sheet surface appearance quality, such as uneven dew condensation, is increasing.In order to meet such performance demands of customers, special processing is performed on the steel sheet by performing a chromate treatment. A painted metal plate with an organic composite film based on it has been developed. For example, Japanese Patent Publication No. 411,191 discloses the formation of an organic composite film on a steel plate coated with chromate by adding an aqueous organic resin to a colloid sol with a specific fine particle size and adding corrosion resistance. A method for producing a surface-treated steel sheet with improved performance such as resistance and fingerprint resistance is disclosed.

However, the resin film used for such a steel sheet has only a heat resistance of about 150 to 250 ° C, and it cannot be said that it has a sufficient function for the heat resistance. Specifically, for example, in a heat link band used for a cathode ray tube, a heat treatment of about 600 ° C. is performed, and for a stove or the like, a heat treatment is performed at about 200 to 400 ° C. for a long time. used . Therefore, it is necessary to maintain sufficient performance such as corrosion resistance even under such heating.

To deal with such issues, Japanese Patent Publication No. Hei 6-23889 discloses an organic-inorganic composite having an organic-inorganic composite film on a chromate-coated steel sheet with excellent heat resistance, heat resistance, discoloration resistance and corrosion resistance. A steel plate is disclosed. Japanese Patent Application Laid-Open Publication No. 2000-15741 discloses that a zinc-based plated steel sheet has a straight silicone resin film formed on a surface thereof, which is resistant to discoloration upon heating, smoke generation upon heating, and corrosion resistance after heating. Further, a steel sheet having excellent scratch resistance is disclosed, and can be suitably used for applications such as a heat shrink band stove.

Japanese Unexamined Patent Publication (Kokai) No. 3-394855 discloses that after subjecting a zinc-based plated steel sheet to a close mate treatment, the aqueous resin has silica and a glass transition point (T g point) of 40 ° C. A coating material in which the above-mentioned paint is dispersed is coated with a dry mass of 0.3 to 3.0 g / m ² . Also, Japanese Patent Application Laid-Open No. 3-28380 discloses that after a chromate treatment is applied to a galvanized steel sheet, a carboxylated polyethylene resin and a Teflon ™ lubricant are used. A lubricated steel sheet coated with 0.5 to 4.0 g / m ^{2 of} paint as a dry mass is disclosed. Furthermore, in order to meet the demands of customers who require severe galling resistance, such as deep drawing workability, a solid lubricant has been added to the organic film to improve the lubricity. Steel plate was developed. For example, Japanese Patent Application Laid-Open No. Hei 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. 41141/91 has excellent 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 surface-treated steel sheets coated with such an organic film may have scratches during handling, galling during press working, and abrasion during product transportation. .

On the other hand, the techniques disclosed in Japanese Patent Application Laid-Open Nos. 3-39485 and 3-28380 have a problem that galling and abrasion occur during the press working described above. In particular, the technology disclosed in Japanese Patent Application Laid-Open No. 6-173730 has excellent press galling resistance even in severe processing such as deep drawing workability. .

On the other hand, with the growing interest in global environmental issues in recent years, the movement to eliminate environmentally incompatible materials such as hexavalent chromium has been activated. However, in order to obtain sufficient corrosion resistance, any of the steel sheets disclosed in Japanese Patent Publication No. Hei 6-23989 and Japanese Patent Application Laid-Open No. 2000-15741 are required Need to be processed. Therefore, development of a heat-treated steel sheet that does not contain hexavalent chromium and has excellent corrosion resistance after heating has been desired. Japanese Patent Publication No. 4-141,191 mentioned above; Japanese Patent Publication No. Hei 3-39485, Japanese Patent Publication No. Hei 3-28380, or Japanese Patent Publication No. However, the steel sheet disclosed in Japanese Patent Application Publication No. 2000-205,097 also requires a close mate treatment to obtain sufficient corrosion resistance. Therefore, development of an organic-coated steel sheet that does not contain hexavalent chromium and has excellent corrosion resistance has been desired.

Furthermore, the corrosion resistance and paint adhesion of Phosphate treatment is also used for the purpose of improvement. Phosphate treatment has attracted attention from an environmental point of view, but the phosphatized film itself does not have sufficient corrosion resistance and adhesion. Therefore, in general

Sealing treatment using an aqueous solution containing hexavalent chromium is performed to improve corrosion resistance and adhesion. Therefore, there is a need for the development of a sealing treatment technique that does not contain hexavalent chromium and can improve the corrosion resistance and adhesion of a phosphate treated film.

In order to solve such a problem, for example, Japanese Patent Application Laid-Open No. 58-197284 describes that after treatment with phosphate, treatment with an aqueous solution containing polyacrylic acid and an aromatic polyhydric alcohol is carried out. However, the corrosion resistance and the adhesion are inferior to those of the conventional sealing chromate treatment.

In addition, Japanese Patent Publication No. 59-141114 discloses a technique in which the surface of a chemical conversion treatment film is contacted with a post-treatment compound selected from poly (141-biphenol) or a derivative or a salt thereof. However, there are problems such as insufficient corrosion resistance and adhesion, and high processing cost.

Japanese Patent Publication No. 60-34912 discloses that one or two or more of oxidized and precipitated inhibitors other than chromic acid may be used alone or on a phosphate film. A technique is disclosed in which an aqueous solution containing 10 ppm to 20% in a complex is applied by means of spraying, coating, etc., and then dried.However, the corrosion resistance and adhesion are also higher when compared with conventional sealing chromate treatment. Poor nature. Disclosure of the invention

An object of the present invention is to solve the above problems and provide a heat-resistant metal plate excellent in corrosion resistance, an organic coated metal plate excellent in flat plate corrosion resistance, processed portion corrosion resistance, paint adhesion and weldability, and Excellent corrosion resistance and adhesion An object of the present invention is to provide a metal plate coated with a phosphate-based zinc.

As a result of various studies to solve the above problems, the present inventors have found that a titanium compound film containing a phosphoric acid compound and a guanidine compound as a pre-treatment film is formed on the surface of a metal or plated metal plate. And z or a zirconium compound film, and further, by forming a silicate film on the zirconium compound film, a heat-treated metal sheet having excellent corrosion resistance can be obtained.

That is, the first aspect of the present invention provides the following heat-resistant metal plate.

(1) on the surface of a metal plate or plated metal plate, pre-treatment coating and to (a). 1 to a 1 ~ 1 0 0 mg / m 2 or the zirconium compound in terms of zirconium in titanium terms of titanium compound 10 O mg / m ² , or the sum of titanium compound and zirconium compound in terms of titanium and zirconium:! ~ 1 0 O mg / m ² have, and be one containing pretreatment coating and (b)-phosphate compound (c) guanidine compound, 0.1 the upper layer to be al-3. A heat-resistant metal plate with excellent corrosion resistance, characterized in that a silicate film of O g Zm ² is formed.

(2) The above (1), wherein the content of the phosphoric acid compound is from 10 to 150 parts by mass relative to 100 parts by mass of the component (a) (in terms of titanium or zirconium). A heat-resistant metal plate having excellent corrosion resistance as described in (1).

(3) The above-mentioned (1), wherein the content of the guanidine compound is 15 to 150 parts by mass with respect to the component (a) 100 parts by mass (in terms of titanium or zirconium). ) And (2) a heat-resistant metal sheet having excellent corrosion resistance.

(4) Magnesium, zinc, aluminum, and run One or more selected from the group consisting of tan, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, and nickel compound, in an amount of 5 to 5 parts by mass per component (a) 100 parts by mass (in terms of titanium or zirconium). The heat-resistant metal sheet having excellent corrosion resistance according to any one of (1) to (3), which contains 200 parts by mass.

(5) One or more water-soluble resins should be contained in the pretreatment film in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). The heat-resistant metal sheet excellent in corrosion resistance according to any one of (1) to (4), which is characterized by the above-mentioned.

(6) The silicate film is composed of an alkali metal silicate, colloidal silica, a silane coupling agent, and a polyolefin wax dispersion, and the content of alkali metal is 10%. The heat-resistant metal sheet having excellent heat resistance according to any one of (1) to (5), wherein the heat-treated metal sheet has a content of up to 20% by mass.

(7) The silicate film is composed of an alkali metal silicate, colloidal silica, a silane coupling agent, a phosphate, and a polyolefin wax dispersion, and (1) to (1) characterized in that the Si / P mass ratio in the coating is 30 to 150, and the alkali metal content is 10 to 2 ° mass%. 5) A heat-treated metal sheet having excellent corrosion resistance as described in 5).

The present inventors also provide a pretreatment film based on a titanium compound, a zirconium compound, or a mixture of a titanium compound and a zirconium compound, and a phosphoric acid compound and a guanidine compound. Using these materials, the film-forming properties of the pretreatment film with titanium compound and zirconium compound, the barrier properties, adhesion, the inhibitory effect of phosphoric acid compounds and guanidine compounds, and the upper layer By adjusting the barrier effect of the formed organic-inorganic composite film, It has made it possible to dramatically improve the corrosion resistance of organic coated metal sheets. That is, in a second aspect, the present invention provides the following organically coated metal plate.

(1) As a pretreatment film on the surface of a metal plate or a plated metal plate, (a) a titanium compound of 1 to 10 O mg / m ^{2 in} terms of titanium or a zirconium compound of zirconium 1 to 1 ◦ O mg Zm

² , or a titanium compound and a zirconium compound each having a total of 1 to 10 Omg / m ^{2 in} terms of titanium and zirconium, and the pretreatment film comprises (b) a phosphoric acid compound and (c) a guanidine compound. be those containing, organic-inorganic composite film is 0.1 to 3 containing from 5 to 35% weight% of colloidal silica mosquitoes in terms of solid content in the upper layer is et. 0 g / m ² is formed An organically coated metal plate with excellent corrosion resistance.

(2) The above-mentioned (1), wherein the content of the phosphoric acid compound is 10 to 150 parts by mass relative to 100 parts by mass of the component (a) (in terms of titanium or zirconium). The organic-coated metal sheet having excellent corrosion resistance according to (1).

(3) The above (1), wherein the content of the guanidine compound is 15 to 150 parts by mass relative to the component (a) 100 parts by mass (in terms of titanium or zirconium). The organic coated metal sheet having excellent corrosion resistance described in 2).

(4) One or more kinds selected from magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, and a nickel compound are contained in the pretreatment film as a component (a) 1 The organic-coated metal sheet excellent in corrosion resistance according to any one of (1) to (3), wherein the content is 5 to 200 parts by mass relative to 100 parts by mass (in terms of titanium or zirconium). (5) One or more water-soluble resins are contained in the pretreatment film in an amount of 0.5 to 40 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). The organic coated metal sheet having excellent corrosion resistance according to any one of the above (1) to (4).

(6) The above-mentioned (1) to (5), characterized in that the organic-inorganic composite film further contains 35% by mass or less of a polyolefin wax dispersion in terms of a solid content. 2. An organically coated metal plate having excellent corrosion resistance as described in 1.

The present inventors have further developed a titanium compound film containing a phosphoric acid compound and a guanidine compound as a sealing treatment on the surface of a metal plate coated with zinc or a zinc-based alloy that has been treated with zinc phosphate. Alternatively, it has been found that by forming a zinc and zirconium compound film, a phosphate-treated zinc-coated steel sheet having excellent corrosion resistance and adhesion can be obtained.

That is, in a third aspect, the present invention provides the following zinc-coated zinc-coated steel sheet.

(1) A zinc phosphate coating and a sealing coating on the zinc phosphate coating on the surface of a metal plate coated with zinc or a zinc-based alloy. (A) Titanium compound is 1 to 20 Omg / m ² or zirconium of compound 1 to zirconium terms ² 0 O mg / m 2, or titanium two © beam compound and a zirconium compound in total 1 ~ ² 0 O mg Zm 2 formed of titanium and zirconium two © beam converted respectively A metal plate coated with a phosphatized zinc, characterized in that the lacquered coating contains (b) a phosphoric acid compound and (c) a guanidine compound in the sealing film.

(2) The above (1), wherein the content of the phosphoric acid compound is 10 to 150 parts by mass relative to 100 parts by mass of the component (a) (in terms of titanium or zirconium). 2. A metal plate coated with a phosphatized zinc according to claim 1. (3) The above-mentioned (1), wherein the content of the guanidine compound is 15 to 150 parts by mass with respect to the component (a) 100 parts by mass (in terms of titanium or zirconium). ) And (2) a metal plate coated with a zinc-treated zinc phosphate.

(4) At least one selected from the group consisting of magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, and nickel compound is contained in the sealing film. The phosphate-treated zinc according to any one of (1) to (3), which is contained in an amount of 5 to 200 parts by mass with respect to 100 parts by mass (in terms of titanium or zirconium). Metal plate with metal plating.

(5) The sealing film contains 0.5 to 40 parts by mass of at least one water-soluble resin based on 100 parts by mass of component ('a) (in terms of titanium or zirconium). The phosphate-treated zinc-coated metal plate according to any one of (1) to (4), which is characterized in that: BEST MODE FOR CARRYING OUT THE INVENTION

The heat-resistant metal sheet having excellent corrosion resistance according to the first aspect of the present invention will be described in detail. In the heat-resistant metal sheet of the present invention, a titanium compound or a zirconium compound, or a titanium compound and a zirconium Based on a mixture of compounds, use a mixture containing a phosphate compound and a guanidine compound. The titanium compound and the zirconium compound form the pretreatment film, have a barrier property, adherence, inhibit the phosphoric acid compound and the guanidine compound, and form the silicate film formed on the upper layer. By combining the parier effect, the corrosion resistance of heat-treated metal sheets can be dramatically improved Hereinafter, the method for producing a heat-treated metal sheet having excellent corrosion resistance according to the present invention will be described in detail.

Examples of the metal or plated metal plate usable in the heat-resistant treated metal plate of the present invention include a steel plate and a zinc-plated metal plate plated with an upper layer thereof, a zinc-nickel plated metal plate, a zinc-iron plated metal plate, Zinc-chrome plated metal plate, zinc-aluminum plated metal plate, zinc-aluminum-magnesium plated metal plate, zinc-aluminum-magnesium-silicon plated metal plate, zinc-titanium-plated metal plate, zinc-magnesium-plated metal Sheet, zinc-based manganese-plated metal sheet, zinc-based electric plating, hot-dip plating, vapor-deposited steel plate, aluminum or aluminum alloy-plated metal plate, lead or lead alloy-plated metal plate, tin or tin alloy A small amount of dissimilar metal elements or impurities can be added to the plating metal plate and these plating layers. , Molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, antimony, tin, copper, cadmium, silicon, arsenic, and / or silica, Includes those in which inorganic substances such as alumina and titania are dispersed. Furthermore, the present invention can be used for multi-layer plating in combination with the above plating and other types of plating, for example, iron plating, iron monolith plating, and the like. However, when exposed to a high temperature exceeding 500 ° C, it is preferable to use an alloy plating such as zinc-nickel having a high melting point.

The coating weight on the 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.

In the pretreatment liquid for forming the pretreatment film in the present invention, the component (a) is a titanium compound alone, a zirconium compound alone, or a mixture of a titanium compound and a zirconium compound, or a component (b). Phosphoric acid compound, guanidine compound as component (c) Use

Examples of the titanium compound as the component (a) include titanium hydrofluoric acid, titanium ammonium fluoride, titanium oxalate, titanium sulfate, titanium chloride, titanium isopropoxide, isopropyl titanate, titanium ethoxide, and the like. Titanium 2-ethyl-1-hexanolate, tetraisopropyl propyl titanate, tetra-n-butyl titanate, potassium titanium fluoride, sodium titanium fluoride and the like. Examples of zirconium compounds include zirconium carbonate ammonium, dinolecon hydrofluoric acid, dinolecon fusidium ammonium, ginole konfujidani potassium, dinolecon fluoride sodium, zirconium acetyl acetate, Zirconium butoxide-1-butanol solution, dinoreconium-n-propoxide, dinoleconine nitrate, dinoleconium chloride, zirconium carboxylate, and the like.

The phosphoric acid compound as the component (b) includes, for example, orthophosphoric acid and orthophosphoric acid salts, polyphosphoric acid, metallic acid, pyrrolic acid, phenolic acid, etc. And the salts thereof. The phosphoric acid compounds may be used alone or in combination of two or more. The content of the phosphoric acid compound is 10 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the phosphoric acid compound is less than 10 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is not economically desirable.

The guanidine compound as the component (c) includes, for example, guanidine hydrochloride, guanidine nitrate, guanidine carbonate, rodanguanidine, aminoguanidine bicarbonate, aminoguanidine hydrochloride, guanidine phosphate, and guanidine sulfamate. And the like. The guanidine compound may be used alone or in combination of two or more. As the content of guanidine compound The amount is 15 to 150 parts by mass based on 100 parts by mass of component (a) (converted value of titanium or zirconium). If the content of the guanidine compound is less than 15 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically unfavorable.

By adding a metal compound to the pretreatment film, the corrosion resistance can be further improved. Metal compounds include magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, nickel oxides, hydroxides, complex fluorides, nitrates, and sulfuric acid. Salts and phosphates. The metal compounds may be used alone or in combination of two or more. The content of the metal compound is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the metal compound is less than 5 parts by mass, the effect of improving corrosion resistance cannot be obtained, and if it exceeds 200 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.

Corrosion resistance can be improved by adding a water-soluble resin to the pretreatment film. Examples of the water-soluble resin include an acrylic resin, a urethane resin, an ethylene acryl copolymer, a phenol-based resin, a polyester-based resin, a polyolefin resin, an alkyd resin, and a polycarbonate-based resin. The water-soluble resins may be used alone or in combination of two or more. The content of the water-soluble resin is preferably in the range of 0.5 to 20 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the water-soluble resin is less than 0.5 part by mass, the effect of improving the corrosion resistance cannot be obtained. If the content exceeds 20 parts by mass, not only the appearance after heating but also the corrosion resistance is deteriorated, which is preferable. Absent The adhesion amount of the pre-treatment film may be 1 to 100 mg Zm ² in titanium conversion, 1 to 100 mg / m ² in zirconium compound in titanium conversion, or 1 to 100 mg / m ² in zirconium conversion. A total of l-100 mg Zm ^{2 of the} ruconium compound is deposited on titanium and zirconium respectively. If the amount of adhesion is less than 1 mg nom ² in the above conversion value, sufficient corrosion resistance cannot be obtained, and if it exceeds 100 mg / m ² , the effect of improving corrosion resistance saturates, which is economically undesirable.

In the present invention, after forming a pretreatment film on a metal or plated metal plate, a silicate film is formed to complete a heat-resistant metal plate.

The silicate compound used in the present invention is generally represented by M ₂₀ · n SiO ₂ (M is sodium, potassium, or an alkali metal of lithium, and n is an arbitrary number). Yes, at least one selected from sodium silicate, potassium silicate, and lithium silicate. N, which is the molar ratio of M ₂ O to S i O ₂ , is preferably in the range of 1 to 10. If the value of n is less than 1, the obtained film is likely to absorb moisture, and the water resistance and the adhesion of the film become insufficient, and the corrosion resistance deteriorates, which is not preferable. 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 alkali metal contained in the silicate compound preferably has a content in the silicate film of 10 to 20% by mass in terms of solid content. If the amount is less than 10% by mass, the film-forming properties are poor and the corrosion resistance is poor.

As the colloidal silica used in the present invention, any of spherical, linear, or beaded silica having a branched spherical colloidal 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 silicic force, the diameter is 5 to 50 nm and the length / thickness ratio is 1 to 5 chemically bonded, with branching Beaded silica It is preferable that the ratio of [the average particle diameter of the spherical force] to the length of the Z-bond is 4 or more and has one or more branches.

Examples of the silane coupling agent used in the present invention include γ- (2-aminoethyl) aminopropyltrimethoxysilane, and y- (2-aminoaminoethyl) amino. Propylmethyl dimethyl xylan, _γ- (2_aminoethyl) amino propyl triethoxysilane, _γ- (2—aminoethyl) amino propylmethyl xylan, y-meth Taku Li Russia Kishipuro building door Li main door Kishishira down, _ meta-click _re-γ Russia Kishipu opening Pinoreme Chinorejime door Kishishiran, γ - meta-click Li Rokishipuro building door Li E door Kishishira down, γ - meta data Li Russia Kishipuro Pirume Tilgetoxysilan, Ν-β- (Ν-vinylbenzylaminoethyl) _γ-amino propyl trimethoxysilane, Ν-i3- (N_bierbenziluraminoe ) _ Γ —Amino propylmetyldimethoxysilane, Ν—] 3 ― (Ν—Vininolebenzinorea minoethinole) _γ —Aminopropinole triethoxysilane, キシ -β- ( Ν — Vininolebenzilaminoamino etinole)-γ-Aminopropyryl thiethyl ethoxysilane, γ-dalicidoxypip Mouth pinoretrimethycsilane, y-glycidoxypropynolemethyldimethyxylane, y-glycidoxypropyl Triethoxysilane, γ-Dalicidoxypropylmethylethyl ethoxysilane, γ-Mercaptopropyl trimethoxysilane, γ-Mercaptopropyl ^ 7 Remethyldimethoxysilane, γ-Mercaptopropyl Liethoxysilane, 7-mercapto propylmethyl xyletoxysilane, methyl Limethoxy silane, dimethyl dimethoxy silane, methyl triethoxy silane, dimethyl jet xylan, butyl triacetoxy silane, ゥ -chloroprovir trimethoxy silane, γ-co-mouth propinolemethinoresime methoxysilane, γ-cro-mouth propyl triethoxysilane, γ-chloro mouth pinoremetyl xylet xylan, hexamethoxydisilazane, γ-anilinopropyl trimethoxysilane, γ-anilinopropyl methyldimethoxysilane, Τ / -anilinopropyl methylethoxysilane, _Υ- anilinopropylmethyl ethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, butylethoxysilane Sisilane, vinyl methyl ethoxysilane, octadecyl dimethyl [3— (trimethoxysilyl) propyl] ammonium chloride

Octadecyl dimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl [3-(triethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl [3-(methyl methoxysilyl) ) Propyl] ammonium chloride, methinoletrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc., and γ-daricoxypropyl trimethyl group having a glycidyl ether group can be used. The use of toxic silane or glycidoxypropyl triethoxysilane further improves the corrosion resistance of the silicate coating.

The mixing ratio of the silane coupling agent is preferably in the range of 1% by mass to 20% by mass in terms of solid content in the silicate film. If the amount is less than 1% by mass, the corrosion resistance is poor. If the amount exceeds 20% by mass, the stability and the corrosion resistance of the processing solution deteriorate, which is not preferable.

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 an emulsifier. Use a solution dispersed in water or an aqueous solution without using a solution. The polar group is an oxidized polyolefin wax obtained by oxidizing a polyolefin with an oxidizing agent such as oxygen, ozone or nitric acid in the presence of a catalyst, or acrylic acid, methacrylinoleic acid, Tonic acid, maleic acid, Ethylene unsaturated carboxylic acid monomers such as fumaric acid and itaconic acid and polyolefin wax are dissolved with benzol, etc., and heated in a nitrogen stream with a polymerization initiator (peroxide, redox, heavy metal catalyst, etc.) to obtain a graph. .

The mass average particle diameter of the polyolefin wax dispersion is preferably from 0.1 to 5.〜 μπι, more preferably from 0.3 to 1.Ο μπι. If the mass average particle size is less than 0.1 μπι, it is not preferable because the coagulation and the stability are poor. On the other hand, when the mass average particle size exceeds 5.0 μπι, the dispersion stability is poor, which is not preferable. Further, the ratio between the mass average particle diameter and the number average particle diameter is preferably in the range of mass average particle diameter / number average particle diameter, that is, approximately 3.

The mixing ratio of the polyolefin wax is preferably within a range of 35% by mass or less in terms of solid content in the silicate film. If it exceeds 35% by mass, the corrosion resistance after heating deteriorates, which is not preferable.

Is a as a-phosphate salt used in the present invention, Seiri phosphate (H ₃ P 0 _4), TsugiAri phosphate (H ₃ P 0 _2), there phosphate (H ₃ P 0 _3), pyro-phosphate _{_{_{(Η 4 Ρ 2 Ο 7)}}} , Application Benefits poly-phosphate _{_{_{(H 5 P 3 O 1C)}}} ) and chemical formula _{_{H X + 2 PXO 3X + 1}} ( where X is an integer of three or more )), And all acids and salts thereof. In particular, orthophosphate, phosphite, hypophosphite, and pyrophosphate are preferred because they are economical.

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

Adhesion amount range Kei acid coating to 0. 1~ 3. 0 g / m ² as a dry weight. Preferably 0. 3~ 1. O g Zm ² to al of. Adhesion amount The but 0. Lg Z in m less than ² poor scratch resistance and corrosion resistance of interest, or 3. 0 g / m ² and more than a pre undesirable because weldability becomes difficult treatment film and Kei salt coating As a coating method for forming, any method such as spraying, curtain, flow coater, Rhono recorder, Nor coater, brush coating, dipping, and air knife drawing may be used.

The baking temperature of the pretreatment film is not particularly specified, but is preferably in the range of 40 to 200 ° C. The baking temperature of the silicate film is preferably in the range of 100 to 200 ° C.

Although there is no particular limitation on the drying equipment, a method using hot air blowing, a method using indirect heating using a heater, a method using infrared rays, a method using induction heating, and a method using these in combination can be adopted.

Next, an organic-coated metal plate having excellent corrosion resistance according to the second aspect of the present invention will be described in detail.

In the organic coated metal sheet of the present invention, as the pretreatment film, as in the heat-resistant metal sheet of the first aspect, a titanium compound, a zirconium compound, or a mixture of a titanium compound and a zirconium compound is used. It is used as a base and contains a phosphoric acid compound and a guanidine compound. The titanium compound and the zirconium compound impart the film-forming properties, barrier properties, and adhesion of the pre-treated film, the inhibitory effect of the phosphate compound and the guanidine compound, and the organic-inorganic composite film formed thereover. The interaction can dramatically improve the corrosion resistance of the organically coated metal sheet.

Hereinafter, the method for producing an organic coated metal sheet having excellent corrosion resistance according to the present invention will be described in detail.

Metal or plating that can be used in the organic coated metal plate of the present invention The metal plate may be the same as that used for the heat-resistant metal plate on the first side.

In the pretreatment liquid for forming the pretreatment film in the present invention, the components

(a) a titanium compound alone, a zirconium compound alone, or a mixture of a titanium compound and a zirconium compound, a phosphoric acid compound as the component (b), and a guanidine compound as the component (c) use.

The titanium compound of component (a) is the same as that used in the first aspect.

The zirconium compound is the same as that used in the first aspect.

The phosphoric acid compound as the component (b) is the same as that used in the first aspect. The phosphoric acid compounds may be used alone or in combination of two or more. The content of the phosphoric acid compound is 10 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium- or zirconium). If the content of the phosphoric acid compound is less than 10 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.

The guanidine compound as the component (c) is the same as that used in the first aspect. The guanidine compound may be used alone or in combination of two or more. The content of the guanidine compound is 15 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the guanidine compound is less than 15 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.

Also in the second aspect, the corrosion resistance can be further improved by adding a metal compound to the pretreatment film. As metal compounds, the first The same ones used on the sides can be used. The metal compounds may be used alone or in combination of two or more. The content of the metal compound is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the metal compound is less than 5 parts by mass, the effect of improving the corrosion resistance cannot be obtained. The corrosion resistance can be improved by adding a water-soluble resin to the pretreatment film. The same water-soluble resin as used in the first aspect can be used. The water-soluble resins may be used alone or in combination of two or more. The content of the water-soluble resin is preferably in the range of 0.5 to 40 parts by mass relative to 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the water-soluble resin is less than 0.5 parts by mass, the effect of improving corrosion resistance cannot be obtained.

The adhesion amount of the pretreatment film is as follows: titanium compound: 1 to 100 mg Zm ² in titanium conversion; zirconium compound: 1 to 100 mg / m ² in zirconium conversion; or titanium compound And zirconium compounds in total in terms of titanium and zirconium, respectively.

Deposit 1 to 10 O mg / m ² . If the amount of adhesion is less than 1 mg / m ² in the above conversion value, sufficient corrosion resistance cannot be obtained, and if it exceeds 10 O mg Zm ² , the effect of improving corrosion resistance is saturated, which is economically undesirable.

In the present invention, an organic-inorganic composite film is formed after forming a pretreatment film on a metal or plated metal plate to complete an organic-coated metal plate. Next, the organic-inorganic composite film will be described.

Aqueous resins for the organic-inorganic composite film used in the present invention include acryl ester / acrylic acid copolymer, epoxy'acrylic acid, olefin acrylic acid copolymer, olefin ionomer, and styrene. Acrylic acid copolymers, urethane acrylic acid copolymers, urethane epoxy resins, ethylene imide acrylic resins and the like can be used. It is preferable to use an emulsion dispersed in an aqueous solvent as a coating for forming a film. If necessary, a bridging agent such as various melamine resins and amino resins may be added. Among these, when considering both performance and cost, it is preferable to use an acrylic resin such as a copolymer of acrylic acid and the like. When strict deep drawing is required, it is preferable to use a urethane epoxy resin having both hardness and elongation.

As the colloidal silica used in the organic-inorganic composite film, any of spherical, linear, or branched colloidal silica having a branched colloidal silica force may be used. In the case of a spherical silica, the particle diameter is 5 to 50 nm, and in the case of a linear silica force, the diameter is 5 to 50 nm and the length-to-thickness ratio is chemically bonded to 1 to 5; In the case of having a bead-like die force, it is preferable that the ratio of [average particle diameter of spherical die force / length of the binder] is 4 or more and has one or more branches.

The colloidal force is incorporated in the aqueous organic / inorganic composite film in an amount of 5 to 35% by mass in terms of solid content. If it is less than 5% by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 35% by mass, paint adhesion deteriorates, which is not preferable. In the present invention, the scratch resistance can be further improved by adding a predetermined amount of polyolefin wax dispersion to the organic-inorganic composite coating. As the polyolefin wax used in the present invention, polyethylene wax, polypropylene wax, polybutylene wax or a modified polyolefin wax having a polar group added to these waxes has an emulsifier concentration of 5% or less, preferably without using an emulsifier. Use those dispersed in water or an aqueous solution. Polar groups convert polyolefin waxes to oxygen, ozone or nitric acid in the presence of a catalyst. Oxidized polyolefin wax obtained by oxidizing with an oxidizing agent such as an acid, or ethylenically unsaturated carbon such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid An acid monomer and a polyolefin wax are dissolved with benzol or the like, and are heated and graphed together with a polymerization initiator (peroxide, redox, heavy metal catalyst, etc.) in a nitrogen stream.

The mass average particle diameter of the polyolefin wax purge ion is preferably from 0.1 to 5.1 μμη, more preferably from 0.3 to: 1.1 μμπι. When the mass average particle size is less than 0.1 μιη, it is not preferable because the aggregation and the stability are poor. On the other hand, if the mass average particle size exceeds 5.0 μπι, 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 blended in the organic-inorganic composite film in a range of 35% by mass or less in terms of solid content. If it exceeds 35% by mass, paint adhesion is deteriorated, which is not preferable.

Adhesion amount range of organic-inorganic composite coating film is a dry weight and ^{0. 1~3. 0 g / m 2} . More preferably, it is 0.3 to 1.5 g / m ² . If the adhesion amount is less than 0.1 g / m ² , the intended corrosion resistance is inferior, and if it exceeds 3.0 g / m ² , the weldability becomes difficult.

Coating methods for forming the pretreatment film and the organic-inorganic composite film in the second aspect include spray, curtain, flow coater, roll coater, per coater, brush coating, immersion, and analytic drawing. Either method may be used.

The baking temperature of the pretreatment film is preferably in the range of 40 to 200 ° C. On the other hand, the baking temperature of the organic-inorganic composite film is preferably in the range of 80 to 250 ° C. If the temperature is lower than 80 ° C, water in the organic-inorganic composite paint However, it is difficult to completely volatilize, so that the corrosion resistance is lowered. If the temperature exceeds 250 ° C., the skin is hardened too much and the workability is lowered, which is not preferable.

Next, the phosphate-treated zinc-coated metal plate according to the third aspect of the present invention will be described in detail.

The sealing treatment film in the phosphate-treated zinc-coated metal sheet of the present invention is based on a titanium compound, a zirconium compound, or a mixture of a titanium compound and a zirconium compound, It contains a compound and a guanidine compound. Titanium compound and zirconium compound provide film-forming properties, barrier properties and adhesion of sealing film, and sealing film by inhibitor effect of phosphoric acid compound and guanidine compound The corrosion resistance can be dramatically improved.

Hereinafter, the method of the present invention for producing a phosphate-treated zinc-coated metal sheet having excellent corrosion resistance and adhesion will be described in detail.

The plating metal plate usable in the phosphate-treated zinc plating metal plate of the present invention includes a zinc plating metal plate, a zinc-nickel plating metal plate, a zinc-iron plating metal plate, and a zinc plating metal plate. Chrome plated metal plate, zinc-aluminum plated metal plate, zinc-aluminum-magnesium plated metal plate, zinc-aluminum-magnesium-silicon plated metal plate, zinc-titanium plated metal plate, zinc-magnesium plated metal Includes zinc-based electric plating, hot-dip plating, and vapor-deposited steel sheets, such as sheets and zinc-manganese-plated metal sheets. It is preferable that the coating weight on one side of the plated metal plate is 0.2 g Zm ² or more, and if it is less than this, the corrosion resistance decreases. In the present invention, the zinc-coated steel sheet is first subjected to a zinc phosphate treatment, and then subjected to a sealing treatment.

The zinc phosphate treatment method is not particularly limited as long as it can be used industrially. The coating amount of the zinc phosphate treated film is preferably in the range of 1.0 to 3.0 gm ² . If it is less than 1.0 g Zm ² , the corrosion resistance deteriorates, and if it exceeds 3.0 g Zm ² , the weldability deteriorates.

As the sealing solution for forming the sealing film in the present invention, a titanium compound alone, a zirconium compound alone, or a mixture of a titanium compound and a zirconium compound as the component (a), )) And a guanidine compound as the component (c).

The titanium compounds of component (a) are the same as those used in the first aspect.

The zirconium compound is the same as that used in the first aspect. The phosphoric acid compound as the component (b) is the same as that used in the first aspect. The phosphoric acid compounds may be used alone or in combination of two or more. The content of the phosphoric acid compound is 10 to 150 parts by mass with respect to 100 parts by mass of the component (a) (in terms of titanium or zirconium). If the content of the phosphoric acid compound is less than 10 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.

The guanidine compound as the component (c) is the same as that used in the first aspect. The guanidine compound may be used alone or in combination of two or more. The content of the guanidine compound is 15 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium). The guanidine compound content is less than 15 parts by mass. When the amount exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.

By adding a metal compound to the sealing film, the corrosion resistance can be further improved. The same metal compound as that used in the first aspect can be used. The metal compounds may be used alone or in combination of two or more. The content of the metal compound is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the metal compound is less than 5 parts by mass, the effect of improving corrosion resistance cannot be obtained, and if it exceeds 200 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.

Corrosion resistance can also be improved by adding a water-soluble resin to the sealing film. The same water-soluble resin as that used in the first aspect can be used. The water-soluble resins may be used alone or in combination of two or more. The content of the water-soluble resin is preferably in the range of 0.5 to 40 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the water-soluble resin is less than 0.5 part by mass, the effect of improving corrosion resistance cannot be obtained, and if it exceeds 40 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.

As the amount of adhered-Ceiling treatment film, a titanium compound is 1 ~ 2 0 0 mg / m 2 or zirconium compound is 1 ~ 2 0 0 mg / m or titanium of compound in terms of zirconium, in Chita Niumu terms The zirconium compound is deposited on titanium and zirconium in a total amount of 1 to 20 mg / m ^{2, respectively} . If the amount of adhesion is less than 1 mg / m ² in the above conversion value, sufficient corrosion resistance cannot be obtained, and if it exceeds ²⁰⁰ mg / m ² , the effect of improving corrosion resistance is saturated, which is not economically preferable.

The coating method for forming the sealing film is '~~, power' ~ ten, flow ¹ ~ co ¹ ~ ta ¹ ~ ~, mouth ¹ ~ noreko ¹ ~ ~ ta ¹ ~, no ¹ ~ ¹ ~ ¹ ~, brush coating, dipping and air knife drawing etc. The above method may be used.

The baking temperature is not particularly specified, but is preferably

It is desirable that the temperature be 40 to 200 ° C.

Example

The present invention is not limited by these Examples, the power S for specifically explaining the present invention by Examples and Comparative Examples.

First, an example of the first aspect of the present invention will be described.

(1) Type of pretreatment chemical

Table 1 shows a list of pretreatment chemicals used in the examples. Pretreatment chemical

Drug type No.Drug

Titanium compound A 1 Titanium hydrofluoric acid (reagent)

Ginorekonidumi A2 Titanium Ammonium Fluoride (Reagent)

Compound A 3 Zircon hydrofluoric acid (reagent)

Phosphoric acid compound B 1 Orthophosphoric acid (reagent)

C 1 Guanidine phosphate (manufactured by Sanwa Chemical Co.) Guanidine compound C 2 Guanidine nitrate (reagent)

Product C 3 Guanidine carbonate (reagent)

D 1 Zinc oxide (reagent)

Metal compound D 2 Magnesium sulfate (reagent)

D 3 Aluminum hydroxide (reagent)

D 4 Colloidal silica (Snowtex 0, manufactured by Nissan Kagaku)

Water-soluble resin E 1 Polyacrylic acid (reagent)

E 2 Polymethacrylic acid (reagent) Table 2 shows a list of chemicals for silicate coating used in the examples.Table 2 Chemicals for silicate coating

(2) Kind of metal plate

The metal plates shown in Table 3 were used. Table 3 Types of metal plates and coating weight (plate thickness: 1.2 mm)

(3) Preparation of pretreatment liquid

The titanium compound, zirconium compound, phosphoric acid compound, guanidine compound, metal compound, and water-soluble resin shown in Table 1 were distributed in the ratio shown in Table 5. Then, a pretreatment liquid was prepared.

(4) Preparation of silicate treatment solution

An aqueous silicate coating was prepared by mixing the silicate, colloidal silica, silane coupling agent, phosphate and polyolefin as shown in Table 2 in the proportions shown in Table 6.

(5) Application and drying method of pretreatment liquid and silicate treatment liquid

The pretreatment liquid prepared in (3) was applied so as to have the values shown in Tables 7 to 9 in terms of dry weight, and dried at a final plate temperature of 80 ° C. Next, the silicate treatment solution prepared in (4) was applied so that the values shown in Tables 7 to 9 were obtained, dried at a plate temperature of 120 ° C, and cooled with water to obtain a sample for evaluation. Produced. The amounts of the pretreatment film and the silicate film were calculated by measuring the amount of the liquid film at the time of application 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% aqueous NaCl solution on the coated steel sheet at an ambient temperature of 35 ° C in accordance with the salt water fog test method described in JIS Z 2371. The whitening occurrence rate after the time 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 piece of the evaluation sample prepared in (5) was subjected to 6 mm Elixen processing, and was subjected to a salt water spray test method described in JIS Z 2371, at an ambient temperature of 35 ° C and 5% NaCl. The aqueous solution was sprayed on the coated steel sheet sample, and the occurrence of white spots in the processed portion after 48 hours was measured. The following reviews 価 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

3) Corrosion resistance after heating

The sample prepared in (5) is subjected to a heat treatment up to 600 ° C by an induction heating method, and is subjected to 5% at an ambient temperature of 35 ° C according to the salt spray test method described in JIS Z 2371. NaCl aqueous solution was sprayed on the coated steel sheet sample, and after 48 hours, the reddish emission rate in the processed part was measured and evaluated. In the following evaluations, ◎ and Δ were determined 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 rectangular cylinder crank press test was performed on the sample prepared in (5). The conditions of the square cylinder crank press test were as follows: a sample (0.8 x 220 x 180 mm) was molded to 65 x 115 mm and a height of 5 Omm with a blank 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: Area of less than 50% of the sliding part is blackened, with sliding flaws △: 50% or more of the sliding part is blackened, with sliding flaws

X: Base metal is exposed and galling

5) Continuous weldability

For the sample prepared in (5), the continuous spot A welding test was performed to determine the number of hit points at which a nugget diameter of 3 mm or more could be formed stably.

Table 4 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

Table 79 shows the above evaluation results. From Table 79, 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 a processed portion, and corrosion resistance after heating but also in scratch resistance and weldability. o. Ti / Zr-f ligated compound Phosphorus ligated compound Anisin's compound Metallic ligated compound Water-soluble tree

Plant type Halo M.

X1 Α1 100 B1 50 C1 100

X2 Α2 100 B1 50 C1 100

X3 A3 100 B1 50 C1 100

X4 Α1 100

X5 Α1 100 B1 10 C1 100

X6 Α1 100 B1 150 C1 100

X7 Α1 100 B1 50 C1 15

X8 Α1 100 B1 50 C1 150

X9 Α1 100 B1 50 C2 100

X10 Α1 100 B1 50 C3 100

X11 Α1 100 B1 50 C1 100 D1 15

X12 Α1 100 B1 50 C1 100 D2 15

X13 Α1 100 B1 50 C1 100 D3 .15

X14 Α1 100 B1 50 C1 100 D4 50

X15 Α1 100 B1 50 C1 100 D3 5

X16 Α1 100 B1 50 C1 100 D3 200

X17 Α1 100 B1 50 C1 100 E1 5

X18 Α1 100 B1 50 C1 100 E2 5

X19 Α1 100 B1 50 G1 100 E1 0.5

X20 Α1 100 B1 50 G1 100 E1 20

X21 Α1 100 B1 50 C1 100 D1 15 E1 5

X22 Α1 100 B1 50 C1 100 D1 / D3 10/10 Table 6 Composition of silicate coating

No. silicate silica silane? / Purige ') wax ² ) phosphate alkali type kind M.

Y1 A1 B1 c

0 D1 5 10

Y2 A1 B1 c

1 0 Dl 5 12 丫 3 A1 B1 c

Then 1 0 Dl 5 15

Y4 A1 B1 CI 5 D1 5

1 one 17

Y5 A B1 01 0 D1 5 1 fl

Y6 A2 B1 CI 5 D1 5 17

Y7 A3 B1 CI 5 D1 5 1 17

Y8 A1 B2 CI 5 D1 5 17

Y9 A1 B3 CI 5 D1 5 17

Y10 A1 B4 G1 5 D1 5 17

Y11 A1 B1 2 2 5 D1 5 ■■ ~ 17 ~ 丫 12 A1 B1 d d 0 Dl 5 17 17

Y13 A1 B1 5 D1 5 1 7

Y14 A1 B1 CI 5 D2 5 "~ ~~ 17 f 丫 15 A1 B1 CI 5 D3 5 17

Y16 A1 B1 C I 5 D1 5 Ε1 50 inn

Y17 A1 B1 Cl 5 D1 5 Ε1 50 1 0

Y18 A1 B1 C1 5 D1 5 Ε1 50 i \ K

Y19 A1 B1 J on

U I 0 t (r

1 0U 1 /

Y20 A1 B1 G1 5 D1 5 E1 50 20

Y21 A1 B1 C 5 D1 5 El 30 17

Y22 A1 B1 C1 5 D1 5 E1 70 17

Y23 A1 B1 C1 5 D1 5 E1 100 17

Y24 A1 B1 C1 5 Dl 5 E1 150 17 丫 25 A1 B1 C1 5 D1 5 E2 50 17

Y26 A1 B1 C1 5 D1 5 E3 50 17 丫 2f A1 B1 C1 5 D1 5 E1 50 17 丫 28 A1 B1 C1 5 D1 1 E1 50 17 丫 29 A1 7

Y30 B1 0

Table 7

CO

Table 8

CO

t

Table 8 continued

Table 9

^ Release ¾ ^-

Table 9 continued

Metal plate Pre-treatment Ca-silicate performance

Coating amount Type Coating amount 付着 Coating amount Flat plate Scratch resistance after processing section Weldability fffl Consideration number (g / m ² ), mg / m ² ) (g / m ² ) Corrosion resistance

101 ΖΝ 20 X1 20 Y13 0.5 ® ◎ ◎ ◎ The present invention

102 2Ν 20 X1 20 Y14 0.5 ◎ © ◎ ■ ◎ The present invention

103 ΖΝ 20 X1 20 Y15 0.5 © ◎ The present invention

104 ΖΝ 20 X1 20 Y16 0.5 〇 Ο o ◎ © The present invention

105 ΖΝ 20 X1 20 Y17 0.5 ◎ ®-◎ The present invention

106 ΖΝ 20 X1 20 Y18 0.5 ◎ ◎ ◎ The present invention

107 ΖΝ 20 X1 20 Y19 0.5 ◎ ◎ © ◎ The present invention

108 ΖΝ 20 X1 20 Y20 0.5 ◎ O ◎ ◎ ◎ The present invention

109 ΖΝ 20 X1 20 Y21 0.5 o ◎ The present invention

110 ΖΝ 20 X1 20 Y22 0.5 ◎ ◎ ◎ ◎

111 ΖΝ 20 X1 20 Y23 0.5 ◎ ◎ ◎

112 ΖΝ 20 X1 20 Ϋ 24 0.5 ◎ 0 ◎ ◎ ◎ The present invention

113 ΖΝ 20 X1 20 Y19 0.3 ◎ ο ο © The present invention

114 ΖΝ 20 X1 20 Y19 1.0 ◎ ® ◎ ◎ @ The present invention

115 ΖΝ 20 X1 20 Y19 3.0 ◎ ◎ Ο Takaaki Moto

116 ΖΝ 20 X1 20 Y25 0.5 ◎ ◎ ◎ ◎ The present invention

117 ΖΝ 20 X1 20 Y26 0.5 ◎ ◎ ◎ ◎ ◎ The present invention

118 ΖΝ 20 X1 20 Y27 0.5 ◎ ◎ ◎ ◎ ◎ The present invention

119 ΖΝ 20 X1 20 Y28 0.5 ◎ ◎ ◎ 〇 ◎ The present invention

120 2Ν 20 X1 20 Y29 0.5 X X X ◎ Comparative example

121 ΖΝ 20 X1 20 Y30 0.5 XXXX ◎ Comparative example

Next, an example of the second aspect will be described.

(1) Type of pretreatment chemical

A list of pretreatment drugs used in the examples is shown in Table 10. Table 10 Pretreatment drugs

Table 11 lists the chemicals for organic-inorganic composite coatings used in the examples.Table 11 Chemicals for organic-inorganic composite coatings

34 (2) Metal plate type ''

The metal plates shown in Table 12 were used. Table 1 2 Types of metal plates and coating weight (plate thickness 2 mm)

(3) Preparation of pretreatment liquid

A titanium compound, a zirconium compound, a phosphoric acid compound, a guanidine compound, a metal compound, and a water-soluble resin shown in Table 10 were blended in the ratio shown in Table 13 to prepare a pretreatment liquid.

(4) Preparation of organic-inorganic composite solution

The organic resin, colloidal silica, and polyolefin wax shown in Table 11 were blended in the ratio shown in Table 14 to prepare an organic-inorganic composite paint.

(5) Application and drying method of pretreatment liquid and organic-inorganic composite treatment liquid

The pretreatment liquid prepared in (3) was applied so as to have the values shown in Tables 15 to 17 as a dry weight, and dried at a final plate temperature of 80 ° C. Next, the organic-inorganic composite treatment solution prepared in (4) was applied so that the values shown in Tables 15 to 17 were applied, dried at a final plate temperature of 120 ° C, and then cooled with water to obtain a sample for evaluation. Was prepared. The amounts of the pretreatment film and the organic-inorganic composite film were calculated by measuring the amount of the liquid film at the time of application by a gravimetric method.

(6) Performance evaluation items

1) Flat plate corrosion resistance

The evaluation sample prepared in (5) was evaluated in the same manner as in the example of the first aspect, except that the whitening rate after 48 hours was measured and evaluated.

35 2) Corrosion resistance of processed part

The evaluation sample prepared in (5) was evaluated in the same manner as in the example of the first aspect, except that the evaluation was performed by measuring the whitening rate in the processed portion after 24 hours.

3) Paint adhesion

Using a percoater, apply a melamine-alkyd resin paint (Amilac # 1000, manufactured by Kansai Paint Co., Ltd.) on the surface-treated metal plate so that the dry film thickness becomes 25 μπι. Bake at ° C for 20 minutes. Next, a 7 mn ^ Erichsen process was applied, and an adhesive tape (Nichipan Co., Ltd .: Cellotape) was attached to the Eriksen portion of the test piece. The adhesive tape was immediately pulled obliquely at an angle of 45 °, and the appearance of the Erichsen-processed portion was visually evaluated. In the following evaluations, ◎ and Δ were judged to be good.

◎: No peeling

〇: Peeling area ratio less than 5%

△: Peeling area ratio 5% or more, less than 50%

X: Peeling area ratio 50% or more

4) Continuous weldability

The sample prepared in (5) was evaluated as described in the example for the first aspect.

Tables 15 to 17 show the above evaluation results. From Tables 15 to 17, it is clear that the organically coated metal sheet of the present invention is excellent in flat plate corrosion resistance, corrosion resistance in processed parts, paint adhesion and weldability.

36 f "i A_Pretreatment coating composition

No. teriyaki ¹ les SSI teriyagi ku 7 2'non-compound tertiary compound water-soluble resin type type type K ■■ type, .m type

X1 A1 100 B1 50 G1 100 ― ―

X2 A2 100 B1 50 C1 100 One--

X3 A3 100 B1 50 C1 100 ― ― ―

X4 A1 100------

X5 A1 100 B1 10 C1 100 One-

X6 A1 100 B1 150 C1 100 ― one

XI ΑΊ 100 B1 50 C1 15

X8 A1 100 B1 50 C1 150 —

X9 Al 100 B1 50 C2 100

Enter Yi I n U A I I uu b I ou C3 100

X1 1 A1 100 B1 50 C1 100 D1 15

X12 A1 100 B1 50 01 100 D2 15

X13 A1 100 B1 50 C1 100 D3 15

X14 A1 100 B1 50 C1 100 D4 50

X15 A1 100 B1 50 C1 100 D3 5

X16 A1 100 B1 50 C1 100 D3 200

X17 A1 100 B1 50 C1 100 E1 5

X18 A1 100 B1 50 C1 100 E2 5

X19 A1 100 B1 50 C1 100 E1 0.5

X20 A1 100 B1 50 C1 100 E1 40

X21 A1 100 B1 50 C1 100 D1 15 E1 5

X22 A1 100 B1 50 C1 100 D1 / D3 10/10

37 L Composition of organic-inorganic composite coating

No. Organic resin Silica ¹ ) Wax

type

Y1 F1 I

Y2 F1 G1 5 '1 ■■■■■-

Y3 F1 G1 10

Y4 F1 G1 15

Y5 F1 G1 20

Y6 F1 G1 25

Y7 F1 G1 30

Y8 F1 G1 35

Y9 F1 G1 40

丫 10 F2 G1 10

Y1 1 F2 G1 20

丫 12 F2 G1

Y13 F3 G1 20

Y14 F4 G1 20

Y15 F1 G2 20

Y16 F1 G1 20 H1 5

Y17 F1 G1 20 H1 10

Y18 F1 G1 20 H1 20

Y19 F1 G1 20 H1 30

Y20 F1 G1 20 H1 35

Y21 F1 G1 20 H1 40

Y22 F1 G1 20 H2 5

Y23 F1 G1 20 H3 5

Y24 F2 G1 20 H2 5

Y25 F2 G1 20 H3 5) Solid content ratio of wax contained in organic-inorganic composite coating (W

) Solica solid content ratio in organic-inorganic composite coating (%)

38 Table 15

39 Table 16

40 Table 17

41 As shown by these results, the organic-coated metal sheet of the present invention is a metal sheet having good flat plate corrosion resistance, corrosion resistance in a processed portion, paint adhesion and weldability, and is therefore suitable as a material in the fields of home appliances, building materials and automobiles. It is.

Next, an example of the third aspect will be described.

(1) Drug type

Table 18 shows a list of drugs used in the examples. Table 18 Drugs

(2) Kind of metal plate

The metal plates shown in Table 19 were used.

42 Table 19 Types of metal plates and coating weight (plate thickness: 1.2 mm)

(3) Zinc phosphate treatment

After EG, ZN and GI shown in Table 19 were degreased, surface conditioning and phosphate treatment were performed under the following conditions. The surface was adjusted using a surf fin 5N_5 manufactured by Nippon Paint Co., Ltd. and sprayed at a temperature of 50 ° C for 2 seconds. Using Hudine ZS910, spray treatment, water washing and drying were performed at a temperature of 65 ° C. for 8 seconds to form a zinc phosphate film. The amount of the zinc phosphite coating was determined by quantifying the amount of phosphorus by X-ray fluorescence analysis and converting it to the amount of the coating.

(4) Preparation of sealing solution

A titanium compound, a zirconium compound, a phosphoric acid compound, a guanidine compound, a metal compound, and a water-soluble resin shown in Table 18 were blended at the ratios shown in Tables 20 and 21 to prepare a sealing treatment solution.

(5) Applying and drying the sealing solution

On the plated metal sheet treated with zinc phosphate by the method shown in (3), apply the sealing solution prepared in (4) to the values shown in Tables 20 and 21 as the dry weight. Then, the sample was dried at a final plate temperature of 80 ° C. to prepare an evaluation sample. The adhesion amount of the sealing film was calculated by measuring the amount of the liquid film at the time of application by a gravimetric method.

(6) Performance evaluation items

1) Flat plate corrosion resistance

The evaluation sample prepared in (5) was evaluated for the whitening rate after 48 hours.

43 The evaluation was performed in the same manner as in the example for the first aspect, except that measurement and evaluation were performed.

2) Corrosion resistance of processed part

The evaluation sample prepared in (5) was evaluated in the same manner as in the example of the first aspect, except that the evaluation of the white spots in the processed portion after 24 hours was performed.

3) Paint adhesion

The paint adhesion of the surface-treated metal sheet sample was evaluated as described in the example for the second aspect.

4) Continuous weldability

Tables 20 and 21 show the above evaluation results. From Tables 20 and 21, it is clear that the phosphate-treated zinc-coated metal sheet of the present invention is excellent in flat plate corrosion resistance, processed part corrosion resistance, adhesion and weldability.

44 Table 20

Metal sheet Phosphorous acid Sealing coating

-Type 1 adhesion amount. Adhesion amount Ti / Zr compound Phosphoric acid compound 7 Nissinen compound Metal compound Water-soluble resin Adhesion amount

/ m ² ) (g / m ² )

1 EG 20 2 A1 100 B1 50 C1 100 ― ―.

2 EG 20 2 A1 100 B1 50 C1 too ― ― one ― 1.0

3 EG 20 2 A1 100 B1 50 C1 100 11-10

-4 EG 20 2 A1 100 B1 50 C1 100 ― ― ― ― 50

5 EG 20 2 A1 100 B1 50 ct 100 One---100

6 EG 20 2 A1 100 B1 50 C1 100 ― One ― 200

7 EG 20 2 A2 100 B1 50 C1 100 One--One 50

8 EG 20 2 A3 100 B1 50 C1 00 1 ― ― ― 50

9 EG 20 2 A1 100 ― one ― ― ― one ― one 50

1 0 EG 20 2 A1 100 B1 10 C1 100 ― ― ― One 50

1 1 EG 20 2 A1 100 B1 150 G1 100 1 ― ― ― 50

1 2 EG 20 2 A1 100 B1 50 C1 15 ― 11 ― 50

1 3 EG 20 2 A1 100 B1 50 C1 150 ― ― ―― ― 50

1 4 EG 20 2 A1 100 B1 50 C2 100 ― ― One 50

1 5 EG 20 2 A1 100 B1 50 C3 100 ― 110

1 6 EG 20 2 A1 100 B1 50 C1 100 D1 15 1 1 50

1 7 EG 20 2 A1 100 B1 50 C1 100 D2 15 50

1 8 EG 20 2 A1 100 Bt 50 C1 100 D3 15 1 ― 50

1 9 EG 20 2 A1 100 B1 50 C1 100 D4 50 1 50

20 EG 20 2 A1 100 B1 50 C1 100 D3 5 50

21 EG 20 2 A1 100 B1 50 ct 100 D3 200 50

22 EG 20 2 A1 100 B1 50 C1 100 E1 5 50

23 EG 20 2 A1 100 B1 50 C1 100 E2 5 50

24 EG 20 2 A1 100 B1 50 C1 100 E1 0.5 50

25 EG 20 2 A1 100 B1 50 .C1 100 E1 40 50

26 EG 20 2 A1 100 B1 50 C1 100 D1 15 E1 5 50

27 EG 20 2 A1 100 B1 50 C1 100 D1 / D3 10/10 50

28 EG 20 1 A1 100 B1 50 C1 100 50

29 EG 20 3 At 100 B1 50 C1 100 One I One 50

Table 20 continued

45/1 Replacement Form (Rule 26i Table 2

Industrial applicability

Since the heat-resistant metal sheet of the present invention is a heat-resistant metal sheet having good corrosion resistance, it is suitable as a heat-resistant material in the fields of home appliances, building materials and automobiles.

The organic coated metal plate of the present invention is also a metal plate having good flat plate corrosion resistance, corrosion resistance in a processed portion, paint adhesion and weldability, and is therefore suitable as a material in the fields of home appliances, building materials and automobiles.

The phosphate-treated zinc-coated metal sheet of the present invention is also a metal sheet having good corrosion resistance and adhesion, and is therefore suitable as a material for use in home appliances, building materials, and automobiles.

47

Claims

The scope of the claims

1. On the surface of the metal plate or plated metal plate, as a pretreatment film: (a) 1 to 100 mg of titanium compound in terms of titanium Zm ² or 1 to 10 O in terms of zirconium compound of zirconium compound mg / m ² , or a titanium compound and a zirconium compound each having a total of 1 to 10 O mg / m ^{2 in} terms of titanium and zirconium, and the pre-treatment film is composed of (b) a phosphoric acid compound and (C) A heat-resistant metal sheet having excellent corrosion resistance, characterized by containing a guanidine compound and further having a silicate film of 0.1 to 3.0 O g Zm ² formed thereon.

2. The phosphoric acid compound content is from 10 to 150 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). Heat-resistant metal plate with excellent corrosion resistance described in 1

3. The method according to claim 1, wherein the content of the guanidine compound is 15 to 150 parts by mass with respect to 100 parts by mass of the component (a) (in terms of titanium or zirconium). Heat-resistant metal plate with excellent corrosion resistance.

4. In the pre-treatment film, one or more components selected from magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, and nickel compounds are used as components. The corrosion resistance according to any one of claims 1 to 3, wherein the content is 5 to 200 parts by mass based on (a) 100 parts by mass (a titanium or zirconium conversion value). Excellent heat-resistant metal plate.

5. One or more water-soluble resins are added to the pretreatment film in an amount of 0.5 to 100 parts by mass of component (a) (in terms of titanium or zirconium).

48 The heat-resistant metal sheet having excellent corrosion resistance according to any one of claims 1 to 4, characterized in that the metal sheet contains from 20 to 20 parts by mass.

6. The silicate film is composed of an alkali metal silicate, colloidal silica, a silane coupling agent, and a polyolefin dispersant, and the content of alkali metal is 10 to 10. The heat-resistant metal sheet having excellent corrosion resistance according to any one of claims 1 to 5, wherein the content is 20% by mass.

7. The silicate film is composed of an alkali metal silicate, colloidal silica, a silane coupling agent, a phosphate, and a polyolefin wax dispersion. 6. The method according to claim 1, wherein the i / P mass ratio is 30 to 150, and the content of the alkali metal is 10 to 20% by mass. Heat-resistant metal sheet with excellent corrosion resistance.

8. On the surface of the metal plate or plated metal plate, as a pretreatment film: (a) 1 to 100 mg Zm ^{2 of} titanium compound in terms of titanium or 1 to 10 O in terms of zirconium compound of a zirconium compound. mg / m ² , or a titanium compound and a zirconium compound each having a total of 1 to 10 O mg / m ^{2 in} terms of titanium and zirconium, and the pretreatment film is composed of (b) a phosphoric acid compound and (c) An organic-inorganic composite film containing a guanidine compound and having a colloidal sily force of 5 to 35% by mass in terms of solid content in an upper layer of 0.1 to 3

An organic-coated metal plate with excellent corrosion resistance, characterized in that it is formed with a thickness of 0 g / m ² .

9. The content of the phosphoric acid compound is 10 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium). Organic coated metal plate with excellent corrosion resistance as described

49

10. The guanidine compound content is 15 to 150 parts by mass with respect to 100 parts by mass of component (a) (calculated as titanium or zirconium). Or an organic-coated metal sheet excellent in corrosion resistance according to item 9.

1 1. Magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantanole, niobium, tungsten in the pretreatment film

And at least one selected from silicon, manganese, cobalt, and nickel compounds in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of component (a) (titanium or zirconium conversion value). The organic-coated metal sheet excellent in corrosion resistance according to any one of claims 8 to 10.

1 2. One or more water-soluble resins are contained in the pretreatment film in an amount of 0.5 to 40 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium). The organic coated metal sheet having excellent corrosion resistance according to any one of claims 8 to 11.

13. The organic-inorganic composite film further comprises a polyolefin wax dispersion of 35% by mass or less in terms of solid content mass, according to any one of claims 8 to 12, wherein Organic coated metal sheet with excellent corrosion resistance.

1 4. A zinc phosphite film and a sealing film on the zinc phosphite film on the surface of a metal plate coated with zinc or a zinc-based alloy. (A) Titanium compound is 1 to 2 in terms of titanium. 0 O mg / m ² or zirconium compound is 1 to 20 O mg / m ^{2 in} terms of zirconium, or titanium compound and zirconium compound is 1 to 20 O mg / m ² in total in terms of titanium and zirconium, respectively. A zinc plate coated with a phosphate, characterized in that the sealing coating contains (b) a phosphate compound and (c) a guanidine compound.

1 5. The phosphoric acid compound content is 100 parts by mass of component (a)

50 15. The metal plate coated with a phosphate-treated zinc according to claim 14, wherein the amount is from 10 to 150 parts by mass with respect to the amount of the metal or zirconium.

16. The guanidine compound content is 15 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium). Phosphate-treated zinc-based metal plate described in 5 above.

1 7. One or more selected from magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tantalum, silicon, manganese, cobalt, and nickel compounds in the sealing coating. The composition according to any one of claims 14 to 16, characterized in that the component (a) is contained in an amount of 5 to 200 parts by mass with respect to 100 parts by mass (in terms of titanium or zirconium). The metal plate with zinc phosphate treatment described in the above.

18. One or more water-soluble resins in the sealing coating are 0.5 to 40 parts by mass based on 100 parts by mass of component (a) (titanium or zirconium equivalent). The metal plate coated with a phosphate-based zinc according to any one of claims 14 to 17, wherein the metal plate is contained.

51