JP2001081392A - Treating agent for water-based coating substrate having excellent adhesion, production of metal material and metal material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-chromium-based substrate treating agent for obtaining a metal having excellent corrosion resistance and coating adhesion and to provide a method for producing a metal material using the treating agent. SOLUTION: This substrate treating agent comprises (a) at least one kind of resin selected from a urethane resin, an epoxy resin and an acrylic resin, (b) a silane coupling agent and (c) a fine particle having <=1 μm average particle diameter in the ratio of 20-70 wt.% of the component (a), 10-60 wt.% of component b and 10-40 wt.% of the component c calculated as solid content based on 100 wt.% of the total solid content. The component c can be selected from colloidal silica, fumed silica, alumina sol, zirconia sol, titania sol, phosphorus- based rust-preventive pigment and plastic pigment and has preferably pH 2-10. The substrate treating agent is applied to at least one surface of a metal material or a chemically plated metal material and dried to form a coating film having 0.05-1.0 g/m2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a treatment agent for an aqueous coating base used for a colored steel sheet or a coated steel sheet called a PCM steel sheet, a method for producing a metal material having excellent adhesion using the same, and a metal material. .

[0002]

2. Description of the Related Art A functional surface-treated steel sheet called a color steel sheet coated with an organic film is used for home appliances, building materials, automobiles and the like. Since this steel sheet is subjected to chromate treatment as a base treatment and coated with an organic film, it has a feature that it is excellent in designability in addition to workability and corrosion resistance. However, as interest in global environmental protection has increased in recent years, there has been a strong movement to minimize the use of substances harmful to the human body (in the case of color steel sheets, hexavalent chromium contained in the base and organic coating). . For this reason, recently, chromium-free (non-chromate) base treatment agents,
There is a growing demand for chromium-free (non-chromate) organic film chemicals.

The prior arts relating to this are (1) JP-A-59-116381 and (2) JP-A-4-66.
No. 173, for example.

(1) In the technique disclosed in Japanese Patent Application Laid-Open No. Sho 59-116381, a zinc and zinc alloy surface is treated with an aqueous solution containing tannic acid and a silane coupling agent to form a film on the surface. Is the way. However, due to the solubility of tannic acid in water, the film obtained by this method could not achieve the adhesion we aimed at.

(2) The technique disclosed in Japanese Patent Application Laid-Open No. 4-66173 discloses that at least one member selected from the group consisting of titanium or zirconium fluorine compounds is provided on the surface of an aluminum-plated metal plate or an aluminum plate;
At least one selected from the group consisting of silane coupling agents having an amino group, an epoxy group or a mercapto group
The present invention relates to a metal plate on which a treatment liquid containing at least a seed as an essential component is applied and dried, and a heat-resistant resin having S atoms is formed thereon. Although the metal plate obtained by this method has excellent heat resistance, it was not possible to obtain the adhesion that we aimed for.

As described above, at present, a film having excellent corrosion resistance and adhesion that can be applied to a coating substrate as a substitute for a chromate film has not been obtained by any of the methods.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides an aqueous coating base for forming a coating having excellent corrosion resistance and coating adhesion on the surface of a metal material. It is an object of the present invention to provide a treatment agent, a method for producing a metal material using the same, and a metal material.

[0008]

The present inventors have made intensive studies to solve the problems of the prior art, and as a result, have found that a specific resin, a silane coupling agent and 1 μm
By treating the surface of the metal material with an aqueous treatment agent having the following fine particles, not to mention corrosion resistance,
The inventors have newly found that a film having excellent adhesion can be formed, and have completed the present invention.

That is, the water-based undercoating treatment agent of the present invention having excellent adhesion is at least one resin selected from the group consisting of urethane resin, epoxy resin and acrylic resin as component (a); It contains a silane coupling agent as a component, fine particles having an average particle diameter of 1 μm or less as a component (c), and the solid content of the component (a) is 20 to 70% by weight based on 100% by weight of the total solid content, and (b) ) The solid content of the component is 10 to 60% by weight, and the solid content of the component (c) is 10% by weight.
-40% by weight.

In the present invention, the component (c) is preferably at least one selected from the group consisting of colloidal silica, fumed silica, alumina sol, zirconia sol, titania sol, phosphorus-based rust preventive pigment and plastic pigment. . Moreover, it is preferable that the pH of the aqueous coating base treating agent of the present invention is in the range of 2 to 10.

Further, in the method for producing a metal material according to the present invention, the aqueous coating base treating agent may be at least one of a metal, a metal subjected to a chemical plating treatment, and a metal material subjected to a phosphate chemical treatment. was applied to the surface immediately dried, characterized in that to form a coating of 0.05 to 1.0 g / m ² as a film weight on the surface.

Further, the metal material of the present invention is characterized by being manufactured by using the above manufacturing method.

Hereinafter, the contents of the present invention will be described in detail.
The feature of the coating base treating agent of the present invention is that it is composed of three components (a), (b) and (c), and that the composition ratio of these components is characterized. In the present invention, at least one resin selected from the group consisting of a urethane resin, an epoxy resin and an acrylic resin is used as the component (a).

The urethane resin used in the present invention includes:
Those having a hydrophilic group such as a carboxyl group, a hydroxyl group or an amino group as a functional group are preferred. The production method is not particularly limited, and examples thereof include a self-emulsification method in which the hydrophilic functional group is used to form an aqueous system, and an emulsion polymerization method using a surfactant. Examples of such a urethane resin include Superflex 90 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Super Flex 107M, Super Flex 11
0, Superflex 130, Superflex 1
50, Superflex 300, Superflex 410, Superflex 700, Superflex 820, Adeka Bon Titer H manufactured by Asahi Denka Kogyo Co., Ltd.
UX-550, Adekabon titer HUX-232, Adekabon titer HUX-670, Adekabon titer HUX-293, Permarine U manufactured by Sanyo Chemical Industries, Ltd.
A-200, UA-300, and the like.

The epoxy resin used in the present invention includes:
Examples thereof include a compound obtained by reaction with epichlorohydrin or a compound obtained from this compound, and particularly preferable are compounds obtained from bisphenol A, bisphenol F, hydrogenated bisphenol A, and a novolak resin. The production method is not particularly limited, and examples thereof include a self-emulsification method in which a hydrophilic group such as a carboxyl group or an amino group is used to form an aqueous system, and an emulsion polymerization method using a surfactant. Examples of such a resin include, for example, Epilets 3519W50, Epilets 3522W60, Epilets 3540WY55, Epilets 3551WY43, Epilets 5003W5 manufactured by Yuka Shell Epoxy Co., Ltd.
5, Epiletz 6006W70, Adeka Resin EPE-0410, Adeka Resin EPE-0425 manufactured by Asahi Denka
W, and the like.

The acrylic resin used in the present invention includes:
It is preferable that (meth) acrylic acid or a derivative thereof is a main component. The production method is not particularly limited, but is preferably an emulsion polymerization method using a surfactant (particularly a reactive emulsifier). Examples of such a resin include Primal K-3, Primal TR-934 and Primal HA- manufactured by ROHM AND HAAS.
8, Primal NW-1402, Primal NW-17
15, Primal E-693, Primal E-1242
E, Movinyl 860, Movinyl 940, Movinyl 700, Movinyl 709, Movinyl 745, Movinyl 931 manufactured by Hoechst Gosei Co., Ltd., Boncoat 3625, Boncoat 366 manufactured by Dainippon Ink and Chemicals, Inc.
0K, Boncoat EC-863, Boncoat EC-89
8, Bon coat EC-818, Bon coat EC-84
0, Bon Coat EC-846, Bon Coat EC-85
6, etc.

The solid content of the component (a) is 20 to 70% by weight, preferably 25 to 65% by weight, more preferably 30 to 60% by weight based on 100% by weight of the total solids. When the solid content of the component (a) is less than 20% by weight based on 100% by weight of the total solid content, the retention of the component (c) in the coating film is reduced, and thus the corrosion resistance is undesirably reduced. on the other hand,
When the solid content of the component (a) exceeds 70% by weight,
Since the ratio of the component (b) and the component (c) is decreased, the corrosion resistance and the adhesion are undesirably decreased.

As the silane coupling agent of the component (b) used in the present invention, those having a functional group having reactivity with the resin are preferable. Examples of such silane coupling agents include, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, β- (3,
4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacrylic Roxypropyltriethoxysilane, N-β (aminoethyl)
γ-aminopropylmethyldimethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-amino Propyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like. The silane coupling agent used in the present invention may be used in combination of two or more kinds.

The solid content of the component (b) is 10 to 60% by weight, preferably 15 to 50% by weight, more preferably 20 to 40% by weight based on 100% by weight of the total solid content. When the solid content of the component (b) is less than 20% by weight based on 100% by weight of the total solid content, the adhesion of the film is undesirably reduced. On the other hand, when the solid content of the component (b) exceeds 60% by weight, the ratio of the component (a) to the coating film is decreased, so that the corrosion resistance is undesirably reduced.

The fine particles having an average particle size of 1 μm or less of the component (c) used in the present invention are selected from the group consisting of colloidal silica, fumed silica, alumina sol, zirconia sol, titania sol, phosphorus-based rust preventive pigment and plastic pigment. It is preferred to use at least one selected. When the average particle size of the component (c) exceeds 1 μm, the particles are protruded from the surface of the film, so that moisture easily penetrates from the interface of the particles to the surface of the material, and the corrosion resistance and adhesion are undesirably reduced. .

The fine particles having an average particle size of 1 μm or less of the component (c) include, for example, colloidal silica such as Snowtex 20, Snowtex 30, Snowtex 40, and Snowtex manufactured by Nissan Chemical Industries, Ltd. Tex 50, Snowtex C, Snowtex N, Snowtex O, Snowtex S, Snowtex 20L,
Snowtex L, Snowtex UP, Snowtex OUP, Snowtex XL, Snowtex YL,
Snowtex ZL, Snowtex MP-1040,
Snowtex MP-3040, Snowtex MP-
4540, Snowtex AK, Snowtex BK,
CAS-40, CAS-25, and the like.

As the fumed silica, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT6 manufactured by Nippon Aerosil Co., Ltd.
00, Aerosil MOX80, Aerosil MOX17
0 and the like.

Examples of the alumina sol include alumina sol-100 and alumina sol-20 manufactured by Nissan Chemical Industries, Ltd.
0, alumina sol-520 and the like. As zirconia sol, NZS-20 manufactured by Nissan Chemical Industries, Ltd. is used.
A, NZS-30A, NZS-30B, and the like.

Examples of the phosphorus-based rust-preventive pigment include pulverized zinc phosphate, aluminum phosphate and calcium phosphate, and examples of the plastic pigment include Muticle 100P and Muticle 240D manufactured by Mitsui Chemicals, Inc.
Low-Pake OP-62 and Low-Pake HP-91 manufactured by HM AND HAAS, and MP-100 manufactured by Soken Chemical Co., Ltd.
0, MP-1100, MP-1201, MP-145
0, MP-1451, MP-1600, MP-270
1, MP-3100, MP-4009, and the like. The fine particles having an average particle diameter of 1 μm or less used in the present invention may be a composite of two or more kinds.

The solid content of the component (c) is 10 to 40% by weight, preferably 10 to 35% by weight, more preferably 10 to 30% by weight based on 100% by weight of the total solid content. If the solid content of the component (c) is less than 10% by weight based on 100% by weight of the total solid content, the adhesion is undesirably reduced.
On the other hand, when the solid content of the component (c) exceeds 30% by weight, the coating is hard and brittle, so that the corrosion resistance and the adhesion are undesirably reduced.

The pH of the water-based paint base treating agent of the present invention is 2
Is preferably in the range of 2.5 to 9.5. When the pH of the treating agent is less than 2, it is not preferable because the corrosion resistance may be reduced by etching the metal as a raw material. On the other hand, if the pH exceeds 10, it is not preferable because the alkali component remaining in the film lowers the water resistance of the film. Incidentally, the method of adjusting the pH of the treating agent is not particularly limited, but when adjusting to the acidic side, for example, formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid,
Organic acids such as L-ascorbic acid, tartaric acid, citric acid, DL-malic acid, malonic acid, maleic acid, phthalic acid,
Use phosphoric acid such as metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, and tetraphosphoric acid, and fluoride such as zirconium hydrofluoric acid, titanium hydrofluoric acid, hydrosilicofluoric acid, and hydrofluoric acid Is preferred.

On the other hand, when adjusting to the alkali side, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine, triethylamine, tripropylamine, triisopropylamine It is preferable to use an amine compound such as an amine, ammonia, or the like.

The solid content concentration of the treating agent for water-based coating base of the present invention is preferably in the range of 0.1 to 50%. When the solid content is less than 0.1%, it is difficult to obtain a target film amount. On the other hand, when the solid content is more than 50%, it becomes difficult to adjust the treating agent, which is not preferable.

The metal material which can be used as the coating base treating agent of the present invention is steel, for example, a cold-rolled steel sheet, a hot-rolled pickled plate, etc., and a zinc-based coated steel sheet, for example, an electro-galvanized steel sheet, a hot-dip galvanized steel sheet, Examples include an aluminum plate such as an alloyed galvanized steel plate, an aluminum-containing galvanized steel plate, a zinc nickel-plated steel plate, a zinc cobalt-plated steel plate, and a vapor-deposited galvanized steel plate.

In the present invention, a leveling agent, a thickening agent, a film-forming auxiliary, and the like, which are generally used in an aqueous treatment agent, may be added to the treatment agent for an aqueous coating base.

The method for producing a metal material according to the present invention is characterized in that the treating agent for an aqueous coating underlayer according to the present invention is at least one of a metal material, a metal subjected to chemical plating and a metal material subjected to a phosphate chemical treatment. Apply directly to the surface and immediately dry,
A film having a film amount of 0.05 to 1.0 g / m ² is formed on the surface. The aqueous coating base treating agent of the present invention can impart excellent corrosion resistance and adhesion to the metal material by directly applying it to the surface of the metal material and drying it. As a result, more excellent corrosion resistance and adhesion can be imparted to the metal material. Although there is no particular limitation on the method of chemical plating, it is preferable to deposit a metal such as Fe, Co, and Ni in an amount of 1 to 50 mg / m ^{2 in} terms of metal atoms. The method of the phosphate chemical conversion treatment is not particularly limited.
３3 g / m ² is preferred.

The amount of the film formed on the surface of the metal material of the present invention is 0.05 to 1.0 g / m ² , preferably 0.05 to 1.0 g / m ² .
It is in the range of 0.5 g / m ² . The amount of film is 0.05g / m
If it is less than ² , the corrosion resistance and adhesion are insufficient, which is not preferable. On the other hand, when the coating amount exceeds 1.0 g / m ² , the coating itself is liable to cause cohesive failure, and thus the adhesion may be reduced, which is not preferable.

The method of directly applying the water-based coating treatment agent of the present invention to the surface of a metal material and drying it is not particularly limited, but the method of application is a roll coater method, a dipping method, an electrostatic coating method, or the like. And drying methods include hot air, induction heating, and the like. In this case, the reaching plate temperature is preferably 50 to 250 ° C, more preferably 60 to 250 ° C.
220 ° C.

The paint applied to the surface of the metal material treated with the water-based paint base according to the present invention is not particularly limited, but the chromic acid-based rust preventive pigments conventionally used are not limited. And a paint containing a phosphate-based rust preventive pigment, a molybdate-based rust preventive pigment, silica fine powder, a metal oxide such as TiO ₂ , the above-described rust preventive pigment, a coloring pigment, and the like. After the primer is applied, a top coat for giving a design property is usually applied. Such a coating for the top coat is not particularly limited, and examples thereof include an epoxy resin, a polyester resin, an acrylic resin, a urethane resin, an alkyd resin, and a fluororesin.

[0035]

EXAMPLES Examples of the present invention will be described below together with comparative examples.
The present invention will be specifically described. The scope of the present invention is not limited by these examples. The test pieces used in the examples and comparative examples, the pretreatment, and the method of applying the treating agent for the aqueous coating base will be described below.

1. Preparation of test piece (1-1) Test material The following commercially available materials were used as test materials. - hot-dip galvanized steel sheet (GI) thickness = 0.5 mm, basis weight = 90/90 (g / m 2) · 5% aluminum-containing hot-dip galvanized steel sheet (GF) thickness = 0.5 mm, basis weight = 90 / 90 (g / m ² ) ・ Dip 55% zinc alloy plated steel sheet (GL) Sheet thickness = 0.8mm, weight per unit area = 90/90 (g / m ² ) ・ A-1100 series aluminum sheet (AL) = 0.8mm

(1-2) Degreasing treatment The test materials were fine cleaner 4336 of alkaline degreasing agent.
Spraying was performed for 2 minutes under the conditions of a concentration of 20 g / L and a temperature of 60 ° C. using (registered trademark: manufactured by Nippon Parkerizing Co., Ltd.), washed with pure water for 30 seconds, and then dried.

(1-3) Pre-treatment ・ Chemical plating treatment The sample material subjected to the degreasing treatment is prepared by using Preparen 40 as a surface conditioner.
Using 15 (registered trademark: manufactured by Nippon Parkerizing Co., Ltd.), a spray treatment was performed under the conditions of a concentration of 100 g / L and a temperature of 50 ° C., followed by washing with deionized water for 30 seconds and drying. The amount of nickel deposited at this time is 20 mg / m ² .・ Phosphorylation treatment The sample material that has been degreased is used as the surface conditioner Preparen Z.
(Registered trademark: manufactured by Nippon Parkerizing Co., Ltd.), immersed for 10 seconds at a concentration of 1 g / L and a temperature of 30 ° C., and then Palbond L3300, a phosphatizing agent (registered trademark: Nippon Parkerizing Co., Ltd.) Immersion treatment under the conditions of a concentration of 60 g / L and a temperature of 60 ° C., washing with deionized water for 30 seconds, and drying. In this case, the coating amount was 2 g / m ² .

(1-4) Application of Surface Treatment Agent for Metallic Material The following aqueous base treatment agent was applied with a bar coater and dried at an ambient temperature of 300 ° C.

2. Test level <Treatment solution A> 100 parts of a superflex 700 (solid content: 35%) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which is a urethane resin as the component (a), and Toshiba Silicone Co., Ltd. as the component (b) 35 parts of γ-glycidoxypropyltriethoxysilane (solid content: 100%) and 150 parts of colloidal silica, Snowtex 20 manufactured by Nissan Chemical Industries, Ltd. (solid content: 20%) as the component (c). The parts were weighed and dispersed in 1710 parts of deionized water using propeller agitation. Further, the pH of the treatment liquid was adjusted to 8 by appropriately dropping a 5% aqueous ammonia solution. The solid weight of the component (a) is 35% based on 100% by weight of the total solid content of the treatment liquid.
% By weight, the solid content weight of the component (b) is 35% by weight, and (c)
The solids weight of the components is 30% by weight. The solid concentration of the treatment liquid is 5%.

<Treatment Liquid B> Epilet 50 manufactured by Yuka Shell Epoxy Co., Ltd. which is an epoxy resin as the component (a)
100 parts of 03W55 (solid content concentration 55%) and 25 parts of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane (solid content concentration 100%) manufactured by Toshiba Silicone Co., Ltd. as the component (b). , Zirconia sol NZS manufactured by Nissan Chemical Co., Ltd.
Measure 100 parts of -20A (solids concentration 20%),
Dispersed in 2275 parts of deionized water using propeller agitation. Further, a 5% acetic acid aqueous solution was appropriately added dropwise to the treatment liquid to adjust the pH to 4. The solid weight of the component (a) was 55% by weight based on 100% by weight of the total solids of the processing solution.
The solid weight of the component (b) is 25% by weight, and the solid weight of the component (c) is 20% by weight. The solid concentration of the treatment liquid is 4%.

<Treatment liquid C> Primal K manufactured by ROHM AND HAAS which is an acrylic resin as the component (a)
-3 (46% solid content), 20 parts of γ-mercaptopropyltrimethoxysilane (100% solid content) manufactured by Toshiba Silicone Co., Ltd. as component (b).
(C) Snowtex OUP manufactured by Nissan Chemical Industries, Ltd., which is a colloidal silica as a component (solid concentration: 15%)
Was measured and dispersed in 2286 parts of deionized water using propeller agitation. Further, a 5% aqueous solution of triethylamine was appropriately added dropwise to the treatment liquid to adjust the pH to 9. still,
The solid weight of the component (a) is 58% by weight, and the solid weight of the component (b) is 25% by weight based on 100% by weight of the total solid content of the treatment liquid.
% By weight, and the solid content of the component (c) was 17% by weight.
The solid concentration of the treatment liquid is 4%.

<Treatment Solution D> Epilet 50 manufactured by Yuka Shell Epoxy Co., Ltd. which is an epoxy resin as the component (a)
80 parts of 03W55 (concentration of solid content: 55%) and Finetex ES-2200 manufactured by Dainippon Ink and Chemicals, Inc.
(Solid content 25%) 60 parts, (b) 31 parts of Toshiba Silicone Co., Ltd. γ-glycidoxypropyltriethoxysilane (solid content 100%), (c)
As an ingredient, 100 parts of an alumina sol, alumina sol-100 (solid content: 10%) manufactured by Nissan Chemical Industries, Ltd. was measured and dispersed in 729 parts of deionized water using propeller stirring. Further, a 5% phosphoric acid aqueous solution was appropriately added dropwise to the treatment liquid to adjust the pH to 3. In addition, the total solid content of the processing liquid 1
The solid weight of the component (a) is 59% by weight, the solid weight of the component (b) is 31% by weight, and the solid weight of the component (c) is 10% by weight based on 00% by weight. The solid concentration of the treatment liquid is 10%.

<Treatment Solution E> Primal K manufactured by ROHM AND HAAS, which is an acrylic resin as the component (a)
-3 (46% solid content), 10 parts γ-glycidoxypropyltriethoxysilane (100% solid content) manufactured by Toshiba Silicone Co., Ltd. as component (b), and Toshiba Silicone Co., Ltd. 10 parts of γ-chloropropyltrimethoxysilane (100% solid content) manufactured by Mitsui Chemicals, Inc. as a component (c)
Mutex 240D (solid content: 44%)
Measure 2 parts and use deionized water 10 with propeller agitation.
Dispersed in 98 parts. Further, the pH of the treatment liquid was adjusted to 8 by appropriately dropping 5% aqueous ammonia. The weight of the solid content of the component (a) is 5% based on 100% by weight of the total solid content of the processing solution.
8% by weight, the solid content weight of the component (b) is 25% by weight,
The solid content weight of the component (c) is 17% by weight. Further, the solid content concentration of the treatment liquid is 8%.

<Comparative treatment solution F> 35 parts of γ-glycidoxypropyltriethoxysilane (solid content: 100%) manufactured by Toshiba Silicone Co., Ltd. as the component (b), and colloidal silica as the component (c). Measure 150 parts of Snowtex 20 (solid content: 20%) manufactured by Nissan Chemical Industry Co., Ltd. and use deionized water 1115 using propeller stirring.
Parts. Further, the pH of the treatment liquid was adjusted to 8 by appropriately dropping a 5% aqueous ammonia solution. The solid content concentration of this treatment liquid is 5%. This treatment liquid does not contain the component (a).

<Comparative treatment liquid G> As the component (a), 100 parts of a superflex 700 (solid content: 35%) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which is a urethane resin, and as the component (c), colloidal silica. 150 parts of Snowtex 20 (solid content: 20%) manufactured by Nissan Chemical Industries, Ltd. was measured and dispersed in 1050 parts of deionized water using propeller stirring. Further, the pH of the treatment liquid was adjusted to 8 by appropriately dropping a 5% aqueous ammonia solution. The solid content concentration of this treatment liquid is 5%. This treatment liquid does not contain the component (b).

<Comparative treatment solution H> 100 parts of a superflex 700 (solid content: 35%) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a component (a) and Toshiba Silicone Co., Ltd. as a component (b) Γ-glycidoxypropyltriethoxysilane (solid concentration 100%)
Measure the parts and use propeller agitation to
Dispersed in 5 parts. Further, the pH of the treatment liquid was adjusted to 8 by appropriately dropping a 5% aqueous ammonia solution. The solid content concentration of this treatment liquid is 5%. This treatment liquid does not contain the component (c).

<Comparative treatment solution I> As a component (a), 220 parts of a superflex 700 (solid content: 35%) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which is a urethane resin, and Toshiba Silicone Co., Ltd. as a component (b) Γ-glycidoxypropyltriethoxysilane (solid content: 100%)
Part, Colloidal silica as component (c), Snowtex 20 (solids concentration 20) manufactured by Nissan Chemical Industries, Ltd.
%) Was weighed out and dispersed in 1717 parts of deionized water using propeller agitation. Further, the pH of the treatment liquid was adjusted to 8 by appropriately dropping a 5% aqueous ammonia solution. The solid content concentration of this treatment liquid is 5%. The solid weight of the component (a) is 7% based on 100% by weight of the total solid content of the processing solution.
7% by weight, the solid weight of the component (b) is 13% by weight,
The solid weight of the component (c) is 10% by weight, and the solid weight of the component (a) is out of the range (exceeding the upper limit).

<Comparative treatment solution J> As the component (a), 40 parts of a superflex 700 (solid content: 35%), a urethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and as the component (b), Toshiba Silicone Co., Ltd. Γ-glycidoxypropyltriethoxysilane (solid concentration 100%)
Part, Colloidal silica as component (c), Snowtex 20 (solids concentration 20) manufactured by Nissan Chemical Industries, Ltd.
%) Was weighed out and dispersed in 1714 parts of deionized water using propeller agitation. In addition, 5%
The pH was adjusted to 8 by appropriately dropping an aqueous ammonia solution.
The solid content concentration of this treatment liquid is 5%. Incidentally, the solid weight of the component (a) was 14% by weight, the solid weight of the component (b) was 46% by weight, based on 100% by weight of the total solid content of the treatment liquid.
The solid weight of the component (c) is 40% by weight, and the solid weight of the component (a) is out of the range (less than the lower limit).

<Comparative treatment solution K> As a component (a), 200 parts of a superflex 700 (solid content: 35%) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a component, and Toshiba Silicone Co., Ltd. as a component (b) Γ-glycidoxypropyltriethoxysilane (solid concentration 100%)
Part, Colloidal silica as component (c), Snowtex 20 (solids concentration 20) manufactured by Nissan Chemical Industries, Ltd.
%) Was weighed out and dispersed in 1670 parts of deionized water using propeller agitation. In addition, 5%
The pH was adjusted to 8 by appropriately dropping an aqueous ammonia solution.
The solid content concentration of this treatment liquid is 5%. The solid weight of the component (a) was 70% by weight, the solid weight of the component (b) was 5% by weight, based on 100% by weight of the total solid content of the treatment liquid.
The solid weight of the component (c) is 25% by weight, and the solid weight of the component (b) is out of the range (less than the lower limit).

<Comparative treatment liquid L> As a component (a), 60 parts of a superflex 700 (solid content: 35%), a urethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and as a component (b), Toshiba Silicone Co., Ltd. )) (64% solids concentration: 100%).
Part, Colloidal silica as component (c), Snowtex 20 (solids concentration 20) manufactured by Nissan Chemical Industries, Ltd.
%) Was weighed out and dispersed in 1801 parts of deionized water using propeller agitation. Further, the pH of the treatment liquid was adjusted to 8 by appropriately dropping a 5% aqueous ammonia solution. The solid content concentration of this treatment liquid is 5%. The solid weight of the component (a) was 2% based on 100% by weight of the total solid content of the treatment liquid.
1% by weight, the solid content weight of the component (b) is 64% by weight,
The solid weight of the component (c) is 15% by weight, and the solid weight of the component (b) is out of the range (exceeding the upper limit).

<Comparative treatment liquid M> As a component (a), 220 parts of a superflex 700 (solid content: 35%), a urethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and as a component (b), Toshiba Silicone Co., Ltd. )-(Γ-glycidoxypropyltriethoxysilane) (solid concentration 100%)
Part, Colloidal silica as component (c), Snowtex 20 (solids concentration 20) manufactured by Nissan Chemical Industries, Ltd.
%) Was weighed out and dispersed in 1737 parts of deionized water using propeller agitation. Further, the pH of the treatment liquid was adjusted to 8 by appropriately dropping a 5% aqueous ammonia solution. The solid content concentration of this treatment liquid is 5%. The solid weight of the component (a) is 7% based on 100% by weight of the total solid content of the processing solution.
7% by weight, the solid content weight of the component (b) is 18% by weight,
The solid weight of the component (c) is 5% by weight, and the solid weight of the component (c) is out of the range (less than the lower limit).

<Comparative treatment liquid N> 100 parts of a superflex 700 (solid content: 35%) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which is a urethane resin, was used as the component (a), and Toshiba Silicone Co., Ltd. was used as the component (b). ) -Produced γ-glycidoxypropyltriethoxysilane (solid concentration 100%)
Part, Colloidal silica as component (c), Snowtex 20 (solids concentration 20) manufactured by Nissan Chemical Industries, Ltd.
%) Was weighed out and dispersed in 1635 parts of deionized water using propeller agitation. In addition, 5%
The pH was adjusted to 8 by appropriately dropping an aqueous ammonia solution.
The solid content concentration of this treatment liquid is 5%. Incidentally, the solid weight of the component (a) was 35% by weight, the solid weight of the component (b) was 15% by weight, based on 100% by weight of the total solid content of the treatment liquid.
The solid content weight of the component (c) is 50% by weight, and the solid content weight of the component (c) is out of the range (exceeding the upper limit).

3. Test plate preparation method A commercially available undercoat paint (V-nit # 200, manufactured by Dainippon Paint Co., Ltd.) was applied to each of the treated plates prepared in Examples and Comparative Examples (5.5 μm in film thickness), baked at 200 ° C, and further overcoated. A paint (V-nit # 500, manufactured by Dainippon Paint Co., Ltd.) was applied (film thickness 17 μm) and baked at 220 ° C. to obtain a test plate.

4. Evaluation test 4.1 Corrosion resistance test A scratch reaching the metal base was cut into the coating film with a cutter,
The salt spray test specified in Z2371 was performed for 480 hours. As a criterion, the rust width (mm) from the cut portion was measured. <Evaluation criteria> ：: less than 3 mm ３: 3 mm or more and less than 5 mm Δ: 5 mm or more and less than 10 mm ×: 10 mm or more

4.2 Bending Adhesion Test 4.2.1 Primary Bending Adhesion Test Each test plate was subjected to 2 folds according to the test method of JIS-G3312.
A 2T bending test was performed on the two folded inner spacing plates at 0 ° C., and the peeled state after the tape was peeled was evaluated according to the following criteria. <Evaluation criteria> 5 points: no peeling 4 points: peeling area less than 10% 3 points: peeling area 10% or more and less than 50% 2 points: peeling area 50% or more and less than 80% 1 point: peeling area 80% or more

4.2.2 Secondary bending adhesion test After the test plate was immersed in boiling water for 2 hours, it was allowed to stand for one day and the same test as the primary bending adhesion test was performed. The criteria are as follows. <Evaluation criteria> 5 points: no peeling 4 points: peeling area less than 10% 3 points: peeling area 10% or more and less than 50% 2 points: peeling area 50% or more and less than 80% 1 point: peeling area 80% or more

4.3 Coin Scratch Test A 10-yen coin was placed at an angle of 45 ° with respect to each test plate.
The coating was rubbed at a constant speed with a load of 3 kg, and the scratch resistance of the coating was determined. The scratch resistance of the coating film was evaluated according to the following criteria. <Evaluation Criteria> 5 points: Base exposure 0% (only primer exposed) 4 points: Base exposure less than 10% 3 points: Base exposure 10% or more and less than 50% 2 points: Base exposure 50% Not less than 80% 1 point: substrate exposure is 80% or more

Table 1 of [Levels] shows a list of test levels of the water-based paint base treating agent, and Table 2 of [Results] shows a list of coated plate performance test results of the water-based paint base treating agent. An example will be described. No. of Table 2 Nos. 1 to 13 are coated plate performances of metal materials obtained by applying a water-based undercoat treatment agent of the present invention (Nos. 1 to 13 of Examples in Table 1) and then drying to form a film, and exhibiting corrosion resistance and primary resistance. The folding adhesion, secondary folding adhesion, and coin scratch performance are all good.
On the other hand, Comparative Example No. 1 in Table 1 different from the present invention. No. 1 in Table 2 using the treatment chemicals Nos. 1 to 11. 14 to 24 are corrosion resistance,
It is inferior in primary bending adhesion, secondary bending adhesion and coin scratching.

[0060]

As described above, by applying the water-based paint base treating agent of the present invention to the surface of a metal material,
Since a film excellent in corrosion resistance, primary bending adhesion, secondary bending adhesion, and coin scratching properties can be obtained, industrial contribution is extremely large.

[0061]

[Table 1]

[0062]

[Table 2]

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[Procedure amendment]

[Submission date] September 6, 2000 (2000.9.6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction contents]

4. Evaluation test 4.1 Corrosion resistance test A scratch reaching the metal base was cut into the coating film with a cutter,
The salt spray test specified in Z2371 was performed for 480 hours. As a criterion, the rust width (mm) from the cut portion was measured. <Evaluation Criteria> ：: less than 3 mm 5 points ○: 3 mm or more and less than 5 mm 3 points to 4 points Δ: 5 mm or more and less than 10 mm 2 points ×: 10 mm or more ...... ……… 1 point

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction contents]

4.2 Bending Adhesion Test 4.2.1 Primary Bending Adhesion Test Each test plate was subjected to 2 folds according to the test method of JIS-G3312.
A 2T bending test was performed on the two folded inner spacing plates at 0 ° C., and the peeled state after the tape was peeled was evaluated according to the following criteria. <Evaluation criteria> 5 points: No peeling ... 4 points: Less than 10% peeled area ... ... 3 points: 10% or more and less than 50% peeled area ... ○ 2 points: Peeling area of 50% or more and less than 80% ... 1 point: Peeling area of 80% or more ………… ×

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction contents]

4.2.2 Secondary bending adhesion test After the test plate was immersed in boiling water for 2 hours, it was allowed to stand for one day and the same test as the primary bending adhesion test was performed. The criteria are as follows. <Evaluation criteria> 5 points: No peeling ... 4 points: Less than 10% peeled area ... ... 3 points: 10% or more and less than 50% peeled area ... ○ 2 points: Peeling area of 50% or more and less than 80% ... 1 point: Peeling area of 80% or more ………… ×

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

4.3 Coin Scratch Test A 10-yen coin was placed at an angle of 45 ° with respect to each test plate.
The coating was rubbed at a constant speed with a load of 3 kg, and the scratch resistance of the coating was determined. The scratch resistance of the coating film was evaluated according to the following criteria. <Evaluation Criteria> 5 points: Base exposure 0% (primer only exposed) 4 points: Base exposure less than 10% ............ 3 points: Base exposure 10% or more and less than 50% ... 2 points: Exposed base material is 50% or more and less than 80% ... 1 point: Exposed base material is 80% or more ............ …… ×

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction contents]

[0061]

[Table 1]

Continuation of front page (72) Inventor Katsuyuki Kawakami F-term (reference) 4J038 CG141 CG142 DA061 DA062 DB061 DB062 DG001 DG002 DL021 DL022 DL051 DL052 DL071 DL072 DL081 DL082 DL091 DL092 DL111 DL112 GA03 GA06 GA09 HA216 HA416 HA446 KA08 MA08 MA10 NA03 NA12 PA07 PA19 PB05 PB07 PB09 PC02

Claims (7)

[Claims] 1. A resin having at least one resin selected from the group consisting of a urethane resin, an epoxy resin and an acrylic resin as the component (a), a silane coupling agent as the component (b), and an average particle diameter as the component (c). Fine particles of 1 μm or less,
And the total solid content is 100% by weight.
(A) the solid content of the component (a) is 20 to 70% by weight;
An aqueous adhesion base treating agent having excellent adhesion, wherein the component (b) has a solid content of 10 to 60% by weight and the component (c) has a solid content of 10 to 40% by weight. 2. The composition according to claim 1, wherein the component (c) is colloidal silica,
The water-based coating base treating agent according to claim 1, which is at least one selected from the group consisting of fumed silica, alumina sol, zirconia sol, titania sol, phosphorus-based rust preventive pigment, and plastic pigment. 3. The treatment agent for an aqueous coating base according to claim 1, wherein the pH of the treatment agent is in the range of 2 to 10. 4. The water-based coating base treating agent according to any one of claims 1 to 3, which is directly applied to at least one surface of the metal material and immediately dried, and the surface has a coating amount of 0.05%. method for producing a metal material, characterized in that to form a film of to 1.0 g / m ^2. 5. An aqueous coating base treating agent according to any one of claims 1 to 3, which is directly applied to at least one surface of a metal material subjected to a chemical plating treatment and immediately dried.
Method for producing a metal material, characterized in that to form a coating of 0.05 to 1.0 g / m ² as a film weight on the surface. 6. The surface treatment agent for water-based coating according to claim 1, which is directly applied to at least one surface of the metal material subjected to the phosphatization and immediately dried, and the surface is dried. 0.05 to 1.0 g / m ²
A method for producing a metal material, characterized by forming a film of (i). 7. A metal material manufactured by using the manufacturing method according to claim 4. Description: