JPH11276987A - Organic multiple coated metallic material excellent in corrosion resistance, coating property and finger print resistance and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve corrosion resistance, coating property and finger print resistance by forming a coating film consisting of a silane coupling agent component and a polymer component expressed by a specific formula, having a specific reactive functional group and a specific average degree of polymerization, on the surface of a metallic material and covering a resin composition containing a specific quantity of silica as an upper layer thereon. SOLUTION: As a 1st layer on the surface of the metallic material used for domestic appliances or building products, the coating film consisting of the silane coupling agent component composed of a silane coupling compound having the reactive functional group selected from active hydrogen-containing amino group, epoxy group, vinyl group and the like and the polymer component containing a polymer expressed by the formula in the average degree of polymerization of 2-50 is formed. Then, as a 2nd layer on the 1st layer, the resin composition containing 5-70 pts.wt. silica per 100 pts.wt. resin is applied. In the formula, X bonded with benzene ring represents hydrogen atom, hydroxyl group, unsaturated hydrocarbon group forming naphthalene ring by the condensation with benzene ring or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal material which can impart excellent corrosion resistance, paintability and fingerprint resistance to the surface of a metal material and is used for home appliances and building materials.

[0002]

2. Description of the Related Art Generally, metal materials such as zinc-containing metal-plated steel sheets and aluminum sheets are used in a wide range of fields such as automobiles, building materials and home appliances. However, zinc and aluminum corrode in the atmosphere and are corrosion products (so-called white rust)
This deteriorates the appearance of the metal material and adversely affects the paintability.Furthermore, when manufacturing the product through various processes at the customer, stains such as fingerprints are likely to adhere to the product due to the handling of workers, and the product value Has the drawback that it may significantly reduce

In order to improve the corrosion resistance, paintability and fingerprint resistance of the surface of the above-mentioned metal material, the surface of the metal material is subjected to a chromate treatment using a processing solution mainly containing chromic acid, dichromic acid or salts thereof. After that, the upper layer is coated with a polyolefin resin having a carboxyl group containing colloidal silica, and a metal material is generally used.

However, in recent years, with increasing awareness of environmental preservation, chromate treatment has been shunned since hexavalent chromium in a chromate treatment solution used for treating the surface of a metal material has a direct adverse effect on the human body. Tends to. Further, wastewater containing hexavalent chromium needs to be subjected to a special treatment specified in the Water Pollution Control Law, which leads to a considerable increase in cost as a whole. In addition, a metal material subjected to a chromate treatment has a serious drawback that it becomes an industrial waste containing chromium and cannot be recycled, which is a serious social problem.

On the other hand, as a surface treatment method other than chromate, a surface treatment agent using tannic acid containing a polyhydric phenol carboxylic acid is well known. It is considered that when a metal material is treated with an aqueous solution of tannic acid, a protective film formed by a reaction between the tannic acid and the metal material serves as a barrier against intrusion of corrosive substances, so that the corrosion resistance of the metal material is improved. .

However, in recent years, as the quality of products has increased,
The coating itself is required to have high corrosion resistance. Therefore, a coating using tannic acid alone or in combination with an inorganic component has insufficient corrosion resistance and cannot be practically used at present.

Therefore, as a treatment method for improving the corrosion resistance of a metal material, a method of applying an aqueous solution comprising water-dispersible silica, an alkyd resin and a trialkoxysilane compound to a metal surface is disclosed in JP-A-53-121034. Have been.

Further, a surface treatment method for imparting corrosion resistance to a metal material using a water-soluble resin comprising a hydroxypyrone compound derivative, and a method using a water-soluble or water-dispersible polymer of a hydroxystyrene compound. Methods for imparting corrosion resistance to a metal material are disclosed in JP-A-57-47451 and JP-A-1-177380.

However, none of the above methods can form a film capable of imparting excellent corrosion resistance to the surface of a metal material as a substitute for a chromate film, and the above problems have not been solved as a practical problem. It is. Therefore, at present, a non-chromium surface treatment agent and a surface treatment method for a metal material having excellent corrosion resistance have not been obtained.

[0010]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems of the prior art, and provides a non-chromium-based organic composite coated metal material excellent in corrosion resistance, paintability and fingerprint resistance. The purpose is to do so.

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the problems of the prior art, and as a result, have specified a silane coupling agent component as a first layer on a metal material surface. Corrosion resistance by coating a composition comprising a polymer component having the chemical structure of 1) as a film, and coating the upper layer of the first layer with a silica-containing resin composition as a second layer,
Organic composite coated metal material with excellent paintability and fingerprint resistance,
The present inventors have found a method for producing the same and have completed the present invention.
Ie

The organic composite-coated metal material of the present invention has the following components as a first layer on the surface of the metal material: (A) active hydrogen-containing amino group, epoxy group, vinyl group,
A silane coupling agent component comprising at least one silane coupling compound having at least one reactive functional group selected from a mercapto group and a methacryloxy group, and (B) one kind represented by the following general formula (I) One or more polymer components containing the above polymers at an average degree of polymerization of 2 to 50:

Embedded image [Wherein, X bonded to the benzene ring is a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, a C1-C5
A hydroxyalkyl group of C5, an aryl group of C6-C12, a benzyl group, a benzal group, an unsaturated hydrocarbon group which forms a naphthalene ring by condensing with the benzene ring, or a group of the following formula (II):

Embedded image Wherein R1 and R2 in the formula (II) each represent a hydrogen atom, a hydroxyl group, a C1 to C5 alkyl group, or a C1 to C10 hydroxyalkyl group,
In the formulas (I) and (II), Y1 and Y2 bonded to the benzene ring are each independently a hydrogen atom or a Z group represented by the following formulas (III) and (IV):

Embedded image And R3, R4 in the above formulas (III) and (IV),
R5, R6 and R7 each independently represent a hydrogen atom, a C1-C10 alkyl group or a C1-C10 hydroxyalkyl group, and X, Y1 and Y2 bonded to each benzene ring in the polymer molecule; Each of the
X, Y1 and Y2 bonded to other benzene rings may be the same as or different from each other, and the average number of substitutions of the Z group in each benzene ring in the polymer molecule Is 0.2 to 1.0. Wherein the second layer is coated on the first layer with a resin composition containing silica in an amount of 5 to 70 parts by weight based on 100 parts by weight of the resin. It is.

The weight ratio (A) / (B) of the silane coupling agent component (A) to the polymer component (B) used in the organic composite coated metal material of the present invention is 1: 1.
It is preferably 0 to 10: 1.

The silane coupling agent component (A) used in the organic composite-coated metal material of the present invention comprises (a) one or more silane coupling compounds having one or more active hydrogen-containing amino groups. It is preferable to include a coupling agent and (b) a silane coupling agent comprising one or more silane coupling compounds having one or more epoxysilane groups.

The equivalent ratio of the active hydrogen-containing amino group contained in the silane coupling agent (a) to the epoxy group contained in the silane coupling agent (b) used in the organic composite-coated metal material of the present invention is as follows. 3: 1
１ ： 1: 3.

The weight ratio of the total amount of the silane coupling agent (a) and the silane coupling agent (b) used in the organic composite coated metal material of the present invention to the polymer component (B) [( a) + (b)] / (B) is 1:
It is preferably 5 to 5: 1.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The first layer film used in the organic composite coated metal material of the present invention is a silane coupling agent component comprising at least one silane coupling compound having a specific reactive functional group. (A) and a polymerization component (B) comprising one or more phenolic resin-based polymers containing a special amino group.

The silane coupling compound contained in the silane coupling agent component (A) used in the present invention comprises 1
As long as the molecule contains at least one selected from the group consisting of an active hydrogen-containing amino group, an epoxy group, a vinyl group, a mercapto group and a methacryloxy group as a reactive functional group,
Although the structure is not particularly limited, specific examples include those having the following compositions. Those having an amino group N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane Those having an epoxy group 3-Gly Sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-
(3,4 epoxycyclohexyl) ethyltrimethoxysilane having a vinyl group vinyltriethoxysilane having a mercapto group 3-mercaptopropyltrimethoxysilane having a methacryloxy group 3-methacryloxypropyltrimethoxysilane, 3-
Methacryloxypropylmethyldimethoxysilane

The silane coupling agent component (A) used in the present invention comprises: a silane coupling agent (a) comprising one or more silane coupling compounds having one or more active hydrogen-containing amino groups; It is preferable to use a silane coupling agent (b) comprising one or more silane coupling compounds having the above epoxy group.

The silane coupling agent component (A) used in the present invention comprises a silane coupling agent (a) comprising a silane coupling compound having an active hydrogen-containing amino group, and a silane coupling agent (b) containing an epoxy group. )
The equivalent ratio of the active hydrogen-containing amino group contained in the silane coupling agent to the epoxy group is
It is preferably in the range of 3: 1 to 1: 3. The equivalent ratio of the active hydrogen-containing amino group to the epoxy group is 3: 1.
If it exceeds 300, the film formability of the obtained film will be poor, and the corrosion resistance and paintability will be insufficient. If the ratio is less than 1: 3, the corrosion resistance and the paintability of the treated film may be saturated.

Next, the polymer component (B) used in the present invention.
Is an oligomer or polymer containing the polymerized unit represented by the formula (I), and the polymerized unit of the formula (I) has an average degree of polymerization of 2 to 50.

In the formula (I), X bonded to the benzene ring is a hydroxyl group, a C1-5 alkyl group such as methyl, ethyl, propyl group or the like, a C1-5 hydroxyalkyl group such as hydroxymethyl, C6-C12 aryl groups such as hydroxyethyl and hydroxypropyl groups, such as phenyl and naphthyl groups, benzyl groups, benzal groups, and unsaturated hydrocarbon groups that condense on the benzene ring to form a naphthalene ring;
H = CH-CH = CH- or = CH-CH = CH-C
H = represents a group or a group of the above formula (II).

R1 and R2 in the formula (II) each independently represent a hydrogen atom, a hydroxyl group, C1-C1
0 alkyl groups such as methyl, ethyl, propyl, etc.
Examples thereof include C1-C10 hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, and hydroxypropyl groups.

In the formulas (I) and (II), Y1 and Y2 bonded to the benzene ring each independently have a hydrogen atom or a Z group represented by the formula (III) or (IV) . R3, R4, R5, R6 and R7 in the formulas (III) and (IV) each independently represent a C1-C10 alkyl group such as a methyl, ethyl, propyl group or the like; Group, for example, a hydroxymethyl, hydroxyethyl, hydroxypropyl group and the like.

Each of X and Y1 in the formula (I) and Y2 in the formula (II) bonded to each benzene ring in the polymer molecule is bonded to another benzene ring. Each of X, Y1 and Y2 may be the same or different from each other. The average number of substitutions of the Z group in each benzene ring in the polymer molecule is 0.2 to 1.0.
It is.

The average value of the number of substitutions of the Z group means the Z value introduced into each benzene ring in the polymer molecule.
It is the average of the number of groups. For example, in the formula (I), n
= 10 and X is a benzene ring-containing group of the formula (II), the number of benzene rings per molecule of the polymer is 20, and 10 benzene rings per molecule of the polymer. When a Z group destined for each one is introduced into the polymer molecule, the average number of Z group substitutions of this polymer molecule is [(1 × 10) + (0
× 10)] / 20 = 0.5.

If the average value of the number of Z group substitution is less than 0.2, the adhesion of the obtained polymer to the metal material is insufficient, and the coatability is deteriorated. When it exceeds 1.0, the hydrophilicity of the obtained polymer becomes large, and the corrosion resistance of the obtained film becomes insufficient.

Each of R3 to R7 in the Z group represented by the formulas (III) and (IV) represents a C1 to C10 alkyl group or a C1 to C10 hydroxyalkyl group. When the number of carbon atoms is 11 or more, the film-forming property of the formed film is reduced, so that the corrosion resistance and the paintability become insufficient.

Next, the coating of the second layer used in the present invention is as follows:
Preferably, silica is contained in a proportion of 5 to 70 parts by weight with respect to 100 parts by weight of the resin. More preferably 10-5
0 parts by weight. If this proportion is less than 5 parts by weight, the effect of improving the corrosion resistance and fingerprint resistance of the upper layer coating is lost, and the corrosion resistance and fingerprint resistance are reduced. On the other hand, if it exceeds 70 parts by weight, the upper layer coating becomes hard and the corrosion resistance after processing decreases.
The compounded silica is commercially available colloidal silica,
Organosilica sol, gas-phase silica, silica powder and the like can be used, Nissan Chemical Co., Ltd. Snowtex O, C,
OS, N, Aerosil 100, Nippon Aerosil Co., Ltd.
00, 300 and the like. The particle size is not particularly limited.

The resin used for coating the second layer is preferably a resin having a hydroxyl group and / or a carboxyl group. Such resins include commercially available epoxy resins,
Examples include alkyd resin, acrylic resin, urethane resin, acryl-modified polyester resin, phenol-modified alkyd resin, polyvinyl butyral resin, phenol resin, melamine resin, ethylene acrylic resin, and the like. Although the structure and molecular weight of these resins are not particularly limited, they need to be within a range in which silica can be uniformly dispersed and contained.

The coating amount of the second layer is 0.1-5.
0 g / m ² is preferred. If the upper layer coating is less than 0.1 g / m ² , corrosion resistance and fingerprint resistance become insufficient. On the other hand, if it exceeds 5.0 g / m ² , the coatability, especially the adhesion, becomes insufficient.

If necessary, the coating of the second layer may contain a wax, thereby providing lubricity.

In the resin used for coating the second layer, if necessary, ordinary rust preventive pigments, for example, molybdate pigments, phosphate pigments, rust preventives (for example, tannic acid, Even if a phenolic carboxylic acid such as gallic acid) is added, the corrosion resistance may be improved synergistically.

The weight ratio (A) / (B) of the silane coupling agent component (A) and the water-soluble polymer component (B) in the surface treatment agent used in the production method of the present invention.
Is preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1. This weight ratio is 1:10
Silane coupling agent component (A)
Is low, the adhesive strength with the substrate surface is reduced,
Corrosion resistance and paintability become insufficient. When it exceeds 10: 1, that is, when the ratio of the silane coupling agent component (A) is high, the film formability of the film is reduced, and the corrosion resistance and coating properties of the obtained film become insufficient.

Next, the method for producing the organic composite coated metal material of the present invention will be described. In the production method of the present invention,
The first layer contains the surface treatment agent composition and has a pH of 2.
The aqueous surface treatment liquid adjusted to the range of 0 to 6.5 is adhered to the surface of the metal material, and is dried. The adhered amount after drying is 10 to 500 mg / m ² , preferably 50 to 500 mg.
/ M ² . At this time, it is preferable to bring the aqueous treatment solution into contact with the surface of the metal material at a temperature of 10 to 60 ° C. for 0.1 to 30 seconds and heat and dry.

The pH of the aqueous surface treatment solution of the first layer is in the range of 2.0 to 6.5 using phosphoric acid, acidic phosphate, fluoride, complex fluoride, sulfuric acid, nitric acid, and organic acid. Adjusted. A more preferred pH value is 3.0 to 5.0. pH
If it is less than 2.0, the reactivity between the composition in the obtained processing solution and the surface of the substrate becomes excessively high, so that a film defect occurs, and the corrosion resistance and coating properties of the obtained film become insufficient. When the pH exceeds 6.5, the water-soluble polymer component (B)
Since the substance itself tends to precipitate and precipitate from the aqueous aqueous surface treatment liquid, the life of the aqueous treatment liquid is shortened.

The method of treating the surface of a metal material using the surface treating agent is not particularly limited, and for example, an immersion method, a spray method, a roll coating method and the like can be applied. The processing temperature and the processing time are not particularly limited, but generally, the processing temperature is preferably from 10 to 60 ° C., and the processing time is preferably from 0.1 to 20 seconds. Further, it is preferable to heat and dry the treated metal material. The heating temperature is preferably from 50 to 280C.

When the surface treatment composition used in the production method of the present invention is brought into contact with a metal material, a metal ion eluted from the metal material and the water-soluble polymer component (B) form a complex. And may cause precipitation. In such a case, a sequestering agent may be added to the surface treatment composition. Examples of the sequestering agent include EDTA, Cy-DTA, triethanolamine, gluconic acid, heptgluconic acid, oxalic acid, tartaric acid, malic acid and the like.

The aqueous resin composition applied to the second layer is not particularly limited with respect to the processing method, the processing temperature and the processing time, but generally the processing temperature is from 10 to 60 ° C. and from 0.1 to 10 ° C.
It is preferable to contact for 2 seconds and heat and dry.

The metal material used in the present invention includes an iron plate,
It can be selected from galvanized steel sheet, aluminum sheet, aluminum alloy sheet, stainless steel sheet and the like.

[0041]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by these examples.

1. Test material Cold rolled steel sheet Commercially available sheet thickness 0.6 mm JIS G3141 Zinc-containing metal plated steel sheet Commercially available sheet thickness 0.6 mm Hot-dip galvanized steel sheet (GI material) Commercially available sheet thickness 0.6 mm Electrogalvanized steel sheet (EG material) Aluminum plate Commercially available plate thickness 0.6 mm JIS A5052

2. Cleaning method for steel sheet The surface of the above metal material is treated with a medium alkali degreasing agent (registered trademark: Fine Cleaner 4336, Nippon Parkerizing Co., Ltd.)
Made) 20g / liter, treatment temperature:
Spray treatment was performed under the conditions of 60 ° C. and treatment time: 20 seconds to remove dust and oil adhering to the surface. Then, the alkali remaining on the surface was washed with tap water to clean the surface of the test material.

3. Composition of first layer surface treatment liquid <Treatment liquid A> 3 as silane coupling agent component (A)
-Mercaptopropyltrimethoxysilane, n = 5 as water-soluble polymer component (B), X = hydrogen, Y1 = Z = -C
H ₂ N (CH ₃ ) ₂ , Z group substitution average value = 1, (A):
(B) = 1: 8 was adjusted. Further, H ₂ SiF ₆
And adjusted to pH 3.0, and then diluted with deionized water to a solid content of 10% by weight.

<Treatment Liquid B> N- (2-aminoethyl) -3-aminopropyltrimethoxysilane as a silane coupling agent component (A) and a water-soluble polymer component (B)
Where n = 5, X = —CH ₂ —C ₆ H ₄ —OH, Y1 = Z
= —CH ₂ N (CH ₃ ) ₂ , Z group substitution number average value = 0.5
0, (A): (B) = 5: 1. After adjusting the pH to 4.0 with HF, the mixture was diluted with deionized water to a solid content of 10% by weight.

<Treatment Solution C> 3-Aminopropyltriethoxysilane + as the silane coupling agent component (A)
3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino group: equivalent ratio of epoxy group = 1: 2)
And n = 5 and X = —CH as the water-soluble polymer component (B).
_{2 -C 6 H 4 -OH, Y1} = Z = -CH 2 N (CH 3) 2, Z
The adjustment was made so that the average number of group substitution = 0.75 and (A) :( B) = 1: 1. After adjusting the pH to 4.0 with H ₂ TiF ₆ , the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

<Treatment Solution D> N- (2-aminoethyl) 3-aminopropyltrimethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in the amino group: silane coupling agent component (A)) Epoxy group equivalent ratio = 1: 2) and water-soluble polymer component (B)
Where n = 5, X = —CH ₂ —C ₆ H ₄ —OH, Y1 = Z
= —CH ₂ N (CH ₃ ) ₂ , Z group substitution number average value = 0.7
5, (A): (B) = 1: 1 was adjusted.
After adjusting the pH to 3.0 with phosphoric acid, the mixture was diluted with deionized water to a solid content of 10% by weight.

<Treatment Solution E> N- (2-aminoethyl) -3-aminopropyltrimethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino group: silane coupling agent component (A)) Epoxy group equivalent ratio = 1: 1) and water-soluble polymer component (B)
Where n = 5, X = hydrogen, Y1 = Z = —CH ₂ N (C
H ₃ ) ₂ , Z group substitution average value = 0.3, (A) :( B) =
It was adjusted to be 1: 1. After adjusting the pH to 4.0 with H ₂ TiF ₆ and phosphoric acid, the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

<Example 1> A treatment liquid A at 25 ° C was applied to a hot-dip galvanized steel sheet (GI) previously cleaned by the method described in (2) by a roll coating method to obtain a dry weight of 0.3%.
g / m ² , and dried at an ultimate plate temperature of 80 ° C. Silica powder (Nippon Aerosil Co., Ltd.)
2g as an aqueous resin composition containing 30 parts by weight of a water-soluble resin composition (trade name: Aerosil 200) based on 100 parts by weight of an acrylic-modified alkyd resin by a roll coating method.
/ M ² and dried at an ultimate plate temperature of 100 ° C.

Example 2 A treatment liquid B at 15 ° C. was applied to an aluminum plate (AL), which had been cleaned in advance by the method described in (2.), at a dry weight of 0.1 g / L by a roll coating method.
m ² , and dried so that the reached plate temperature was 150 ° C. An aqueous resin composition containing silica powder (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 300) in a ratio of 70 parts by weight based on 100 parts by weight of the phenol-modified alkyd resin as a dry weight by a roll coating method in an upper layer of 1 g. / M ² and dried at a plate temperature of 150 ° C.

<Example 3> A treatment liquid B at 30 ° C was applied to a hot-dip galvanized steel sheet (GI) previously cleaned by the method described in (2) by a roll coating method to obtain a dry weight of 0.0
Coating was performed so as to be 5 g / m ² , and drying was performed so that the reached plate temperature was 100 ° C. An aqueous resin composition containing silica powder (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 200) in a ratio of 50 parts by weight to 100 parts by weight of an acrylic resin as a dry layer by a roll coating method in an upper layer of 3 g.
/ M ² and dried at an ultimate plate temperature of 100 ° C.

Example 4 A treatment liquid C at 20 ° C. was applied to an electrogalvanized steel sheet (EG), which had been cleaned in advance by the method described in (2), by roll coating to obtain a dry weight of 0.0
Coating was performed so as to be 5 g / m ² , and drying was performed so that the reached plate temperature was 180 ° C. An aqueous resin composition containing colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex N) at a ratio of 70 parts by weight with respect to 100 parts by weight of the ethylene acrylic resin as a dry layer in a thickness of 1 g by a roll coating method. / M ² and dried at an ultimate plate temperature of 100 ° C.

<Example 5> A treatment liquid D at 20 ° C was applied to a hot-dip galvanized steel sheet (GI) previously cleaned by the method described in (2) by a roll coating method to a dry weight of 0.1%.
g / m ² , and dried so that the reached plate temperature was 80 ° C. An aqueous resin composition containing colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex N) at a ratio of 20 parts by weight to 100 parts by weight of an ethylene acrylic resin as a dry layer in a thickness of 2 g as a dry weight by a roll coating method. / M ² and dried at a reaching plate temperature of 180 ° C.

<Example 6> A treatment liquid E at 20 ° C was applied to a hot-dip galvanized steel sheet (GI) previously cleaned by the method described in (2) by a roll coating method to obtain a dry weight of 0.0
Coating was performed so as to be 3 g / m ² , and drying was performed so that the reached plate temperature was 80 ° C. An aqueous resin composition containing colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex O) at a ratio of 20 parts by weight to 100 parts by weight of an ethylene acrylic resin as a dry layer is 1 g as a dry weight by a roll coating method. / M ² and dried at a plate temperature of 80 ° C.

<Example 7> A treatment liquid E at 20 ° C was applied to a hot-dip galvanized steel sheet (GI) previously cleaned by the method described in (2) by a roll coating method to obtain a dry weight of 0.5%.
g / m ² , and dried so that the reached plate temperature was 80 ° C. An aqueous resin composition containing colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex O) at a ratio of 70 parts by weight to 100 parts by weight of the urethane-modified epoxy resin as a dry weight by a roll coating method. 0.3 g / m ^{2 was} applied and dried at a reaching plate temperature of 180 ° C.

Example 8 A treatment solution E at 20 ° C. was applied to a cold-rolled steel sheet (SPC) previously cleaned by the method described in (2.).
Was 0.5 g / m ² as a dry weight by a roll coating method.
And dried so that the reached plate temperature was 80 ° C. Colloidal silica (Nissan Chemical Co., Ltd.)
And 4 g of an aqueous resin composition containing 70 parts by weight of a synthetic resin (trade name: Snowtex N) based on 100 parts by weight of the urethane-modified epoxy resin by a roll coating method.
/ M ² and dried at a reaching plate temperature of 180 ° C.

<Comparative Example 1> A treatment liquid C at 20 ° C was applied to a hot-dip galvanized steel sheet (GI) previously cleaned by the method described in (2) by a roll coating method to obtain a dry weight of 0.3.
g / m ² , and dried so that the reached plate temperature was 180 ° C.

<Comparative Example 2> A treatment solution A at 20 ° C was applied to an electrogalvanized steel sheet (EG) previously cleaned by the method described in (2) by a roll coating method to obtain a dry weight of 0.0
Coating was performed so as to be 5 g / m ² , and drying was performed so that the reached plate temperature was 80 ° C. An aqueous resin composition containing only a urethane resin was formed on the upper layer by a roll coating method in a dry weight of 1 g /
m ^{2 was} applied and dried at an ultimate plate temperature of 100 ° C.

<Comparative Example 3> A treatment liquid B at 30 ° C. was applied to aluminum (AL) which had been cleaned in advance by the method described in (2.) by a roll coating method to obtain a dry weight of 0.1 g / m 2.
² and dried so that the reached plate temperature was 180 ° C. The upper layer is made of colloidal silica (Nissan Chemical
1 g of an aqueous resin composition containing 90 parts by weight of 100 parts by weight of ethylene acrylic resin and 1 wt.
/ M ² and dried at an ultimate plate temperature of 100 ° C.

<Comparative Example 4> A treatment liquid D at 20 ° C was applied to a galvanized steel sheet (EG), which had been cleaned in advance by the method described in (2), in a roll coating method to obtain a dry weight of 0.0
Coating was performed so as to be 5 g / m ² , and drying was performed so that the reached plate temperature was 180 ° C. An aqueous resin composition containing silica powder (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 200) in a ratio of 50 parts by weight with respect to 100 parts by weight of ethylene acrylic resin as a dry layer by a roll coating method in an amount of 0.1 wt. 05 g / m ^{2 was} applied and dried at an ultimate plate temperature of 100 ° C.

<Comparative Example 5> Colloidal silica (trade name: Snowtex N, manufactured by Nissan Chemical Industries, Ltd., trade name: ethylene acrylic resin 100) was added to electrogalvanized steel sheet (EG) that had been cleaned in advance by the method described in (2.). An aqueous resin composition containing 50 parts by weight with respect to parts by weight was applied at a dry weight of 1 g / m ² by a roll coating method and dried at a final plate temperature of 100 ° C.

3. Evaluation Test Method Evaluation was performed by the following evaluation method. Table 1 shows the results.

[0063]

[Table 1]

3.1. Corrosion resistance The test material was subjected to a salt spray test specified in JIS-Z2371 for 240 hours. The white rust resistance was visually measured and evaluated. The evaluation criteria are as follows. ：: White rust occurrence rate of less than 5% ○: White rust occurrence rate of 5% or more and less than 10% △: White rust occurrence rate of 10% or more and less than 50% ×: White rust occurrence rate of 50% or more

3.2. Coating adhesion A coating was applied to the test surface-treated metal material under the following conditions, and a coating film adhesion test was performed. Coating conditions Paint: Amilac # 1000 manufactured by Kansai Paint Co., Ltd.
(Trademark) (white paint) Coating method: bar coating method, baking: 140 ° C., 20 minutes Film thickness: 25 μm 3.2.1. Primary adhesiveness 100 squares of 1 mm square were cut into the coating film with an NT cutter, and this test material was extruded 5 mm with an Erichsen tester. Evaluation was made based on the number of peeled films. The evaluation criteria are shown below. ◎: No peeling ：: 1 or more peeled and less than 10 △: 11 or more peeled and less than 50 ×: White rust occurrence rate of 51 or more and less than 100 3.2.2. Secondary adhesion After the test plate was immersed in boiling water for 2 hours, a test similar to the primary adhesion test was performed and evaluated.

3.3. Corrosion resistance after coating
The salt spray test specified in JIS-Z2371 was performed at 240
Conducted for hours. After the operation, the cut part was peeled off with an adhesive tape, and the peel width was evaluated. As a criterion, the peeling width (mm) of the coating film from the cut portion was measured. ◎: less than 3 mm ：: 3 mm or more and less than 5 mm Δ: 5 mm or more and less than 10 mm ×: 10 mm or more

3.4. Press your finger against the fingerprint-resistant test board,
The trace state of the fingerprint was visually evaluated. The criteria are as follows. ◎: No trace of fingerprint remains at all ○: Trace of fingerprint remains very slightly △: Trace of fingerprint remains slightly ×: Trace of fingerprint remains clear

As is evident from the results in Table 1, Examples 1 to 8 using the surface treatment composition of the present invention show good corrosion resistance, coating properties, corrosion resistance after coating and fingerprint resistance.
However, in Comparative Example 1 in which the upper layer coating treatment was not performed, the corrosion resistance,
Poor fingerprint resistance. Comparative Example 2, in which the upper resin did not contain silica, was inferior in corrosion resistance and fingerprint resistance. Comparative Example 3, which contained silica outside the scope of the present invention,
A decrease in adhesion was observed. Further, in Comparative Example 4 in which the amount of the upper layer film is out of the range of the present invention, satisfactory corrosion resistance cannot be obtained. In Comparative Example 5 in which no undercoating treatment was performed, the corrosion resistance and adhesion were considerably inferior.

[0069]

The organic composite coated metal material formed by the production method of the present invention can provide high corrosion resistance, paint adhesion and fingerprint resistance without using a chromate, unlike conventional products. In the future, effluent regulations will make it possible to adapt to industries where chromium-free is required. Furthermore, since there is no selectivity to a metal material, rust prevention and paintability can be improved while utilizing the characteristics of the material. Also, it is extremely effective and has a large practical effect as a countermeasure against social problems such as environmental conservation and recyclability.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 201/00 C09D 201/00

Claims (7)

[Claims] 1. The following components as a first layer on the surface of a metal material: (A) an active hydrogen-containing amino group, an epoxy group, a vinyl group,
A silane coupling agent component comprising at least one silane coupling compound having at least one reactive functional group selected from a mercapto group and a methacryloxy group, and (B) one kind represented by the following general formula (I) At least one polymer component containing the above polymer at an average degree of polymerization of 2 to 50: [Wherein, X bonded to the benzene ring is a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, a C1-C5
A hydroxyalkyl group of C5, an aryl group of C6 to C12, a benzyl group, a benzal group, an unsaturated hydrocarbon group which forms a naphthalene ring by condensing with the benzene ring, or a group of the following formula (II): Wherein R1 and R2 in the formula (II) each represent a hydrogen atom, a hydroxyl group, a C1 to C5 alkyl group, or a C1 to C10 hydroxyalkyl group,
In the formulas (I) and (II), Y1 and Y2 bonded to the benzene ring are each independently a hydrogen atom or Z represented by the following formulas (III) and (IV).
Group: And R3, R4 in the above formulas (III) and (IV),
R5, R6 and R7 each independently represent a hydrogen atom, a C1-C10 alkyl group or a C1-C10 hydroxyalkyl group, and X, Y1 and Y2 bonded to each benzene ring in the polymer molecule; Each of the
X, Y1 and Y2 bonded to other benzene rings may be the same as or different from each other, and the average number of substitutions of the Z group in each benzene ring in the polymer molecule Is 0.2 to 1.0. Wherein the second layer is coated on the first layer with a resin composition containing silica in an amount of 5 to 70 parts by weight based on 100 parts by weight of the resin. Organic composite coated metal material with excellent corrosion resistance, paintability and fingerprint resistance. 2. The weight ratio (A) / (B) of the silane coupling agent component (A) to the polymer component (B) is 1: 2.
The organic composite coated metal material according to claim 1, wherein the ratio is 10 to 10: 1. 3. A silane coupling agent wherein said silane coupling agent component (A) comprises (a) one or more silane coupling compounds having one or more active hydrogen-containing amino groups; and (b) one silane coupling agent. The organic composite-coated metal material according to claim 1, comprising a silane coupling agent comprising one or more silane coupling compounds having the epoxy group. 4. An equivalent ratio of an active hydrogen-containing amino group contained in the silane coupling agent (a) to an epoxy group contained in the silane coupling agent (b) is 3: 1.
The organic composite-coated metal material according to claim 3, wherein the ratio is １ ： 1: 3. 5. The weight ratio [(a) + (b)] / (B) of the total amount of the silane coupling agent (a) and the silane coupling agent (b) to the polymer component (B). ) Is 1: 5 to 5: 1, the organic composite-coated metal material according to claim 3 or 4. 6. The organic composite coated metal material according to claim 1, wherein the second layer resin has a structure having a hydroxyl group or a carboxyl group. 7. An aqueous medium and the following components dissolved in the aqueous medium: (A) an active hydrogen-containing amino group, an epoxy group, a vinyl group,
A silane coupling agent component comprising at least one silane coupling compound having at least one reactive functional group selected from a mercapto group and a methacryloxy group, and (B) one kind represented by the following general formula (I) One or more water-soluble polymer components containing the above water-soluble polymer at an average degree of polymerization of 2 to 50: [Wherein, X bonded to the benzene ring is a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, a C1-C5
A hydroxyalkyl group of C5, an aryl group of C6-C12, a benzyl group, a benzal group, an unsaturated hydrocarbon group which forms a naphthalene ring by condensing with the benzene ring, or a group of the following formula (II): Wherein R1 and R2 in the formula (II) each represent a hydrogen atom, a hydroxyl group, a C1 to C5 alkyl group, or a C1 to C10 hydroxyalkyl group,
In the formulas (I) and (II), Y1 and Y2 bonded to the benzene ring are each independently a hydrogen atom or Z represented by the following formulas (III) and (IV).
Group: And R3, R4 in the above formulas (III) and (IV),
R5, R6 and R7 each independently represent a hydrogen atom, a C1-C10 alkyl group or a C1-C10 hydroxyalkyl group, and X, Y1 and Y2 bonded to each benzene ring in the polymer molecule; Each of the
X, Y1 and Y2 bonded to other benzene rings may be the same as or different from each other, and the average number of substitutions of the Z group in each benzene ring in the polymer molecule Is 0.2 to 1.0. An aqueous composition adjusted to a pH value of 2.0 to 6.5 consisting of the following is applied to the surface of the metal material so that the amount of adhesion after drying becomes 10 to 500 mg / m ² , dried, and then applied to the upper layer. The second layer is coated with an aqueous resin composition containing silica in an amount of 5 to 70 parts by weight based on 100 parts by weight of the aqueous resin so that the adhesion amount after drying is 0.1 to 5.0 g / m ^2. A method for producing an organic composite coated metal material having excellent corrosion resistance, paintability, and fingerprint resistance characterized by drying.