WO1999050366A1 - Metallic material with organic composite coating excellent in corrosion resistance and coatability and reduced in finger mark adhesion and process for producing the same - Google Patents

Abstract

A metallic material having a surface excellent in corrosion resistance and coatability and reduced in finger mark adhesion. The coated metallic material comprises a metallic material having on a surface thereof: a first coating layer obtained from (A) a silane coupling agent ingredient having a reactive functional group such as an amino group having active hydrogen or an epoxy group and (B) a polymer ingredient comprising a water-soluble polymer represented by formula (I) having an average degree of polymerization of 2 to 50; and formed on the first layer, a second coating layer made of a resin composition comprising 100 parts by weight of a resin and 5 to 70 parts by weight of silica.

Description

 Description Organic composite coated metal material with excellent corrosion resistance, paintability and fingerprint resistance, and method for producing the same

[Technical field]

 The present invention relates to a metal material that can impart excellent corrosion resistance, paintability and fingerprint resistance to the surface of a metal material, and is used for home appliances and building material products.

[Background technology]

 Generally, metal materials such as copper plates and aluminum plates with zinc-containing metal are used in a wide range of fields such as automobiles, building materials and home appliances. However, zinc and aluminum corrode in the air and produce corrosion products (so-called white), which degrade the appearance of metallic materials and adversely affect paintability. It has the disadvantage that fingerprints and other stains can easily adhere to the product during the manufacture of the product, which can significantly reduce the commercial value.

 Therefore, in order to improve the corrosion resistance, paintability, and fingerprint resistance of the metal material surface, the surface of the metal material was subjected to chromate treatment using a treatment solution mainly containing chromic acid, dichromic acid or salts thereof. 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 protection, hexavalent chromium in the chromate treatment solution used to treat metal material surfaces has a direct adverse effect on the human body. Chromating is often avoided. In addition, wastewater containing hexavalent chromium needs to be treated specially as specified in the Water Pollution Control Law, which leads to an increase in the cost of kana as a whole. In addition, chromate-treated metal materials have the major disadvantage that they cannot be recycled as chromium-containing industrial waste, which has become a major social problem. On the other hand, as a surface treatment method other than chromate, a surface treatment agent using tannic acid containing polyvalent phenolcarbonic acid is well known. When the metal material is treated with an aqueous solution of tannic acid, the protective film formed by the reaction between the tannic acid and the metal material is barrier-free against invasion of corrosive substances, so that the corrosion resistance of the metal material is considered to be improved. ing. However, in recent years, as the quality of products has increased, the coating itself has been 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 practical application at present is not feasible. It is possible.

 Therefore, as a treatment method for improving the corrosion resistance of a metal material, Japanese Patent Application Laid-Open No. 53-121034 discloses an aqueous solution comprising water-dispersible silica, an alkyd resin, and a trioxy silane compound applied to the metal surface. A method for doing so is disclosed.

 Also, a surface treatment method for imparting corrosion resistance to a metal material using a water-soluble resin composed of a hydroxypyrone compound derivative, and a metal treatment using a water-soluble or water-dispersible polymer of a hydroxystyrene compound. A method for imparting corrosion resistance to a material is disclosed in Japanese Patent Application Laid-Open No. 57-444751, and

It is disclosed in, for example, Japanese Patent Application Laid-Open No. 1-177380.

 However, none of the above methods can form a film capable of imparting excellent corrosion resistance that can be substituted for a chromate film on the surface of a metal material, and the above problem has not been solved at all as a practical problem. . Therefore, at present, no non-stick surface treatment agent and surface treatment method for metal materials with excellent corrosion resistance have been obtained.

[Disclosure of the Invention]

 An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a non-chromium-based organic composite coated metal material excellent in heat resistance, corrosion resistance, paintability and fingerprint resistance. is there.

The present inventors have conducted intensive studies to solve these problems of the conventional technology, and as a result, a silane coupling agent component as a first layer on a metal material surface and a polymer component having a specific chemical structure have been developed. As a film, and as a second layer, the upper layer of the first layer is coated with a resin composition containing a silicide force As a result, the present inventors have found an organic composite-coated metal material excellent in corrosion resistance, paintability, and fingerprint resistance, and a method for producing the same, and have completed the present invention. That is, the organic composite-coated metal material of the present invention has the following composition as a first layer on the surface of the metal material:

 (A) Silane coupling comprising one or more silane coupling compounds having at least one reactive functional group selected from active hydrogen-containing amino, epoxy, butyl, mercapto and methacryloxy groups Agent components and

 (B) one or more polymer components containing one or more polymers represented by the following general formula (I) with an average degree of polymerization of 2 to 50:

[Wherein, X bonded to the benzene ring is a hydrogen atom, a hydroxy group, a C1-C5 alkyl group, a C1-C5 hydroxyalkyl group, a C6-C1 2, an aryl group, a benzyl group, a benzal group, an unsaturated hydrocarbon group condensed to the benzene ring to form a naphthalene ring, or a group of the following formula (II):

R 1 — C — R 2

0 H R 1 and R 2 in the formula (II) each represent a hydrogen atom, a hydroxyl group, a C 1 to C 5 alkyl group, or a C 1 to C 10 hydroxyalkyl group, In (I) and (II), Y 1 and Y 2 bonded to the benzene ring are each independently a hydrogen atom or a Z group represented by the following formulas (III) and (IV). :

 — C H 2

R 3, R 4, R 5, R 6 and R 7 in the above formulas (III) and (IV) are each independently a hydrogen atom, a C 1 -C 10 alkyl group or C 1 X represents a hydroxyalkyl group of ~ 10, and each of X, Y1 and Y2 bonded to each benzene ring in the polymer molecule is X, bonded to another benzene ring. Y 1 and Y 2 may be the same 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. is there. 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. Things.

 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, 1:10 to 10; Preferably, there is.

The silane adhesive used in the organic composite coated metal material of the present invention. PT / JP99 / 01437

The pulling agent component (A) is

 (a) a silane coupling agent comprising one or more silane coupling compounds having one or more active hydrogen-containing amino groups, and (b) one or more silane coupling compounds having one or more epoxysilane groups. It is preferable to include a silane coupling agent.

 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 3: It is preferably from 1 to 13.

 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 preferably from 1: 5 to 5: 1. [Best Mode for Carrying Out the Invention]

 The first layer film used in the organic composite coated metal material of the present invention includes a silane coupling agent component (A) composed of at least one silane coupling compound having a specific reactive functional group, It is a polymerization component (B) comprising one or more phenolic resin-based polymers containing an amino group. The silane coupling compound contained in the silane coupling agent component (A) used in the present invention is a compound having a reactive functional group in one molecule comprising an active hydrogen-containing amino group, an epoxy group, a butyl group, a mercapto group and a methacryloxy group. The structure is not particularly limited as long as it includes at least one selected member, but specific examples include those having the following compositions (1) to (4).

 (1) Having an amino group

 N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane

(2) Having epoxy group 3-Glycidoxypropyltrimethoxysilane, 3-Dalicydoxypropylmethyldimethoxysilane, 2- (3,4 epoxycyclohexyl) ethylethyl methoxysilane

(3) Having a bullet group

 Bull triethoxysilane

 も の Having a mercapto group

 3-Mercaptoprovir trimethoxysilane

も の Having a metalloxy group

 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane The silane coupling agent component (A) used in the present invention comprises one or more silane groups having one or more active hydrogen-containing amino groups. The silane coupling agent preferably comprises a silane coupling agent (a) comprising a coupling compound and a silane coupling agent (b) comprising one or more silane coupling compounds having one or more epoxy groups.

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

 Next, the polymer component (B) used in the present invention is an oligomer or a polymer containing the polymerized unit represented by the formula (I), and the polymerized unit of the formula (I) has an average polymerization degree of 2 to 5 It is 0.

In the formula (I), X bonded to the benzene ring is a hydroxyl group, a C1-5 alkyl group such as a methyl, ethyl, propyl group, etc., and a C1-5 hydroxyalkyl group such as a hydroxy group. C6 to C12 aryl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, etc. Benzyl group, benzal group, etc., an unsaturated hydrocarbon group condensed to the benzene ring to form a naphthalene ring,

_CH = CH—CH = CH— or = CH—CH = CH—CH = or a group of the above formula (II).

 R 1 and R 2 in the formula (II) each independently represent a hydrogen atom, a hydroxyl group, a C 1 -C 10 alkyl group, for example, a methyl, ethyl, propyl group or the like; And a hydroxyalkyl group of 0, for example, hydroxymethyl, hydroxyshethyl, hydroxypropyl group and the like. In the formulas (I) and (II), Y 1 and Y 2 bonded to the benzene ring are each independently a hydrogen atom or Z represented by the formula (III) or (IV). Having a group. R 3, R 4, R 5, R 6 and R 7 in the formulas (III) and (IV) each independently represent a C 1 -C 10 alkyl group such as methyl, ethyl, propyl, etc. And C1 to C5 hydroxyalkyl groups, for example, hydroxymethyl, hydroxyshethyl, hydroxypropyl and the like.

 X and Y 1 in Formula (I) and Y 2 in Formula (II) each bonded to each benzene ring in the polymer molecule are X bonded to other benzene rings. , Y 1 and Y 2 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 from 0.2 to 1.0.

 The average value of the number of substitutions of the Z group is an average value of the number of the Z groups introduced into each benzene ring in the polymer molecule. For example, in the formula (I), when 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, If one Z molecule per molecule is introduced into 10 benzene rings per polymer molecule, the average number of Z group substitutions in this polymer molecule is [(1 X 10) + (0 X 10)] / 2 0 = 0.5.

If the average value of the number of Z group substitution is less than 0.2, the recoating property becomes poor because the obtained polymer has insufficient adhesion to metal materials. On the other hand, if it exceeds 1.0, the resulting polymer will have high hydrophilicity and the resulting film will have insufficient corrosion resistance. Each of R 3 to R 7 in the Z group represented by the formulas (III) and (IV) is a C 1 to C 10 alkyl group or a C 1 to C 10 hydroxyalkyl group. Represents 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 preferably contains silica in an amount of 5 to 70 parts by weight based on 100 parts by weight of the resin. Preferably, it is 10 to 50 parts by weight. If the 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 coating of the upper layer becomes hard, and the corrosion resistance after processing decreases. Commercially available colloidal silica, organosilica sol, gas-phase silica, silica powder, etc. can be used for the compounded silica. Snowtex 0, C, OS, N of Nissan Chemical Co., Ltd., Nippon Aerosil Co., Ltd. Aerosil 100, 200, 300, etc. 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. Examples of such resins include commercially available epoxy resins, alkyd resins, acrylic resins, urethane resins, acryl-modified polyester resins, phenol-modified alkyd resins, polybutylbutyral resins, phenol resins, melamine resins, and ethylene acrylic resins. Can be The structure and molecular weight of these resins are not particularly limited, but they must be within a range in which silicic acid can be uniformly dispersed and contained.

As coating adhesion amount of the second layer 0. 1 to 5. O g Zm ² is preferred. When the upper layer coating is less than 0.1 g / m ² , the corrosion resistance and the fingerprint resistance become insufficient. On the other hand, if it exceeds 5.0 g / m ² , the paintability, especially the adhesion, becomes insufficient.

 If necessary, a wax can be contained in the coating of the second layer, and lubricity can also be imparted.

In the resin used for the coating of the second layer, if necessary, an ordinary protective pigment, for example, a molybdate-based pigment, a phosphate-based pigment, or a protective agent (for example, tannic acid, gallic acid) Phenolic carboxylic acids, etc.) may synergistically improve the corrosion resistance. In the surface treatment agent used in the production method of the present invention, the weight ratio (A) Z (B) to the silane coupling agent component (A) and the water-soluble polymer component (B) is 1:10. ~: L 0: 1 is preferred, and preferably 1: 5 to 5: 1. If this weight ratio is less than 1:10, that is, if the ratio of the silane coupling agent component (A) is low, the adhesion to the substrate surface is reduced, and the corrosion resistance and coating properties become insufficient. On the other hand, if it exceeds 10: 1, that is, if the silane coupling agent component (A) ratio is high, the film-forming properties of the film decrease, and the corrosion resistance and paintability of the resulting film become insufficient.

Next, a method for producing the organic composite coated metal material of the present invention will be described. In the production method of the present invention, an aqueous surface treatment solution containing the surface treatment agent composition as the first layer and having a pH adjusted to a range of 2.0 to 6.5 is adhered to the surface of the metal material. the deposition amount after drying was dry 10~500mgZ m ^2, preferably to be 5 0~50 OnigZni ^2. At this time, it is preferable that the aqueous treatment liquid is brought into contact with the surface of the metal material at a temperature of 10 to 60 ° C. for 0.1 to 30 seconds and dried by heating.

 The pH of the first layer aqueous surface treatment solution is adjusted to the range of 2.0 to 6.5 using phosphoric acid, acidic phosphate, fluoride, complex fluoride, sulfuric acid, nitric acid, and organic acid. You. The preferred PH value is between 3.0 and 5.0. If the pH is less than 2.0, the reactivity between the composition in the obtained processing solution and the substrate surface becomes excessively high, so that a film defect occurs and the obtained film has insufficient corrosion resistance and paintability. . If the pH exceeds 6.5, the water-soluble polymer component (B) itself tends to precipitate out of the aqueous aqueous surface treating solution, so that the life of the aqueous treating solution 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 280 ° C. 7

 Ten

When the surface treatment composition used in the production method of the present invention is brought into contact with the metal material, the metal ion eluted and mixed from the metal material and the water-soluble polymer component (B) form a complex. However, precipitation may occur. 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, dalconic acid, heptgluconic acid, oxalic acid, tartaric acid, and malic acid.

 Regarding the aqueous resin composition applied to the second layer, there is no particular limitation on the treatment method, treatment temperature, and treatment time, but in general, the treatment is carried out at a temperature of 10 to 60 ° C for 0.1 to 10 seconds, followed by heating and drying. Is preferred.

 The metal material used in the present invention can be selected from iron plates, zinc-plated copper plates, aluminum plates, aluminum alloy plates, stainless copper plates, and the like.

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

1. Test material

 ① Cold rolled steel sheet

 Commercial thickness 0.6 mm J I S G 3 14 1

 (2) Copper plate with zinc-containing metal

 Commercially available 0.6mm hot-dip galvanized copper plate (GI material)

 Commercially available sheet thickness 0.6 mm Electro-galvanized steel sheet (EG material)

 ③ Aluminum plate

 Commercially available plate thickness 0.6 mm J I S A 505 2

 2. How to clean copper plate

 The surface of the above metal material is treated with a medium alkali degreasing agent (registered trademark: Fine Talina 4336, manufactured by Nippon Parkerizing Co., Ltd.). Chemical concentration: 20 gZ liter, treatment temperature: 60 ° C, treatment time: 20 seconds Spray treatment was performed under the following conditions to remove dust and oil adhering to the surface. Next, 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 solution

 Processing solution A>

3-mercaptopropyl tri as silane coupling agent component (A) Main Tokishishiran, n = 5, X = hydrogen as a water-soluble polymer component (B), Y 1 = Z = -CH 2 N (CH 3) 2, Z group substitution number average = 1, (A): ( B ) = 1: Adjusted to 8. After adjusting the pH to 3.0 with H ₂ SiF ₆ , the mixture was diluted with deionized water to a solid content of 10% by weight.

 <Treatment liquid B>

N- (2-aminoethyl) -13-aminopropyltrimethoxysilane as the silane coupling agent component (A) and n = 5, X = —CH ₂ — C as the water-soluble polymer component (B) ₆ H ₄ —OH, Y 1 = Z = _CH ₂ N (CH ₃ ) ₂ , Z-group substitution average value = 0.50, (A): (B) = 5: 1. After adjusting the pH to 4.0 with HF, the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

 <Treatment liquid C>

As silane coupling agent component (A), 3-aminopropyltriethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino group: equivalent ratio of epoxy group = 1: 2) and water solubility n as the polymer Ingredient (B) = 5, X = - CH 2 - C 6 H 4 - OH, Y 1 = Z = -CH 2 n (CH 3) 2, Z group substitution number average = 0.75 , (A): (B) = 1: 1 Further, the pH was adjusted to 4.0 with H ₂ Ti F ₆ , and then diluted with deionized water to obtain a solid content of 10% by weight.

 <Treatment liquid D>

As the silane coupling agent component (A), N- (2-aminoethyl) 3 -aminopropyltrimethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino group: equivalent ratio of epoxy group = 1) : 2) and n = 5, X = -CH ₂ -C ₆ H ₄ —OH, Y 1 = Z = -CH ₂ N (CH ₃ ) ₂ , Z group substitution number as the water-soluble polymer component (B) The average value was adjusted to 0.75, and (A): (B) = 1: 1. After adjusting the pH to 3.0 with phosphoric acid, the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

 <Treatment liquid E>

N- (2-aminoethyl) -one as silane coupling agent component (A) 3-aminopropyltrimethoxysilane + 3-dalicidoxypropylmethyldimethoxysilane (equivalent ratio of active hydrogen in epoxy group to epoxy group == 1: 1) and n = 5 as water-soluble polymer component (B) , X = hydrogen, Y 1 = Z = —CH ₂ N (CH ₃ ) ₂ , Z group substitution average value = 0.3, (A): (B) = 1: 1. Further, after adjusting the pH to 4.0 with H ₂ Ti F ₆ and phosphoric acid, the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

 Example 1>

Treatment liquid A at 25 ° C is roll-coated on a hot-dip galvanized steel sheet (GI) that has been previously cleaned by the method described in (2.) to a dry weight of 0.3 g / m ^2. And dried at an ultimate plate temperature of 80 ° C. An aqueous resin composition containing silica powder (manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL 200) in an upper layer at a ratio of 30 parts by weight to 100 parts by weight of the acryl-modified alkyd resin by a roll coating method. The coating was applied at a dry weight of 2 g / m ² and dried at an ultimate plate temperature of 100 ° C.

 <Example 2>

The treatment liquid B at 15 ° C was applied to the aluminum plate (AL) previously cleaned by the method described in (2.) by a roll coating method so as to have a dry weight of 0.1 gm ² . Drying was performed 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 to 100 parts by weight of the phenol-modified alkyd resin was dried by a roll coating method. 1 gZm ^{2 and} dried at an ultimate plate temperature of 150 ° C.

 Example 3>

The treatment liquid B at 30 ° C is applied to a copper plate (GI) coated with hot-dip zinc that has been cleaned in advance as described in (2.) by a roll coating method to a dry weight of 0.05 g / m ^2. And dried so that the plate temperature reached 100 ° C. An aqueous resin composition containing 50 parts by weight of silica powder (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) in 100 parts by weight of acryl resin as a dry weight by a roll coating method in an upper layer of the aqueous resin composition. g / m ² was applied and dried at an ultimate plate temperature of 100 ° C. Example 4>

Apply 2 CTC treatment solution C by roll coating to a dry weight of 0.05 gZm ² on an electrogalvanized copper plate (EG) that has been cleaned in advance as described in (2.). Then, drying was performed so that the reached plate temperature was 180 ° C. An aqueous resin composition containing 70 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex N) in an amount of 100 parts by weight of ethylene acryl resin is roll-coated on the upper layer. Was applied as a dry weight of 1 g Zm ^{2 and} dried at an ultimate plate temperature of 100 ° C.

 Example 5>

A treatment liquid D at 20 ° C is applied to a hot-dip zinc-plated copper plate (GI) previously cleaned by the method described in (2.) by a roll coating method so as to have a dry weight of 0.1 lg / 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 100 parts by weight of ethylene acryl resin to the upper layer by a roll coating method. Was applied at a dry weight of 2 g / m ^{2 and} dried at an ultimate plate temperature of 180 ° C.

 <Example 6>

To a molten zinc plated copper plate (GI) previously cleaned by the method described in (2.), apply a treatment liquid E at 20 ° C by a roll coating method to a dry weight of 0.03 g nom ² . And dried so that the reached plate temperature was 80 ° C. The upper layer is roll-coated with an aqueous resin composition containing colloidal silica (produced by Nissan Chemical Co., Ltd., trade name: SNOTETUS TAS O) in a ratio of 20 parts by weight to 100 parts by weight of ethylene acryl resin. and dried in a dry weight 1 gZ m ² coating reached plate temperature 8 0 law.

 <Example 7>

Applying a treatment solution E at 20 ° C to a copper plate (GI) coated with hot-dip zinc, which was previously cleaned by the method described in (2.), using a roll coat 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) in an upper layer at a ratio of 70 parts by weight to 100 parts by weight of the urethane-modified epoxy resin was roll-coated. 0.3 as dry weight by g / m ^{2 was} applied and dried at an ultimate plate temperature of 180 ° C.

 Example 8>

Apply the treatment liquid E at 20 ° C to a cold-rolled steel sheet (SPC) previously cleaned by the method described in (2) by a roll coating method to a dry weight of 0.5 gZm ^2. Then, 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 N) at a ratio of 70 parts by weight to 100 parts by weight of the urethane-modified epoxy resin is dried by a roll coating method. 4 g / m ^{2 and} dried at an ultimate plate temperature of 180 ° C.

 <Comparative Example 1>

Applying a treatment liquid C at 20 ° C to a dry zinc coated copper plate (GI) previously cleaned by the method described in (2.) by a roll coating method to a dry weight of 0.3 g / m ^2. And dried to reach a plate temperature of 180 ° C.

 <Comparative Example 2>

Apply a treatment solution A at 20 ° C to a copper plate (EG) coated with electro-zinc that has been cleaned in advance as described in (2.) by a roll coating method so that the dry weight becomes 0.05 gZm ^2. It was applied and dried so that the plate temperature reached 80 ° C. The upper layer was coated with an aqueous resin composition containing only a urethane resin by a roll coating method at a dry weight of 1 g / m ² , and dried at an ultimate plate temperature of 100 ° C.

 <Comparative Example 3>

Apply the treatment liquid B at 30 ° C to the aluminum (AL) previously cleaned by the method described in (2) by the roll coating method so that the dry weight becomes 0.1 gZm ^2. Drying was performed at a temperature of 180 ° C. An aqueous resin composition containing, as an upper layer, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex N) in a ratio of 90 parts by weight to 100 parts by weight of ethylene acryl resin is dried by a roll coating method. 1 gZm ^{2 and} dried at an ultimate plate temperature of 100 ° C.

 <Comparative Example 4>

The treatment liquid D at 20 ° C was applied to a copper plate (EG) plated with electro-zinc which had been cleaned in advance according to (2. g / m ² , and dried so that the reached plate temperature was 180 ° C. An aqueous resin composition containing silica powder (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) in an upper layer at a ratio of 50 parts by weight to 100 parts by weight of ethylene acryl resin was subjected to a roll coating method. in the 0. 0 5 gZm ² applied it was dried at peak metal temperature 1 00 ° C as dry weight.

 <Comparative Example 5>

Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex N) was added to 100 parts by weight of ethylene acryl resin on an electro-zinc-plated copper plate (EG) previously cleaned by the method described in (2). The aqueous resin composition contained in a ratio of 1 part by weight was applied as a dry weight of 1 gZm ² by a roll coating method, and dried at a temperature of 100 ° C. of the arrival plate.

3. Evaluation test method

 The evaluation was performed by the following evaluation method. The results are shown in Table 1.

[Table 1] Evaluation test results

 3. 1. Corrosion resistance

For the test material, the salt spray test specified in JISZ 237 Performed for 40 hours. The whiteness resistance was visually measured and evaluated. The evaluation criteria are as follows.

 ◎: White 鲭 Occurrence rate of less than 5%

 ：: Whiteness occurrence rate 5% or more, less than 10%

 Δ: Whiteness occurrence rate 10% or more, less than 50%

 X: White 鲭 incidence rate 50% or more

 3. 2. Paint adhesion

 The test surface-treated metal material was coated under the following conditions, and a coating film adhesion test was performed.

Painting conditions

Paint: Amilac # 100 (trademark) manufactured by Kansai Paint Co., Ltd. (white paint)

Painting method Bar coating method,

Baking 140 ° C, 20 minutes

Film thickness 25 μ τη

3.2.1 Primary adhesion

 100 mm square, 100 squares of the coating film were cut and cut with an NT cutter, and this test material was extruded with a Erichsen tester for 5ππη. And the number of peeled coating films was evaluated. The evaluation criteria are shown below.

 ：: No peeling

 〇: 1 or more peeled, less than 10

 △: Number of peeled 1 1 or more, less than 50

 X: White bleed rate 5 1 or more, less than 100

3. 2. 2. Secondary adhesion

 After immersing the test plate in boiling water for 2 hours, the same test as the primary adhesion test was performed and evaluated.

3. 3. Corrosion resistance after painting

A scratch reaching the copper plate body was made in the coating film with an acryl cutter, and a salt spray test specified in JIS-2372 was carried out for 240 hours. After the operation, the cut portion was peeled off with an adhesive tape, and the peel width was evaluated. Judgment standard is cut part The peeling width (mm) of the coating film from was measured.

 ◎: less than 3 mm

 Re: j mm or more, less than 5 mm

 Δ: 5 mm or more, less than 10 mm

 X: 10 mm or more

 3.4. Fingerprint resistance

 A finger was pressed against the test plate, and the trace state of the fingerprint was visually evaluated. The criteria are as follows.

 ：: No trace of fingerprint remains

 〇: Traces of fingerprints remain very slightly

 △: Traces of fingerprints remain slightly

 X: Fingerprint traces remain clear

 As is clear from the results in Table 1, Examples 1 to 8 using the surface treating agent composition of the present invention show good corrosion resistance, coating properties, corrosion resistance after painting, and fingerprint resistance. However, Comparative Example 1 in which the upper layer coating treatment was not performed was inferior in corrosion resistance and fingerprint resistance. Comparative Example 2, in which no silica was contained in the upper layer resin, was inferior in corrosion resistance and fingerprint resistance. Comparative Example 3, which contained silica outside the scope of the present invention, exhibited a decrease in adhesion. 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 the undercoating treatment was not performed, the corrosion resistance and adhesion were extremely poor.

[Industrial applicability]

 The organic composite coated metal material formed using the manufacturing method of the present invention can provide high corrosion resistance, paint adhesion and fingerprint resistance without using chromate, unlike conventional products. Regulations make it possible to adapt to industries that are forced to go chrome-free. Furthermore, since there is no selectivity for the metal material, it is possible to improve the heat resistance and the paintability while utilizing the characteristics of the material.

 It is also extremely effective and has a large practical effect as a countermeasure against social issues such as environmental conservation and recyclability.

Claims

The scope of the claims

(1) The following components as a first layer on the metal material surface:

 (A) Silane coupling comprising one or more silane coupling compounds having at least one reactive functional group selected from active hydrogen-containing amino, epoxy, bull, mercapto and metathalyloxy groups. Agent components and

 (B) one or more polymer components containing one or more polymers represented by the following general formula (I) with an average degree of polymerization of 2 to 50:

[Wherein, X bonded to the benzene ring is a hydrogen atom, a hydroxy group, a C1-C5 alkyl group, a C1-C5 hydroxyalkyl group, a C6-C1 Condensed with the aryl group, benzyl group, benzal group and the benzene ring

An unsaturated hydrid carbon group forming a ring or a group of the following formula (II):

R 1 — c R 2

0 ¹¹

Wherein R 1 and R 2 in the formula (II) are each a hydrogen atom, Represents a droxyl group, a C1-C5 alkyl group, or a C1-C10 hydroxyalkyl group, and in formulas (I) and (Π), Y 1 and Y 2 bonded to a benzene ring; Are each independently a hydrogen atom or a Z group represented by the following formulas (III) and (IV):

 C H 2 ― N

R 3, R 4, R 5, R 6 and R 7 in the above formulas (III) and (IV) are each independently a hydrogen atom, a C 1 -C 10 alkyl group or C 1 X represents a hydroxyalkyl group of ~ 10, and each of X, Y1 and Y2 bonded to each benzene ring in the polymer molecule is X, bonded to another benzene ring. Each of Y 1 and Y 2 may be the same or different from each other, and the average value of the number of substitution of the Z group in each benzene ring in the polymer molecule is 0.2 to 1.0. is there. 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 of the silane coupling agent component (A) to the polymer component (B), wherein (A) / (B) force is 1:10 to: L0: 1. Organic composite coated metal material.

(3) the silane coupling agent component (A) force S (a) a silane coupling agent comprising 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) 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) is 3 ::! To 1: 3, The organic composite-coated metal material according to claim 3.

(5) The weight ratio of the total amount of the silane coupling agent (a) and the silane coupling agent (b) to the polymer component (B) [(a) + (b)] / (B) is: The organic composite-coated metal material according to claim 3, wherein the ratio is 1: 5 to 5: 1.

(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) As a first layer component, an aqueous medium, and the following components dissolved in the aqueous medium:

 (A) Silane coupling consisting of one or more silane coupling compounds having at least one reactive functional group selected from active hydrogen-containing amino, epoxy, butyl, mercapto and methacryloxy groups Agent components and

(B) one or more water-soluble polymer components containing one or more water-soluble polymers represented by the following general formula (I) at an average degree of polymerization of 2 to 50:

[Wherein, in the formula, X bonded to the benzene ring is a hydrogen atom, a hydroxy group, a C1-C5 alkyl group, a C1-C5 hydroxyalkyl group, a C6-C1 2, an aryl group, a benzyl group, a benzal group, an unsaturated hydrocarbon group condensed with the benzene ring to form a naphthalene ring, or a group represented by the following formula (II):

 0 H

R 1 and R 2 in the formula (II) each represent a hydrogen atom, a hydroxyl group, a C 1 to C 5 alkyl group, or a C 1 to C 10 hydroxyalkyl group, In (I) and (II), Y 1 and Y 2 bonded to the benzene ring are each independently a hydrogen atom or a Z group represented by the following formulas (III) and (IV):

 — C H 2 ― N

R 3, R 4, R 5, R 6 and R 7 in the above formulas (III) and (IV) are each independently a hydrogen atom, a C 1 -C 10 alkyl group or C 1 ~ (: Represents a 10 hydroxyalkyl group, and each of X, Y1 and Y2 bonded to each benzene ring in the polymer molecule is X bonded to another benzene ring , Y 1 and Y 2 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. in it.] Do that PH value from a 2.0 to 6. applying a 5 aqueous composition is adjusted to such deposition amount after drying on the metal material surface is 1 0~50 OmgZm ^2, dried An aqueous resin composition containing silica in an amount of 5 to 70 parts by weight per 100 parts by weight of the aqueous resin as a second layer on the second layer has an adhesion amount after drying of 0.1 to 5.0 gZm. ^{2. A} method for producing an organic composite coated metal material having excellent corrosion resistance, paintability, and fingerprint resistance, which is characterized by being applied and dried so as to be ² .