WO1999046342A1 - Surface treatment composition for metallic material and method of treatment - Google Patents

Abstract

A surface treatment composition which can impart excellent corrosion resistance and coatability to the surface of a metallic material; and a method of surface treatment. The composition comprises (A) a silane coupling agent ingredient having a reactive functional group such as an amino group containing active hydrogen or an epoxy group, (B) at least one water-soluble polymer ingredient comprising a water-soluble polymer represented by formula (I) having an average degree of polymerization of 2 to 50, and (C) a colloidal dispersion of an inorganic compound selected among silica, silicates, metal chlorides, etc. The method comprises applying an aqueous surface-treating fluid containing the composition and having a pH adjusted to 2.0 to 6.5 to form a film in an amount of 0.01 to 2.0 g/m2 on a dry basis.

Description

 Description Surface treatment agent composition for metal material and treatment method [Technical field]

 The present invention relates to a surface treatment composition and a treatment method capable of imparting excellent corrosion resistance and coatability to the surface of a metal material.

[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 have the drawback that they corrode in the air and produce corrosion products (so-called white), which degrade the appearance of metallic materials and adversely affect paint adhesion. I have.

 Therefore, in order to improve the corrosion resistance and coating adhesion of the metal material surface, chromate treatment is generally performed on the surface of the metal material with a treatment liquid mainly containing chromic acid, dichromic acid or salts thereof.

 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. Chromate processing is often avoided. Also, wastewater containing hexavalent chromium needs to be treated specially as stipulated in the Water Pollution Control Law, which will increase the cost of kana as a whole. In addition, chromate-treated metal materials have the major drawback 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 a 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 the intrusion of corrosive substances, so that the corrosion resistance of the metal material is considered to be improved. its dependent _c However, in recent years, along with the quality of the product, demand a high corrosion resistance of the coating itself Therefore, a film 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 metal materials, Japanese Patent Application Laid-Open

JP-A-53-2012 discloses a method of applying an aqueous solution comprising water-dispersible silica, an alkyd resin and a trialkoxysilane compound to a metal surface.

 Further, using a hydroxypyrone compound--a water-soluble resin composed of a conductor--a surface treatment method for imparting corrosion resistance to a metal material and a water-soluble or water-dispersible polymer of a hydroxystyrene compound. Methods for imparting corrosion resistance to metal materials are disclosed in Japanese Patent Application Laid-Open Nos. 57-4751 and 1-177380, and the like.

 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 chromium-free surface treatment agent and surface treatment method for metal materials with excellent corrosion resistance have not been obtained.

[Disclosure of the Invention]

 An object of the present invention is to solve the problems of the prior art and to provide a surface treatment agent for non-chromium-based metal materials which is excellent in hardness, corrosion resistance, and coatability.

 The present inventors have conducted intensive studies to solve these problems of the prior art, and as a result, dispersed a silane coupling agent component, a water-soluble polymer component having a specific chemical structure in a colloidal state. By treating the surface of the metal material with a surface treatment agent that contains the treated inorganic compound, the corrosion resistance and paintability, especially the slip resistance when applying a forming process such as bending after painting (coin) The present inventors have newly found that a film having excellent scratch resistance can be formed, and have completed the present invention. Ie

 The surface treatment composition for a metal material of the present invention comprises an aqueous medium, and the following components dissolved in the aqueous medium:

(A) Active hydrogen-containing amino, epoxy, bull, mercapto and other groups A silane coupling agent component comprising at least one silane coupling compound having at least one reactive functional group selected from methacryloxy groups 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, X bonded to the benzene ring is a hydrogen atom, a hydroxy group, a C1-C5 alkyl group, a C1-C5 hydroxyalkyl group. C6-C1 2, an aryl group, a benzyl group, a benzal group, an unsaturated hydrid carbon group condensed with the benzene ring to form a naphthalene ring, or a group represented by the following formula (II):

 R C ― R 2

(Π)

R 1 and R 2 in the formula (II) represent a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, or a C1-C10 hydroxyalkyl group, respectively. In formulas (I) and (II), Y 1 and Y 2 bonded to the benzene ring are each independently a Z group represented by the following formula (III) or (IV): CH 2

 R 3, R 4, R 5, R 6 and R 7 in the above formulas (III) and (IV) each independently represent a hydrogen atom, a C 1 -C 10 alkyl group or a C 1- Represents a C 10 hydroxyalkyl group, and the average value of the number of substitutions of the Z group in each benzene ring in the polymer molecule is 0.2 to 1.0. ] When

 (C) at least one inorganic compound component selected from the group consisting of silica, a silicate, a metal salt compound and a mixture thereof dispersed in a colloidal state in the aqueous medium. Is what you do.

 In the surface treatment agent composition of the present invention, the silane coupling agent component

Weight ratio of (A) to water-soluble polymer component (B) (A) / (B) Force 1: 10-: L 0: 1; (A) + (B) of inorganic compound (C) It is preferred that the weight ratio (C) / [(A) + (B)] to the weight ratio be 1: 5 to 5: 1.

 In the surface treatment agent composition of the present invention, the silane coupling agent component (A) may comprise (a) a silane coupling agent comprising one or more silane coupling compounds having one or more active hydrogen-containing amino groups. And (b) a silane coupling agent comprising one or more silane coupling compounds having one or more epoxysilane groups.

In the surface treatment agent composition of the present invention, 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: 1 to 1: 1. : 3 to be preferable.

 In the surface treating agent composition of the present invention, the weight ratio of the total amount of the silane coupling agent (a) and the silane coupling agent (b) to the water-soluble polymer component (B) [(a) + (b)] / (B) is preferably 1: 5 to 5: 1.

The surface treatment method for a metal material of the present invention comprises the step of preparing an aqueous surface treatment solution containing the above-mentioned surface treatment chemical composition for a metal material of the present invention and adjusted to a pH value of 2.0 to 6.5. deposited on the material, dried, is 0.0 to 2. which is characterized in that to form a coating having a dry weight of O g / m ^2.

 In the surface treatment method for a metal material according to the present invention, it is preferable that the surface of the metal material is previously subjected to a phosphate treatment or a chemical plating treatment before the aqueous surface treatment solution is attached to the metal material.

 The surface treating agent composition for a metal material of the present invention comprises a silane coupling agent component (A) comprising at least one silane coupling compound having a specific reactive functional group, and a silane coupling agent component containing a special amino group. Selected from the group consisting of the water-soluble polymerization component (B) comprising the above phenolic resin-based polymer, silica, silicate and metal salt compounds dispersed in a colloidal state in the aqueous medium, and a mixture thereof. It is an aqueous solution in which at least one inorganic compound (C) is dissolved in an aqueous medium.

 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 contains 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) ethylethylmethyxsilane

(3) Having a vinyl group

 Burt Triethoxysilane

 も の Having a mercapto group

 3 _ mercaptoprovir trimethoxysilane

 ⑤Methacrylic having a hydroxyl group

 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane The silane coupling agent component (A) used in the present invention comprises one or more silane coupling agents having one or more active hydrogen-containing amino groups. It is preferable that the silane coupling agent comprises a silane coupling agent (a) composed of a compound and a silane coupling agent (b) composed of one or more silane coupling compounds having one or more epoxy groups.

 Further, the silane coupling agent component (A) in the surface treatment agent composition according to the present invention is a silane coupling agent (a) comprising a silane coupling compound having an active hydrogen-containing amino group, and an epoxy group-containing silane coupling agent. When comprising the agent (b), the equivalent ratio of the active hydrogen-containing amino groups contained in the silane coupling agent to the epoxy groups 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 has poor film-forming properties, resulting in 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 water-soluble 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 average polymerization degree of the polymerized unit of the formula (I) is 2 ~ 50.

In the formula (I), X bonded to the benzene ring is a hydroxyl group, a C1-5 alkyl group, for example, a methyl, ethyl, propyl group, etc., a C1-5 hydroxyalkyl group, for example, C6-12 aryl groups such as hydroxymethyl, hydroxyxethyl, 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; Examples include a hydroxyalkyl group, 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 each independently have a Z group represented by the formula (III) or (IV). 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 C 1 to C 5 hydroxyalkyl groups, for example, hydroxymethyl, hydroxyxethyl, hydroxypropyl group 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.

Further, the average value of the number of substitution of the 前 記 group in each benzene ring in the polymer molecule is from 0.2 to 1.0. Further, η in the formula (I) represents an average degree of polymerization of 2 to 50. When η is less than 2, the molecular weight of the obtained polymer is too small, the corrosion resistance of the obtained film is insufficient, and when it exceeds 50, the obtained surface treating agent composition and The stability of the aqueous treatment solution containing the compound is poor, causing practical inconvenience.

The average value of the number of substituted Ζ groups is the average value of the number of Ζ groups introduced into each benzene ring in the polymer molecule. For example, in the formula (I), when η = 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 Ζ group is introduced into each of 10 benzene rings per polymer molecule, the average number of Ζ group substitutions in this polymer molecule is [(1 X 10) + (0 X 10)] / 20 = 0.5.

 If the average value of the number of Z group substitution is less than 0.2, the resulting polymer will have insufficient water solubility, and the stability of the surface treatment composition will be poor. On the other hand, if the force exceeds 1.0, the water solubility of the obtained polymer becomes excessive, and the effect of improving the corrosion resistance and coating property of the obtained film becomes insufficient.

 Each of R 3 to R 7 in the Z group represented by the formulas (III) and (IV) represents a C 1 to C 10 alkyl group and a C 1 to C 10 hydroxyalkyl group. Represent. 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, at least one inorganic compound (C) selected from the group consisting of silica, a silicate, a metal salt compound and a mixture thereof used in the present invention is uniformly dispersed in a colloidal state in the aqueous medium. It must be a liquid. Therefore, use of fine particles is preferred. For this purpose, fumed or colloidal silica, precipitated silica, powdered quartz of natural origin, diatomaceous earth, loess, silicates such as montmorillonite, synthetic magnesium silicate, commercially available as Rabonite (trade name), titanium aerosol, Zirco urea, alumina sol, barium sulfate, zinc phosphate, red iron oxide, etc.

 In the surface treatment agent of the present invention, the weight ratio (A) / (B) to the silane coupling agent component (A) and the water-soluble polymer component (B) is from 1:10 to 10: 1. And preferably 1: 5 to 5: 1. If the 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 are 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 will be reduced, and the resulting film will have insufficient corrosion resistance and paintability. .

In the surface treatment agent composition of the present invention, the weight ratio of the inorganic compound component (C) to the total amount of the silane coupling agent component (A) and the water-soluble polymer component (B) (C) / [( A) + (B)] is 1: 5 to 5: 1, preferably-. When the polymerization ratio is less than 1: 5, that is, when the ratio of the inorganic compound component (C) is small, the physical strength of the obtained film becomes insufficient, Paintability, especially coin scratching, is insufficient. On the other hand, if it exceeds 5: 1, that is, if the content of the inorganic compound component (C) is too large, the film-forming properties of the obtained surface treatment composition will decrease, so that the corrosion resistance of the resulting film. In particular, the adhesion becomes insufficient.

Next, the surface treatment method of the present invention will be described. In the method of the present invention, the aqueous surface treating solution containing the surface treating agent composition described above, having a pH adjusted to a range of 2.0 to 6.5, is adhered to the surface of the metal material, and dried to obtain a solution. 0 to 2.0 g / ni ² , preferably 0.05 to: A film having a dry weight of L.O g / m ² is formed. In this case the aqueous treatment liquid in contact from 0.1 to 30 seconds at a temperature of 1 0~6 0 ° C to the metal surface, the surface treatment method that is preferable _c The present invention for heating drying, an aqueous surface treatment liquid The surface treatment agent is adjusted by diluting or undiluted the composition with an aqueous medium, for example, water. At this time, the PH value is, for example, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, complex acid, etc. It is adjusted to a range of 2.0 to 6.5 using fluoride and organic acid.

 Phosphoric acid, acidic phosphate, fluoride, and complex fluoride are preferably used for adjusting the pH value of the aqueous surface treatment solution used in the present invention. The preferred PH value is 3.0-5.0. If the pH is less than 2.0, the reactivity between the composition in the obtained treatment liquid and the surface of the substrate becomes excessively high, resulting in poor coating, resulting in insufficient corrosion resistance and coating properties of the obtained coating. become. If the pH exceeds 6.5, the water-soluble polymer component (B) itself tends to precipitate out of the aqueous surface treatment solution, so that the life of the aqueous treatment 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, a dipping method, a spraying 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 10 to 60 ° C, and the processing time is preferably 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.

When the surface treating agent composition 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) are complexed. May form body and precipitate. In such a case, a sequestering agent may be added to the surface treatment composition. As a sequestering agent, EDTA, Cy-DTA, triethanolamine, dalconic acid, heptgluconic acid, oxalic acid, tartaric acid, lingic acid and organic phosphonic acid are effective.

 Further, a surfactant for improving coatability may be added to the aqueous surface treatment solution used in the surface treatment method of the present invention. Examples of the surfactant include commercially available anionic surfactants such as a carboxylate type, a sulfate type, a sulfonate type, and a phosphate type, a polyethylene glycol type nonionic surfactant, and a polyhydric alcohol type. Examples include an ionic surfactant and an amine-based cationic surfactant.

 The metal material used in the present invention can be selected from an iron plate, a zinc-plated copper plate, an aluminum plate, an aluminum alloy plate, a stainless steel plate and the like. In addition, the steel sheet may be selected from steel sheets which have been subjected to a phosphate treatment or a chemical plating treatment. In this case, the corrosion resistance and the paintability are improved. Note that the chemical plating treatment includes, for example, substitution plating of metals such as cobalt, nickel, copper, iron, silver, and gold.

Although there are still many unclear points about the effects of the metal material treated with the surface treatment composition of the present invention, which can improve the corrosion resistance and the paintability, the inventors consider as follows. First, the metal surface is etched by phosphoric acid, acid phosphate, fluoride and complex fluoride in the surface treatment composition. As a result, the pH at the interface increases, and a reaction between the eluted metal ions and the water-soluble polymer component forms a poorly soluble film at the interface. It is thought that the corrosion resistance is improved because this hardly soluble film exerts a barrier effect. However, since the adhesion between the metal material and the film is low in this state, the functional group (—OR group) in the hydrolyzed silane coupling agent can be brought into contact with the metal material surface by using the silane coupling agent component in combination. Oxane bond, and the other reactive functional group in the silane coupling agent reacts with the water-soluble polymer component, presumably improving the adhesion between the metal material and the water-soluble polymer component. Is done. In addition, the inorganic compound component dispersed in a colloidal state forms fine irregularities on the surface of the metal material, and the irregularities exert an anchoring effect on the paint applied on the metallic material. It is presumed that they exhibit workability after painting such as inscratching property. 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 copper plate

 Commercially available plate thickness 0.6 mm J I S G 3 141

 ②Zinc-containing steel sheet

 Commercially available sheet thickness 0.6mm hot-dip galvanized steel sheet (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 5052

 2. How to clean copper plate

 The surface of the above metal material is treated with a medium alkaline degreasing agent (registered trademark: Fine Cleaner 4336, manufactured by Nippon Parkerizing Co., Ltd.). Chemical concentration: 20 g / 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 surface treatment liquid

 <Treatment liquid>

Silane coupling agent component (A) as a 3-mercaptopropyl trimethinecyanine Tokishishiran, n = 5 as a water-soluble polymer component (B), X = _{hydrogen, Y 1 = Z = -CH 2} N (CH 3) 2, Z Average number of group substitution = 1, using colloidal silica as inorganic compound component (C), (A): (B) = 1: 8, (C): [(A) + (B)] = 1: Adjusted to be 5. After adjusting the pH to 5.0 with H ₂ SiF ₆ , the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

 <Treatment liquid B>

N— (2-aminoethyl) -3-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 = Ζ = -CH ₂ N (CH ₃ ) 2, 置換 group substitution number average = 0.75, Al as inorganic compound component (C) It adjusted so that (A) :( B) = 5: 1 and (C): [(A) + (B)] = 1: 1 using minasol. 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 = 5 as the polymer Ingredient (B), X = - CH 2 _C 6 H 4 - OH, Y 1 = Z = -. CH 2 n (CH 3) 2, Z group substitution number average = 0 75, Barium sulfate was used as the inorganic compound component (C), and adjustment was performed so that (A): (B) = l: l, and (C): [(A) + (B)] = 1: 2. Further, after adjusting the pH to 4.0 with H ₂ Ti F ₆ , the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

 <Treatment liquid D>

As a silane coupling agent component (A), 3-aminopropyltriethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino groups: equivalent ratio of epoxy groups = 1: 3) and water solubility As polymer component (B), n = 5, X = — CH ₂ — C ₆ H ₄ — OH, Y 1 = Z =-CH ₂ N (CH ₃ ) ₂ , average number of Z group substitutions = 0.75 The composition was adjusted so that (A) :( B) = 1: 1 and (C): [(A) + (B)] = 4: 1 using colloidal silica as the inorganic compound component (C). 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>

The silane coupling agent component (A) is N- (2-aminoethyl) -13-aminopropyltrimethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino group: equivalent ratio of epoxy group) = 1: 1) and n = 5, X = hydrogen, Y l = Z = -CH ₂ N (CH ₃ ) 2, water-soluble polymer component (B), Z group substitution average = 1, inorganic compound Using colloidal silica as the component (C), adjustment was made so that (A) :( B) = 1: 1 and (C): [(A) + (B)] = 1: 1. Further: H ₂ T i F ₆ After adjusting the pH to 4.0 with phosphoric acid, the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

 Comparative processing solution F>

N = 5, X = hydrogen, Y 1 = Z = —CH ₂ N (CH ₃ ) ₂ , average number of Z group substitution = 1 as water-soluble polymer component (B), colloidal silica as inorganic compound component (C) Was adjusted so that (C) :( 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.

 Comparative processing solution G>

As the silane coupling agent component (A), N- (2-aminoethyl) -13-aminopropyltrimethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino group: equivalent ratio of epoxy group = 1: 1) and n = 5, X = hydrogen, Y l = Ζ = — CH ₂ N (CH ₃ ) 2, Z group substitution average = 1, as the water-soluble polymer component (B), (A): Adjusted so that (B) = 1: 1. 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.

 Comparative processing solution H>

Silane coupling agent component (A) as a 3-mercaptopropyl trimethinecyanine Tokishishiran, n = 5 as a water-soluble polymer component (B), X = _{hydrogen, Y 1 = Z = -CH 2} N (CH 3) 2, Z Average number of group substitution = 1, using barium sulfate as inorganic compound component (C), (A): (B) = l: 8, (C): [(A) + (B)] = 1: Adjusted to be 20. After adjusting the pH to 4.5 with HF, the mixture was diluted with deionized water to a solid content of 10% by weight.

 <Comparative treatment solution I>

3-Aminopropyltriethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino groups: equivalent ratio of epoxy groups == 1: 3) as silane coupling agent component (A), and water-soluble N = 5, X = — CH ₂ —C ₆ H ₄ — OH, Y 1 = Z = _C H ₂ N (CH ₃ ) ₂ , average number of Z group substitution = 0 75, Inorganic compound component (C) And (C): [(A) + (B)] = 1: 2 by using colloidal silica. After adjusting the pH to 1.0 with phosphoric acid, the mixture was diluted with deionized water to obtain a solid content of 10% by weight.

 <Comparative treatment liquid J>

 Coating type chromate (manufactured by Nippon Parkerizing Co., Ltd .; trademark: Zincro Mu 1300 AN)

 <Example 1>

Apply the treatment liquid A at 25 ° C to the hot-dip galvanized steel sheet (GI) previously cleaned by the method described in (2.) by the roll coating method so that the dry weight becomes 0.3 g Zm ^2. It was applied and dried at the ultimate plate temperature of 80 ° C.

 Example 2>

Apply the treatment liquid B at 15 ° C to the aluminum plate (AL), which has been previously cleaned by the method described in (2.), using a roll coating method to a dry weight of 0.1 g / m ^2. Then, drying was performed so that the reached plate temperature became 150 ° C.

 Example 3>

Applying a treatment liquid C at 30 ° C 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 1. O g / m ^2. And dried so that the plate temperature reached 100 ° C.

 <Example 4>

Apply a treatment solution D at 20 ° C to a copper plate (EG) coated with electro-zinc, which has been cleaned in advance as described in (2.), using a roll coat method to a dry weight of 0.05 gZm ^2. Then, drying was performed so that the reached plate temperature was 180 ° C.

 <Example 5>

A hot-dip galvanized steel sheet that had been cleaned in advance by the method described in (2) and then subjected to a Ueckel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Preparen 4015; 2 OmgZm ² as a Ueckel) GI) was applied with a treatment liquid E at 20 ° C by a roll coating method so as to have a dry weight of 1.5 g / m ^2, and was dried so as to have an ultimate plate temperature of 15 (TC). <Example 6>

A hot-dip galvanized steel sheet which has been previously cleaned by the method described in (2), and subsequently subjected to a nickel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Preparen 4015; nickel: 2 OmgZm ² ). (GI) was coated with a treatment liquid C at 20 ° C by a roll coating method so as to have a dry weight of 0.1 lg / m ^2, and was dried so that the reached plate temperature was 100 ° C.

 Example 7>

Preliminary cleaning was performed by the method described in (2.), and treatment with zinc phosphate (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Palbond-1 L3300; coating weight 2 gZm ² ) was performed by a known method. For hot-dip galvanized steel sheet (GI)

The treatment liquid E at 20 ° C was applied by a roll coating method so as to have a dry weight of 0.3 g / m ^2, and was dried so that the reached plate temperature was 100 ° C.

 Example 8>

It was previously cleaned by the method described in (2.), and then treated with zinc phosphate by a known method (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Palbond-L3020; film weight 2 g / m ² ). Apply the treatment solution E at 20 ° C to the cold-rolled copper plate (SPC) by the roll coating method to a dry weight of 0.1 g / m ² , and reach the ultimate plate temperature of 100 ° C. Was dried as described above.

 <Comparative Example 1>

Applying the treatment liquid F at 30 ° C to the hot-dip galvanized steel sheet (GI) previously cleaned by the method described in (2.) by roll coating so that the dry weight becomes 1. O g / m ^2. And dried so that the plate temperature reached 100 ° C.

 <Comparative Example 2>

 The aluminum plate (AL), which was previously cleaned by the method described in (2.),

The treatment liquid G at 30 ° C was applied by a roll coating method so as to have a dry weight of 0.3 g nom ^2, and was dried so that the reached plate temperature was 200 ° C.

 <Comparative Example 3>

A copper plate (GI) coated with a hot-dip galvanized steel which had been cleaned in advance by the method described in (2.), and subsequently treated with a Ugger surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Preparen 4015; nickel: 20 mgZm ² ) ) The treatment liquid H at 20 ° C was applied by a roll coating method so as to have a dry weight of 0.3 gZm ^2, and was dried so that the ultimate plate temperature became 80 ° C.

 <Comparative Example 4>

Fused zinc which had been cleaned in advance by the method described in (2.) and then treated with a nickel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Preparen 410; 20 mg zm ² as Etkel) Treatment solution I at 20 ° C is applied to a coated steel sheet (GI) by a roll coating method to a dry weight of 0.3 g / m ² so that the ultimate sheet temperature reaches 150 ° C Was dried.

 <Comparative Example 5>

A hot-dip galvanized steel which had been cleaned in advance by the method described in (2.) and then treated with an Eckel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (registered trademark) Preparen 410; 2 Om gZm ² as nickel). The treatment solution J was applied to a coated steel sheet (GI) by a roll coating method so as to have a chromium content of 4 OmgZm ^2, and was dried so that the ultimate sheet temperature reached 80 ° C.

3. Test plate preparation method

 A commercially available undercoat recoat (V-nit # 200, manufactured by Dainippon Co., Ltd.) was applied to each of the treated plates prepared in Examples and Comparative Examples (film thickness 5.5 μηι) 200 ° C After baking, a top coat repaint (V-nit # 500, manufactured by Dai Nippon Paint Co., Ltd.) was applied (film thickness: 17 // m) 22 (TC baking to make a test plate.

3. Evaluation test method

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

3. 1. Corrosion resistance test

 A scratch reaching the copper plate base was cut into the coating film with a cutter, and a salt spray test specified in JIS Z 237 1 was performed for 480 hours. As a criterion, the width from the cut part (wake) was measured.

 ©: Less than 3 mm

 ◦: 3 mm or more to less than 5 mm

 Δ: 5 mm or more to less than 10 mm

 X: 1 Omm or more

3. 2. Bending adhesion test

3. 2. 1.—Next bending re-bending adhesion test A 2T bending test was performed on each test plate at 20 ° C in accordance with the test method of JIS-G3312 at 20 ° C. The evaluation was performed according to the following.

 【table 1】

 Evaluation test results

2. 2. Secondary bending / 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 test was performed in the same manner as the primary bending adhesion test.

The criteria are as follows.

 5 points: no peeling

 4 points: Peeling area less than 10%

 3 points: Peeling area 10% or more to less than 50%

 2 points: Peeling area 50% or more to less than 80%

 1 point: Peeling area 80% or more

3. 3. Coinscratch test

A 10-yen coin was placed at an angle of 45 ° with respect to each test plate, and the coating film was rubbed at a load of 3 kg at a constant speed, and the damage of the coating film was determined. The scratch resistance of the coating film was evaluated according to the following criteria. 5 points: substrate exposure is 0% (only primer is exposed)

 4 points: Substrate exposure less than 10%

 3 points: Base exposure of 10% or more to less than 50%

 2 points: Base exposure is 50% or more to less than 80%

 1 point: Base exposure is 80% or more

 As is evident from the results in Table 1, Examples 1 to 8 using the surface treatment composition of the present invention showed good corrosion resistance and coating properties, and Comparative Example 5 which was a general-purpose coating type chromate treatment. It has almost the same performance as. However, Comparative Example 1 containing no silane coupling agent and Comparative Examples 3 and 4 using a composition outside the scope of the present invention exhibited inferior corrosion resistance and paintability (particularly, bending adhesion). I have. In Comparative Example 2 containing no inorganic compound component, the slip resistance (coin scratch resistance) was poor.

[Industrial applicability]

 The surface treatment agent of the present invention can provide excellent corrosion resistance and coating performance without using chromate, so it is suitable for the industry where solvent-based cleaning and water-based cleaning must be performed in accordance with future solvent regulations. It becomes possible. Furthermore, since there is no selectivity for a 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

Range of request

1. An aqueous medium and the following components dissolved in the aqueous medium:

 (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 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, X bonded to the benzene ring is a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, a C1-C5 hydroxyalkyl group. C6-C 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 represented by the following formula (II):

 R ― C ― R 2

(II)

 Y 2

 H

Wherein R 1 and R 2 in the formula (II) are each a hydrogen atom, a hydroxy group, a C 1 -C 5 alkyl group, or a C 1 -C 10 hydroxy group. In the formulas (I) and (II), Y 1 and Y 2 each represents a cycloalkyl group, and each of Y 1 and Y 2 independently of each other is represented by the following formula (式) or (IV) Z group:

— C H 2 ― N

 R3, R4, R5, R6 and R7 in the above formulas (III) and (IV) each independently represent a hydrogen atom, a C1-C10 alkyl group or a C1-C Represents 10 hydroxyalkyl groups, and the average number of substitutions of the Z group in each benzene ring in the polymer molecule is 0.2 to 1.0. ] When

 (C) at least one inorganic compound component selected from the group consisting of silica, a silicate, a metal salt compound and a mixture thereof dispersed in a colloidal state in the aqueous medium. Surface treatment composition for metal materials.

2. The weight ratio of the silane coupling agent component (A) to the water-soluble polymer component (B) (A) / (B) force 1:10 to: 10: 1, the inorganic compound (C The surface treatment agent composition according to claim 1, wherein the weight ratio (C) / [(A) + (B)] of (A) to (A) / (B) is 1: 5 to 5: 1.

3. The 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 or more silane coupling agents. One or more with epoxy group 2. The surface treatment composition according to claim 1, comprising a silane coupling agent comprising the silane coupling compound.

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: 1 to 1: 3. Item 4. The surface treatment agent according to item 3.

5. The weight ratio of the total amount of the silane coupling agent (a) and the silane coupling agent (b) to the water-soluble polymer component (B) [(a) + (b)] / (B) The surface treatment composition according to claim 3, wherein the ratio is 1: 1 to 5: 1.

6. An aqueous surface treatment liquid containing the surface treatment agent composition for a metal material according to any one of claims 1 to 5 and adjusted to a pH value of 2.0 to 6.5, comprising: A surface treatment method for a metal material, wherein the method is applied to a material surface and dried to form a film having a dry weight of 0.01 to ^2. OgZni2.

7. The surface treatment method for a metal material according to claim 6, wherein before the aqueous surface treatment liquid is attached to the surface of the metal material, the surface is subjected to a phosphate treatment or a chemical plating treatment.