JPH11256096A - Surface treatment agent composition for metallic material and treatment process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition providing excellent corrosion resistance and coatability to metallic material surfaces by blending an aqueous medium, a silane coupling component and water-soluble polymer components dissolved in an aqueous medium, and an inorganic compound component dispersed in an aqueous medium as a colloid. SOLUTION: This composition is obtained by blending an aqueous medium, a component comprising one or more silane coupling agents having one or more reactive functional groups selected from the group consisting of an amino having active H, epoxy, vinyl, SH and methacryloyloxy, one or more water-soluble polymer components having one or more water-soluble polymer of formula I having an average degree of polymerization of 2-50 [wherein X is H, OH, a 1-5C (hydroxy)alkyl, the group of formula II or the like; R1 and R2 are each H, OH, a 1-5C alkyl or the like; Y1 and Y2 are each the group of formula III or IV; R3-R7 are each H or a 1-10C (hydroxy)alkyl; and the average value of the substitutions by the group of formula III or IV on each benzene ring in the polymer molecule is 0.2-1.0] and an inorganic compound component having one or more of silica, silicates, metallic salt compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment composition and a treatment method capable of imparting excellent corrosion resistance and paintability to the surface of a metal material.

[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)
Which has the disadvantage of deteriorating the appearance of the metallic material and also adversely affecting the coating adhesion.

Therefore, in order to improve the corrosion resistance and coating adhesion of the metal material surface, a 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 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 has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a surface treatment agent for non-chromium-based metal materials having excellent corrosion resistance and coating properties. It is assumed that.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the problems of the prior art, and as a result, have found that a silane coupling agent component and a water-soluble polymer having a specific chemical structure are dissolved. By treating the surface of a metal material with a surface treatment agent containing a coalesced component and an inorganic compound dispersed in a colloidal state, it has corrosion resistance, paintability, and especially slip resistance when performing molding such as bending after painting. The present inventors have newly found that a film having excellent coinability (coin scratching property) 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) 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:

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 Z group represented by the following formula (III) or (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 the average number of substitutions of the Z group in each benzene ring in the polymer molecule is 0. 0.2 to 1.0. And (C) at least one inorganic compound component selected from the group consisting of silica, silicate, metal salt compounds and mixtures thereof dispersed in a colloidal state in the aqueous medium. Things.

In the surface treatment composition of the present invention, the weight ratio (A) / (B) of the silane coupling agent component (A) to the water-soluble polymer component (B) is 1: 10-1.
0: 1, and (A) + (B) of the inorganic compound (C)
Weight ratio (C) / [(A) + (B)] to 1: 5
Preferably it is 5: 1.

In the surface treatment composition of the present invention, the silane coupling agent component (A) comprises (a) at least one silane coupling compound having at least one active hydrogen-containing amino group. Agent and (b) 1
It is preferable to include a silane coupling agent comprising one or more silane coupling compounds having at least two epoxy silane groups.

In the surface treatment 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: 3.

In the surface treatment 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 1: 5 to 5:
It is preferably 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 chemical composition for a surface treatment for a metal material of the present invention and adjusted to a pH value of 2.0 to 6.5. Attached to metal material, dried, 0.01-2.0
A film having a dry weight of g / m ² is formed.

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.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION 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 special amino group. Selected from the group consisting of a water-soluble polymerization component (B) composed of one or more phenolic resin-based polymers, and silica, silicate, metal salt compounds and a mixture thereof dispersed in a colloidal state in the aqueous medium. 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 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.

Further, the silane coupling agent component (A) in the surface treatment agent composition according to the present invention comprises a silane coupling agent (a) comprising a silane coupling compound having an active hydrogen-containing amino group; When the coupling agent (b) is used, 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 has poor film formability and insufficient corrosion resistance and paintability. And it's 1: 3
If the amount is less than the above, the corrosion resistance and the 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 a polymer unit represented by the above formula (I), and the average polymerization degree of the polymer unit of the formula (I) is as follows. 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 or propyl group, 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 formulas (I) and (II), Y1 and Y2 bonded to the benzene ring each independently have a Z group represented by formula (III) or (IV). In addition, R3, R4 in the formulas (III) and (IV),
R5, R6 and R7 each independently represent C1
It represents a C10 alkyl group, for example, a methyl, ethyl, propyl group and the like, and a C1 to C5 hydroxyalkyl 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. Further, n in the formula (I) represents an average degree of polymerization of 2 to 50. When n is less than 2, the molecular weight of the obtained polymer is too small, and the corrosion resistance of the obtained film becomes insufficient, and when it exceeds 50, the obtained surface treatment agent composition,
In addition, the stability of the aqueous treatment liquid containing them is deteriorated, which causes practical inconvenience.

The average value of the number of substitutions of the Z group means the Z value introduced into each of all the benzene rings 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 resulting polymer will have insufficient water solubility, and the stability of the surface treatment composition will be poor. On the other hand, if it exceeds 1.0, the water solubility of the obtained polymer becomes excessive, and the effect of improving the corrosion resistance and coatability 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, at least one inorganic compound (C) selected from the group consisting of silica, silicate, metal salt compounds and mixtures thereof used in the present invention is dispersed in a uniform 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, naturally occurring powdered quartz, diatomaceous earth, loess, silicates such as montmorillonite, Laponite (trade name)
As synthetic magnesium silicate, titania sol, zirconia sol, alumina sol, barium sulfate, zinc phosphate, red iron oxide and the like.

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 1:10 to 1: 1.
It is preferably 0: 1, more preferably 1: 5
5: 1. When this weight ratio is less than 1:10, that is, when the ratio of the silane coupling agent component (A) is low,
Since the adhesive strength with the substrate surface is reduced, the corrosion resistance and the 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.

In the surface treating agent composition of the present invention, the weight ratio (C) of the inorganic compound component (C) to the total amount of the silane coupling agent component (A) and the water-soluble polymer component (B) / [(A) + (B)] is 1: 5 to 5: 1
It is preferred that 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 is insufficient, and the paintability, especially the coin scratchability, becomes insufficient. 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 be reduced. 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, an aqueous surface treatment liquid containing the above-mentioned surface treatment agent composition and having a pH adjusted to a range of 2.0 to 6.5 is adhered to the surface of the metal material, and then dried to form a 0.1% aqueous solution.
01-2.0 g / m ² , preferably 0.05-1.0 g
A film having a dry weight of / m ² is formed. At this time, the aqueous treatment liquid is applied to the surface of the metal material at a temperature of 10 to 60 ° C. for 0.1%.
It is preferable to contact for 30 seconds and heat and dry.

In the surface treatment method of the present invention, the aqueous surface treatment liquid is prepared by diluting or not diluting the surface treatment agent composition with an aqueous medium, for example, water. Is, for example, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid,
2.0 using hydrofluoric acid, complex fluoride and organic acid
Adjusted to the range of ~ 6.5.

The pH of the aqueous surface treatment solution used in the present invention
It is preferable to use phosphoric acid, acidic phosphate, fluoride, and complex fluoride for adjusting the value. A more preferred pH value is 3.0 to 5.0. When 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 corrosion resistance and coating properties of the obtained film are insufficient. 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 for 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 10 to 10.
The temperature is preferably 60 ° C., and the treatment time is 0.1 to 20.
Preferably, it is seconds. Further, it is preferable to heat and dry the treated metal material. The heating temperature is 50-2
80 ° C. is preferred.

When the surface treating agent composition 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,
Precipitation may occur. In such a case, a sequestering agent may be added to the surface treatment composition. As the sequestering agent, EDTA, Cy-DTA, triethanolamine, gluconic acid, heptgluconic acid, oxalic acid, tartaric acid, malic acid and organic phosphonic acid are effective.

Further, the aqueous surface treating solution used in the surface treating method of the present invention may contain a surfactant for improving coating properties. Examples of the surfactant include commercially available anionic surfactants such as a carboxylate salt type, a sulfate ester type, a sulfonate type and a phosphate ester salt type, a polyethylene glycol type nonionic surfactant, and a polyhydric alcohol type non-ionic surfactant. Examples include an ionic surfactant and an amine-based cationic surfactant.

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. Alternatively, the steel sheet may be selected from steel sheets which have been subjected to a phosphate treatment or a chemical plating treatment, and in this case, the corrosion resistance and the paintability are further improved. 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 regarding the effects of the metal material treated with the surface treating agent composition of the present invention on improving the corrosion resistance and coating properties, the present inventors consider as follows. . First, the phosphoric acid, acidic phosphate, fluoride and complex fluoride in the surface treatment composition cause etching of the metal surface. As a result, the pH of the interface increases, and a reaction between the eluted metal ions and the water-soluble polymer component forms a poorly soluble film on the interface. It is considered that the corrosion resistance is improved because the 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 is combined with the metal material surface by using the silane coupling agent component in combination. Oxane bonds are created, and the other reactive functional group in the silane coupling agent reacts with the water-soluble polymer component.
It is presumed that the adhesion between the metal material and the water-soluble polymer component is improved. 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 thereon,
It is presumed to exhibit sufficient paintability, especially workability after painting such as coin scratching.

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. Surface treatment liquid composition <Treatment liquid A> 3 as silane coupling agent component (A)
-Mercaptopropyltrimethoxysilane, n = 5 as water-soluble polymer component (B), X = hydrogen, Y1 = Z = -C
H2N (CH3) 2, Z group substitution number average value = 1, using colloidal silica as the inorganic compound component (C),
(A): (B) = 1: 8, (C): [(A) + (B)] =
It was adjusted to be 1: 5. After adjusting the pH to 5.0 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) -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 = 0.7
5. Using alumina sol as the inorganic compound component (C), (A) :( B) = 5: 1, (C): [(A) +
(B)] = 1: 1. In addition, p
After adjusting so that H was 4.0, it was diluted with deionized water to obtain 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
Group substitution number average value = 0.75, (A) :( B) = 1: 1 using barium sulfate as inorganic compound component (C),
(C): Adjustment was performed so that [(A) + (B)] = 1: 2. Further, 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.
And

<Treatment Solution D> As the silane coupling agent component (A), 3-aminopropyltriethoxysilane +
3-glycidoxypropylmethyldimethoxysilane (equivalent ratio of active hydrogen in amino group: epoxy group = 1: 3)
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
Group substitution number average value = 0.75, (A) :( B) = 1: using colloidal silica as the inorganic compound component (C).
1, (C): [(A) + (B)] = 4: 1. Further, 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.
And

<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 = 1, inorganic compound component (C)
Using colloidal silica as (A) :( B) =
The ratio was adjusted so as to be 1: 1, (C): [(A) + (B)] = 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.

<Comparative treatment liquid F> Water-soluble polymer component (B)
Where n = 5, X = hydrogen, Y1 = Z = —CH ₂ N (C
H ₃ ) ₂ , Z group substitution average value = 1, inorganic compound component (C)
Using colloidal silica as (C) :( B) =
It was adjusted to be 1: 1. Further, 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.

<Comparative treating solution G> N- (2-aminoethyl) -3-aminopropyltrimethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino group) as silane coupling agent component (A) : Equivalent ratio of epoxy group = 1: 1) and n = 5, X = hydrogen, Y1 = Z = —CH ₂ N as water-soluble polymer component (B)
Using (CH ₃ ) ₂ , Z group substitution number average value = 1, (A):
(B) = 1: 1 was adjusted. Further with phosphoric acid
After adjusting the H to be 3.0, it was diluted with deionized water to obtain a solid content of 10% by weight.

<Comparative treatment liquid H> 3-mercaptopropyltrimethoxysilane as the silane coupling agent component (A), n = 5 as the water-soluble polymer component (B), X = hydrogen, Y1 = Z = -CH ₂ N (CH ₃ ) ₂ , Z group substitution average value = 1, (A) :( B) = 1: 8 using barium sulfate as the inorganic compound component (C), (C): [(A) +
(B)] = 1:20. After further 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> As the silane coupling agent component (A), 3-aminopropyltriethoxysilane + 3-glycidoxypropylmethyldimethoxysilane (active hydrogen in amino group: equivalent ratio of epoxy group = 1: 1)
3) and n = 5 and X = − as the water-soluble polymer component (B).
_{CH 2 -C 6 H 4 -OH,} Y1 = Z = -CH 2 N (C
H ₃ ) ₂ , Z group substitution average value = 0.75, using colloidal silica as the inorganic compound component (C), (A):
Adjustments were made so that (B) = 1: 1 and (C): [(A) + (B)] = 1: 2. After adjusting the pH to 1.0 with phosphoric acid, the mixture was diluted with deionized water to a solid content of 10% by weight.

<Comparative treatment solution J> Coating type chromate (manufactured by Nippon Parkerizing Co., Ltd .; trademark: Zinchrome-130)
0AN)

<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.

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.

<Example 3> A treatment liquid C 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 1.0%.
g / m ² and dried so that the reached plate temperature was 100 ° C.

<Example 4> A treatment liquid D at 20 ° C was applied to an electrogalvanized steel sheet (EG), which had been cleaned in advance by the method described in (2), at a dry weight of 0.00% by a roll coating method.
Coating was performed so as to be 5 g / m ² , and drying was performed so that the reached plate temperature was 180 ° C.

<Example 5> Cleaning was carried out in advance by the method described in (2.), followed by a nickel surface conditioner (Preparen 4015, manufactured by Nippon Parkerizing Co., Ltd .; 20 mg / m ² as nickel). Treatment solution E at 20 ° C is applied to the hot-dip galvanized steel sheet (GI) by roll coating.
Coating was performed so as to have a dry weight of 1.5 g / m ² , and drying was performed so that the reached plate temperature was 150 ° C.

<Example 6> Cleaning was performed in advance by the method described in (2.), and then a nickel surface conditioner (Preparen 4015, manufactured by Nippon Parkerizing Co., Ltd .; 20 mg / m ² as nickel) was applied. Treatment liquid C at 20 ° C is applied to the hot-dip galvanized steel sheet (GI) by roll coating.
Coating was performed so as to have a dry weight of 0.1 g / m ² , and drying was performed so that the reached plate temperature was 100 ° C.

<Example 7> Cleaning was carried out in advance by the method described in (2.), followed by treatment with zinc phosphate (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Palbond-L3).
300; a coating solution E at 20 ° C. is applied to a hot-dip galvanized steel sheet (GI) having a coating weight of 2 g / m ² ) by a roll coating method so as to have a dry weight of 0.3 g / m ² . Drying was performed so that the reached plate temperature was 100 ° C.

<Example 8> Cleaning was carried out in advance by the method described in (2.), followed by treatment with zinc phosphate (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Palbond-L3).
020; cold-rolled steel sheet (SP with a coating weight of 2 g / m ² )
C) was applied with a treatment liquid E at 20 ° C. by a roll coating method so as to have a dry weight of 0.1 g / m ^2, and was dried so that a reached plate temperature was 100 ° C.

<Comparative Example 1> A treatment liquid F 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 1.0%.
g / m ² and dried so that the reached plate temperature was 100 ° C.

<Comparative Example 2> A treatment liquid G at 30 ° C was applied to an aluminum plate (AL), which had been cleaned in advance by the method described in (2), by a roll coating method at a dry weight of 0.3 g / L.
m ² , and dried so that the reached plate temperature was 200 ° C.

<Comparative Example 3> Cleaning was carried out in advance by the method described in (2.), followed by a nickel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (registered trademark) Preparen 4015; nickel: 20 mg / m ² ). The coating solution H at 20 ° C. was applied to a hot-dip galvanized steel sheet (GI) by a roll coating method so as to have a dry weight of 0.3 g / m ² , and dried so that the ultimate sheet temperature reached 80 ° C. went.

<Comparative Example 4> Cleaning was carried out in advance by the method described in (2.), followed by a nickel surface conditioner (Preparen 4015 manufactured by Nippon Parkerizing Co., Ltd .; 20 mg / m ² as nickel). The treatment liquid I at 20 ° C. was applied to the resulting hot-dip galvanized steel sheet (GI) by a roll coating method so as to have a dry weight of 0.3 g / m ² , and dried so that the ultimate sheet temperature reached 150 ° C. went.

<Comparative Example 5> Cleaning was carried out in advance by the method described in (2.), and then a nickel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Preparen 4015; 20 mg / m ² as nickel) was applied. Treatment liquid J was applied to a hot-dip galvanized steel sheet (GI) by a roll coating method so as to have a chromium content of 40 mg / m ² , and the ultimate sheet temperature was 8
Drying was performed at 0 ° C.

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

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

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[Table 1]

3.1. Corrosion resistance test A scratch that reaches the steel plate base is cut into the coating film with a cutter, and JIS-
The salt spray test specified in Z2371 was performed for 480 hours. As a criterion, the rust width (mm) from the cut portion was measured. ◎: less than 3 mm ：: 3 mm or more to less than 5 mm Δ: 5 mm or more to less than 10 mm ×: 10 mm or more

3.2. Bending adhesion test 3.2.1. Primary bending adhesion test For each test plate according to the test method of JIS-G3312, 2
A 2T bending test was performed on the two folded inner spacing plates at 0 ° C., and the peeled state after the tape was peeled was evaluated according to the following criteria. 3.2.2. Secondary bending adhesion test After the test plate was immersed in boiling water for 2 hours, it was left for one day, and the same test as the primary bending adhesion test was performed. 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 ° to each test plate,
The coating was rubbed at a constant speed with a load of 3 kg, and the scratch resistance of the coating was determined. The scratch resistance of the coating film was evaluated according to the following criteria. 5 points: substrate exposure is 0% (only primer exposed) 4 points: substrate exposure is less than 10% 3 points: substrate exposure is 10% or more to less than 50% 2 points: substrate exposure is 50% or more to 80% Less than 1%: Base material exposure is 80% or more

As is clear from the results in Table 1, Examples 1 to 8 using the surface treating agent composition of the present invention exhibited good corrosion resistance and good coating properties, and Comparative Example 5 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 compositions outside the scope of the present invention are considerably inferior in corrosion resistance and coating properties (particularly, folding adhesion).
In Comparative Example 2, which did not contain an inorganic compound component, the slip resistance (coin scratch resistance) was poor.

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As described above, the surface treating agent of the present invention can provide excellent corrosion resistance and coating performance without using a chromate. Adaptation becomes possible. 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,
As a countermeasure against social problems such as environmental conservation and recyclability, it is extremely effective and has a large practical effect.

Claims (7)

[Claims] 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 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 Z group represented by the following formula (III) or (IV): And R3, R4 in the above formulas (III) and (IV),
R5, R6 and R7 each independently represent a hydrogen atom, a C1 to C10 alkyl group or a C1 to C10 hydroxyalkyl group, and the average number of substitutions of the Z group in each benzene ring in the polymer molecule. Is 0.2-1.
0. And (C) at least one inorganic compound component selected from the group consisting of silica, silicate, metal salt compounds and mixtures thereof dispersed in a colloidal state in the aqueous medium. Surface treatment composition for metal materials. 2. A weight ratio (A) / (B) of the silane coupling agent component (A) to the water-soluble polymer component (B).
Is 1:10 to 10: 1, and the inorganic compound (C)
Weight ratio of (C) / [(A) + to (A) / (B)
(B)] is 1: 5 to 5: 1, The surface treating agent composition of Claim 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 surface treatment composition 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 surface treatment agent according to claim 3, wherein the ratio is １ ： 1: 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)] /
The surface treatment composition according to claim 3, wherein (B) is 1: 1 to 5: 1. 6. A composition comprising the surface treating agent composition for a metal material according to claim 1 and having a p-value of 2.0 to 6.5.
An aqueous surface treating solution adjusted to an H value is applied to the surface of the metal material and dried to form a film having a dry weight of 0.01 to 2.0 g / m ² . Surface treatment method. 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. .