JP6092786B2 - Aqueous binder composition for metal surface treatment agent - Google Patents

Description

  The present invention provides a metal surface treatment agent that is suitable for treating the surface of a metal substrate, has excellent paintability and storage stability, and can form a surface treatment film with excellent corrosion resistance, adhesion, and conductivity. The present invention relates to an aqueous binder composition, a metal surface treatment agent containing the aqueous binder composition, a surface treatment method for a metal material using the metal surface treatment agent, and a method for producing the aqueous binder composition.

  In general, as a technology that has excellent adhesion to the metal material surface and can impart corrosion resistance to the metal material surface, the metal material surface contains chromic acid, dichromic acid or a salt thereof as a main component. A method of performing a chromate treatment with a liquid, a method of performing a phosphate treatment, a method of performing a treatment mainly with a chromate-free inorganic component, a method of performing a treatment with a silane coupling agent, and the like are known and provided for practical use. .

  For example, Patent Document 1 includes a vanadium compound and a metal compound including at least one metal selected from zirconium, titanium, molybdenum, tungsten, manganese, and cerium as a technique for performing a treatment with a chromate-free inorganic component. A metal surface treatment agent is disclosed. However, the metal surface treatment agent has a problem that the corrosion resistance and conductivity of the treatment film are inferior.

  As a technique using a silane coupling agent, for example, Patent Document 2 discloses an alkoxysiloxane having a large amount of alkoxysilyl obtained by reacting an amino group-containing silane coupling agent and an epoxy group-containing silane coupling agent, An organic solvent-based surface treatment agent containing siloxane has been proposed, and it has been shown that a siloxane film having improved adhesion to a substrate can be formed by using this surface treatment agent. However, since this surface treatment agent is based on an organic solvent, there are problems in terms of safety and hygiene and the environment, and there is a problem in liquid stability in order to obtain a suitable aqueous system in these aspects.

  Patent Document 3 discloses an aqueous medium, (A) a specific divalent or higher metal ion, (B) an acid component selected from a specific fluoro acid, phosphoric acid and acetic acid, and (C) a silane having a specific functional group. A surface treatment composition for a metal material containing a coupling agent and (D) a specific water-soluble phenol resin polymer is disclosed. However, this surface treatment composition has problems that the liquid stability and paintability are not sufficient and the conductivity of the treated film is inferior.

  Patent Document 4 includes a phosphoric acid compound (A), a fluoro acid (B), and a metal material surface treatment in which a mixture (C) of an amino group-containing silane coupling agent and an epoxy group-containing silane coupling agent is blended. A composition is disclosed. However, this composition has a problem that liquid stability and conductivity are not yet sufficient.

  Patent Document 5 discloses (a) trialkoxysilyl as a functional group, which is a reaction product of a reactive organic group-containing silane coupling agent and an organic compound having at least two groups reactive with the reactive organic group. A surface treatment agent for a metal material has been proposed which contains a compound having two or more groups (silanol groups) and (b) a compound selected from organic acids, phosphoric acids and complex fluorides. However, this composition has a problem that liquid stability and conductivity are not yet sufficient.

  The surface treatment agents of the prior art described above satisfy all the requirements of being excellent in paintability and liquid stability, forming a film excellent in corrosion resistance, adhesion and conductivity, and being chromate-free. It is not a thing, but it still has a problem in practical use.

JP 2002-30460 A JP 11-43647 A JP-A-11-106945 JP 2006-213958 A JP 2001-49453 A

  The main object of the present invention is to solve the above-mentioned problems of the prior art and to form a surface-treated film that is chromate-free, excellent in paintability and liquid stability, and excellent in corrosion resistance, adhesion and conductivity. It is to provide an aqueous binder composition for a possible metal surface treatment.

  A further object of the present invention is to provide a metal surface treatment agent containing the aqueous binder composition, a surface treatment method for a metal material using the metal surface treatment agent, and a method for producing the aqueous binder composition. .

  As a result of intensive studies to solve the problems of these prior arts, the present inventors have obtained a silane coupling agent having an amino group and a silane coupling agent having an epoxy group, and optionally an alkyl group or the like. A binder composition containing two or three reaction products of an alkoxysilane compound such as trialkoxysilane in which the hydrocarbon group is directly bonded to a silicon atom, a specific acid compound and water, the reaction product In which substantially no epoxy group is present and substantially all of the existing hydrolyzable groups are hydrolyzed to form silanol groups, and the condensation of silanol groups is moderately controlled to condense silanol groups. By suppressing the formation of particles and gelation by the water, an aqueous binder composition for a metal surface treatment agent having excellent liquid stability can be obtained. The metal surface treatment agent containing products has excellent paintability and liquid stability, and by using it for the treatment of metal material surfaces, it has been found that a film excellent in corrosion resistance, adhesion and conductivity can be formed, and the present invention has been completed. It came to do.

Thus, the present invention provides (a) a silane coupling agent having at least one primary or secondary amino group and a hydrolyzable group, and (b) at least one epoxy group and a hydrolyzable group. And optionally further (c) Formula: (R) _4-n- Si- (X) _n [wherein R is optionally substituted with a non-reactive substituent. It represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, X represents an alkoxyl group, and n represents an integer of 1 to 3]. A binder composition having a pH of 4.0 to 10.0, containing at least one acid stabilizer (B) selected from a phosphoric acid compound and a nitric acid compound and water. There,
In the silane coupling agent (a), the amount of active hydrogen of the amino group in the silane coupling agent (a) is 1.0 to 5.0 equivalents with respect to 1 equivalent of the epoxy group in the silane coupling agent (b). Is blended at a ratio
At least a part of the reaction product (A) has the amino group and the epoxy group chemically bonded,
The reaction product (A) has substantially no unreacted epoxy group based on the silane coupling agent (b), and water based on the silane coupling agent (a) and the silane coupling agent (b). Substantially all of the decomposable groups as well as the alkoxysilyl groups based on the alkoxysilane compound (c) are hydrolyzed to silanol groups and have a weight average molecular weight in the range of 500 to 20000, and For a metal surface treatment agent, wherein the stabilizer (B) is contained in an amount such that the neutralization equivalent of the amino group in the silane coupling agent (a) is within the range of 0.1 to 2.0. An aqueous binder composition is provided.

  Moreover, this invention provides the metal surface treating agent characterized by containing the said aqueous | water-based binder composition for metal surface treating agents, and a rust preventive agent.

Furthermore, the present invention is to apply the metal surface treatment agent to the surface of the metal material and dry it to form a surface treatment film having a dry film weight of 0.05 to 3.0 g / m ^{2 on} the surface of the metal material. A feature of the present invention is to provide a surface treatment method for a metal material.

Furthermore, the present invention provides (a) a silane coupling agent having at least one primary or secondary amino group and a hydrolyzable group, and (b) at least one epoxy group and a hydrolyzable group. And optionally further (c) Formula: (R) _4-n- Si- (X) _n [wherein R is optionally substituted with a non-reactive substituent. And a hydrocarbon group having 1 to 18 carbon atoms, X represents an alkoxyl group, and n represents an integer of 1 to 3]. A silane reaction product (A ′) is produced, and then at least one acid stabilizer (B) selected from a phosphoric acid compound and a nitric acid compound is added to the silane reaction product (A ′). Silane reaction product by After preparing the aqueous liquid, there is provided a method for producing the aqueous binder composition, characterized in that the solvent is removed.

  In the aqueous binder composition for a metal surface treatment agent of the present invention, substantially all of the hydrolyzable group based on the silane coupling agent and the alkoxyl group of the alkoxysilane compound when present are hydrolyzed to a silanol group, Condensation of silanol groups is moderately suppressed, and since there is substantially no unreacted epoxy group, it has excellent liquid stability and exhibits excellent performance as a binder for metal surface treatment agents.

  The metal surface treatment agent containing the aqueous binder composition of the present invention is excellent in paintability and liquid stability, excellent in corrosion resistance, adhesion and conductivity, and contains a pollution control substance such as hexavalent chromium in the film. It is possible to form a chromate-free metal surface treatment film that does not contain.

According to the surface treatment method using the surface treatment agent of the present invention, it is possible to form a film on the surface of a metal material, which is excellent in both corrosion resistance and electrical conductivity, which have been difficult to achieve at the same time, and has excellent adhesion. Can do.
Therefore, the present invention can also contribute to environmental conservation and recyclability of surface-treated metal materials.

  The method for producing an aqueous binder composition of the present invention has a solvent removal step, whereby alcohol and the like produced by hydrolysis of the silane coupling agent can be removed, and the resulting binder composition is treated as a non-hazardous material. In addition, the solid content ratio can be increased, and the liquid stability of the aqueous binder composition after the solvent removal step and after the solvent removal step can be maintained by containing a specific acid.

  Hereinafter, an aqueous binder composition for a metal surface treatment agent according to the present invention, a metal surface treatment agent containing the binder composition, a surface treatment method of a metal material using the metal surface treatment agent, and the aqueous binder composition described above The manufacturing method will be described in more detail.

First, the aqueous binder composition for metal surface treatment agent will be described.

Aqueous binder composition for metal surface treatment agent

The binder composition for surface treatment of a metal material according to the present invention is an acid selected from at least two silane coupling agents, and optionally a reaction product (A) obtained by further reacting an alkoxysilane compound and a specific acid. A stable binder composition containing a stabilizer (B) and water and having a pH of 4.0 to 10.0, preferably 5.0 to 10.0, and more preferably 6.0 to 10.0. Further, the binder composition of the present invention can reduce the organic solvent content to 3% by mass or less by removing the solvent. As a result, the binder composition has no flash point and can be handled as a non-hazardous material in the Fire Service Act. it can.
Reaction product (A)

The reaction product (A) in the aqueous binder composition of the present invention comprises at least one silane coupling agent (a) having a primary or secondary amino group and a hydrolyzable group, and at least one epoxy. A silane coupling agent (b) having a group and a hydrolyzable group, and optionally (c) Formula: (R) _4-n- Si- (X) _n [wherein R is optionally reactive. Represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a substituent not having X, X represents an alkoxyl group, and n represents an integer of 1 to 3]. It is obtained by addition reaction and / or hydrolysis reaction with an alkoxysilane compound.

In the present specification, the silane coupling agent (a) having at least one primary or secondary amino group and a hydrolyzable group, and at least one epoxy group and a hydrolyzable group. The reaction product obtained by addition reaction and / or hydrolysis reaction of the two components with the silane coupling agent (b) is referred to as “reaction product (A-1)”, and at least one primary or 2 A silane coupling agent (a) having a primary amino group and a hydrolyzable group, a silane coupling agent (b) having at least one epoxy group and a hydrolyzable group, and (c) Formula: ( R) _4-n- Si- (X) _n [wherein R represents a hydrocarbon group having 1 to 18 carbon atoms which may be optionally substituted with a non-reactive substituent, and X represents Represents an alkoxyl group, and n represents an integer of 1 to 3. ] May be referred to as "reaction product (A-2)" at least one alkoxysilane compound with the reaction product obtained by addition reaction and / or hydrolysis reaction three components represented by.

  At least a part of the reaction product (A) forms a chemical bond by an addition reaction between the amino group of the silane coupling agent (a) and the epoxy group of the silane coupling agent (b). It is desirable that the epoxy group is consumed in the addition reaction, and the reaction product (A) is substantially free of unreacted epoxy groups derived from the silane coupling agent (b).

  In addition, the reaction product (A) is substantially composed of a hydrolyzable group based on the silane coupling agent (a) and the silane coupling agent (b) and an alkoxysilyl group based on the alkoxysilane compound (c) when present. Are all hydrolyzed to silanol groups and can have a weight average molecular weight in the range of 500-20000. Specifically, the reaction product (A-1) generally has a weight average molecular weight in the range of 500 to 10000, particularly 1000 to 6000, and the reaction product (A-2) is generally It is preferred to have a weight average molecular weight in the range of 500 to 20000, in particular 1000 to 10,000.

  In the present specification, “substantially all of the hydrolyzable groups based on the silane coupling agent (a) and the silane coupling agent (b) and the alkoxysilyl group of the alkoxysilane compound (c) when present are all silanol groups. "Hydrolyzed to" means a state in which no peaks of hydrolyzable groups and alkoxysilyl groups are observed in nuclear magnetic resonance spectrum analysis (NMR). Usually, among hydrolyzable groups and alkoxysilyl groups, Is at least 95% hydrolyzed into silanol groups. Further, in the present specification, “substantially having no unreacted epoxy group” means a state in which no peak of unreacted epoxy group is observed in nuclear magnetic resonance spectrum analysis (NMR), Usually, the ratio of the unreacted epoxy group in the epoxy group is 5% or less. Furthermore, in the present specification, both “alkoxysilyl group” and “hydrolyzable group” may be collectively referred to as “hydrolyzable functional group”.

  In this specification, the weight average molecular weight of the reaction product (A) is the retention of standard polystyrene with a known molecular weight measured under the same conditions as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). This is a value obtained by converting to the molecular weight of polystyrene based on time (retention capacity). As the gel permeation chromatograph apparatus, "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation) is used, and as the column, "TSKgel GMHRHR-L" (trade name, manufactured by Tosoh Corporation) is used, and detection is performed. A differential refractometer is used as a vessel, and the measurement can be performed under the conditions of mobile phase: dimethylformamide (including 0.5% by mass of triethanolamine), measurement temperature: 25 ° C., and flow rate: 1 mL / min.

  Silane coupling agent (a) (hereinafter sometimes referred to as “component (a)”) is hydrolyzed with at least 1, preferably 1 or 2 primary or secondary amino groups in one molecule. The silane coupling agent having a functional group is not particularly limited. The hydrolyzable group is not particularly limited, and preferred examples include an alkoxy group directly bonded to silicon element, that is, an alkoxysilyl group.

  Specific examples of the silane coupling agent (a) include N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- ( 2-aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like, among others, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane N- (2-aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane can be preferably used.

  As long as the silane coupling agent (b) (hereinafter sometimes referred to as “component (b)”) is a silane coupling agent having at least one epoxy group and hydrolyzable group in one molecule, There is no particular limitation. The hydrolyzable group is not particularly limited, and preferred examples include an alkoxy group directly bonded to silicon element, that is, an alkoxysilyl group.

  Specific examples of the silane coupling agent (b) include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like. However, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane can be preferably used.

Moreover, the alkoxysilane compound (c) (hereinafter sometimes referred to as “component (c)”) used in some cases has the formula: (R) _4-n- Si— (X) _n [wherein R Represents a hydrocarbon group having 1 to 18 carbon atoms which may be optionally substituted with a non-reactive substituent, X represents an alkoxyl group, and n represents an integer of 1 to 3. It is what Examples of the substituent having no reactivity include a chloro group, a fluoro group, a methoxy group, an ethoxy group, and a propoxy group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and a cycloalkyl group. , Aryl group, aralkyl group and the like. Moreover, as an alkoxy group, C1-C6 alkoxy groups, such as a methoxy, an ethoxy, a propoxy, are preferable.

  The alkoxysilane compound (c) includes trialkoxysilane compounds, dialkoxysilane compounds, and monoalkoxysilane compounds. From the viewpoint of solubility in an aqueous medium, the trialkoxysilane compound is at least 80% by mass. What contains, especially what consists only of trialkoxysilane compounds is suitable.

  Examples of the trialkoxysilane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, Pentiltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, methyltris (methoxyethoxy) silane, ethyltris (methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, vinyltris (methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, etc., among these, Tiltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, methyltris (methoxyethoxy) silane, ethyltris (methoxy Ethoxy) silane is preferred.

Examples of the mono- or di-alkoxysilane compound include monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, triethylmethoxysilane, and triethylethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, and dimethyldi propoxysilane, diethyl dimethoxysilane, diethyl diethoxy silane, methyl ethyl dimethoxy silane, and the like dialkoxysilane such as methyl ethyl diethoxy silane, dipropyl di methoxysilane.

  In the production of the reaction product (A), that is, the reaction products (A-1) and (A-2), the mixing ratio of the silane coupling agent (a) and the silane coupling agent (b) The amount of active hydrogen of the amino group in the silane coupling agent (a) is 1.0 to 5.0 equivalents, preferably 1.5 to 4.0 equivalents, relative to 1 equivalent of the epoxy group in the ring agent (b). More preferably, the ratio can be 2.0 to 3.5 equivalents.

  For example, since 3-aminopropyltrimethoxysilane has two active hydrogens in one molecule, 1 mol of 3-aminopropyltrimethoxysilane corresponds to 2 equivalents of active hydrogen groups. N- (2-aminoethyl) 3-aminopropyltrimethoxysilane has a primary amino group having two active hydrogens and a secondary amino group having one active hydrogen in one molecule, Since there are a total of three active hydrogens in one molecule, 1 mol of N- (2-aminoethyl) 3-aminopropyltrimethoxysilane corresponds to 3 equivalents of active hydrogen groups.

In the production of the reaction product (A-2), the blending ratios of the silane coupling agent (a), the silane coupling agent (b) and the alkoxysilane compound (c) are the above (a), (b) and (c). ) Based on 100 parts by weight of the total amount of components, the components (a) and (b) are 30 to 95 parts by weight, preferably 50 to 90 parts by weight, more preferably 60 to 90 parts by weight, and (c ) Component may be 5-70 parts by weight, preferably 10-50 parts by weight, more preferably 10-40 parts by weight. Incidentally, a silane coupling agent (a), as described above, with respect to one epoxy group equivalent of the silane coupling agent (b), the amount of active hydrogen of the amino group in the silane coupling agent (a) 1. It can mix | blend in the ratio which becomes 0-5.0 equivalent, Preferably it is 1.5-4.0 equivalent, More preferably, it is 2.0-3.5 equivalent.

  The reaction product (A-1) was obtained by subjecting the silane coupling agent (a) and the silane coupling agent (b) to addition reaction and hydrolysis reaction in an aqueous medium containing an acid neutralizer. Alternatively, the silane coupling agent (a) and the silane coupling agent (b) are subjected to an addition reaction in an organic solvent or in the absence of a solvent, and the addition reaction product is further added to an aqueous medium containing an acid neutralizing agent. Can be obtained by removing the aqueous solution of the silane reaction product (A′-1) obtained by hydrolysis with a method described later.

  In the present specification, the “aqueous medium” is water or a mixed liquid of water containing at least 80% by mass of water and other liquid, and includes a silane coupling agent (a) and a silane coupling agent (b ), And a liquid capable of dissolving or dispersing the reaction product of the silane coupling agent (a) and the silane coupling agent (b). Examples of other liquids in the mixed liquid include an organic solvent, a neutralizing agent, a surfactant, and a mixture of two or more thereof.

  As the organic solvent in the mixed solution, a water-soluble organic solvent can be preferably used, and examples thereof include methanol, ethanol, isopropanol, n-propanol, ethylene glycol, propylene glycol, and ethylene glycol monobutyl ether. it can.

  Examples of the neutralizing agent in the above mixed solution include acid neutralizing agents such as formic acid, acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lactic acid, succinic acid, glutaric acid, citric acid, methacrylic acid, 1- Organic acids such as hydroxyethane-1,1-diphosphonic acid, hydroxymethane bisphosphonic acid, p-toluenesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and the like, For example, inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, aqueous ammonia; monoethylamine, diethylamine, triethylamine, diisopropylamine, triisopropylamine, dibutylamine, monoethanolamine, diethanolamine, mono (2- Hydroxypropyl) amine, N, N-dimethylaminoeta It can be exemplified amine compounds such Lumpur.

As the surfactant in the above mixture, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants, reactive surfactants and the like are known per se. Surfactants can be used.
As an acid neutralizer which the said aqueous medium contains, what was mentioned as an acid neutralizer in the said liquid mixture can be used.

In the method for producing an aqueous liquid of a silane reaction product (A′-1), first, a typical method for producing an aqueous liquid of a silane reaction product (A′-1) through a step of reacting in an aqueous medium. The manufacturing method 1 and manufacturing method 2, which are various manufacturing methods, will be described.
<Production Method 1 of Aqueous Liquid of Silane Reaction Product (A′-1)>

  In the production method 1 of the aqueous liquid of the silane reaction product (A′-1), a silane coupling agent (a) having at least one primary or secondary amino group and a hydrolyzable group in an aqueous medium. Then, the hydrolysis reaction product and a silane coupling agent (b) having at least one epoxy group and a hydrolyzable group are mixed in an aqueous medium containing an acid neutralizing agent. In this method, a silane reaction product (A ′) is produced by a hydrolysis reaction and an addition reaction. Specifically, a silane coupling agent (a) having at least one primary or secondary amino group and a hydrolyzable group is added to an aqueous medium, and based on the silane coupling agent (a). After hydrolyzing the hydrolyzable group, an acid neutralizing agent is blended, and then a silane coupling agent (b) having at least one epoxy group and hydrolyzable group is added, followed by hydrolysis reaction and addition In this method, an aqueous liquid of the silane reaction product (A′-1) is obtained by reaction.

  In this production method 1, since the silane coupling agent (a) has an amino group and is generally water-soluble, the aqueous medium can be water, but if necessary, the solubility is improved and the pH is increased. For adjustment and the like, a mixed solution containing an acid neutralizing agent, an organic solvent and / or a surfactant may be used.

  In the above production method 1, when the silane coupling agent (a) is added to the aqueous medium, heat is generated by the hydrolysis reaction, so that the silane coupling agent (a) is gradually added to prevent rapid reaction. Is preferred. When an abrupt reaction occurs, a condensation reaction of silanol groups generated by a hydrolysis reaction occurs abruptly, and particle formation and gelation are likely to occur.

  A silanol group is generated by a hydrolysis reaction of a hydrolyzable group based on the silane coupling agent (a) in an aqueous medium. Thereafter, an acid neutralizing agent is added to the resulting reaction solution, and then the silane coupling agent (b) is added. The amount of the acid neutralizer used for acid neutralization of the resulting reaction mixture solution is usually in the reaction mixture solution after neutralization with respect to 1.0 equivalent of the amino group of the silane coupling agent (a). The amount is 0.1 to 1.0 equivalent, preferably 0.1 to 0.5 equivalent. When an acid neutralizing agent is blended in advance in the aqueous medium, the blending amount of the acid neutralizing agent in the reactant solution can be adjusted to be in the neutralization equivalent range. By adding this acid neutralizer, the pH of the aqueous solution of the resulting silane reaction product (A′-1) can be adjusted to usually 4 to 10, preferably 5 to 10, and more preferably 6 to 10.

  It is preferable that all or most of the hydrolyzable groups of the silane coupling agent (a) are hydrolyzed at the time of adding the silane coupling agent (b) to the reactant solution. Only the part may be hydrolyzed.

  Next, a silane coupling agent (b) is added to the acid-neutralized reactant solution, and an amino group based on the silane coupling agent (a) and an epoxy group based on the silane coupling agent (b) are added. An aqueous solution of the silane reaction product (A′-1) can be obtained by performing an addition reaction in step 1 and a hydrolysis reaction of a hydrolyzable group. These reactions can be usually performed at a temperature of 20 to 100 ° C. for about 0.5 to about 20 hours, preferably at a temperature of 40 to 90 ° C. for about 1 to about 10 hours.

The aqueous liquid of the silane reaction product (A′-1) thus obtained is generally 3 to 30% by mass, preferably 5 to 20% by mass, with the silane reaction product (A′-1) as a solid content. It can be contained within the range.
<Method 2 for producing aqueous solution of silane reaction product (A′-1)>

  The production method 2 of the aqueous liquid of the silane reaction product (A′-1) is a hydrolyzable group of the silane coupling agent (b) having at least one epoxy group and a hydrolyzable group in an aqueous medium. In the aqueous medium containing an acid neutralizer by adding a silane coupling agent (a) having at least one primary or secondary amino group and hydrolyzable group. In this method, an aqueous liquid of the silane reaction product (A′-1) is obtained by a hydrolysis reaction and an addition reaction.

  In this production method 2, since the silane coupling agent (b) generally has poor solubility in water, an aqueous medium containing an acid neutralizer is used. When the aqueous medium contains an acid neutralizing agent, hydrolysis of the hydrolyzable group can be promoted, and the water solubility of the reaction product can be improved.

  In the said manufacturing method 2, when adding a silane coupling agent (b) in an aqueous medium, in order to prevent rapid reaction, it is preferable to add silane coupling agent (b) gradually. When the silane coupling agent (b) is added to the aqueous medium, hydrolysis of the hydrolyzable group in the silane coupling agent (b) proceeds to generate a silanol group. In the reaction mixture to be produced, it is preferable that all or most of the hydrolyzable groups of the silane coupling agent (b) are hydrolyzed, but only a part of the hydrolyzable groups may be hydrolyzed.

  Next, a silane coupling agent (a) is added to the reaction mixture solution, and an addition reaction between an amino group based on the silane coupling agent (a) and an epoxy group based on the silane coupling agent (b), And an aqueous liquid of the silane reaction product (A′-1) can be obtained by performing a hydrolysis reaction of the hydrolyzable group.

  The above reaction after addition of the silane coupling agent (a) can be carried out usually at a temperature of 20 to 100 ° C. for about 0.5 to about 20 hours, preferably at a temperature of 40 to 90 ° C. for about 1 to about 10 hours. . At the time when the silane coupling agent (a) is added to the reaction mixture solution, the amount of the acid neutralizing agent compounded in the liquid is 1.0 equivalent of the amino group of the silane coupling agent (a). In general, the amount is preferably 0.1 to 1.0 equivalent, particularly preferably 0.1 to 0.5 equivalent. By adding this acid neutralizing agent, the pH of the aqueous liquid of the silane reaction product (A′-1) can be adjusted to usually 4 to 10, preferably 5 to 10, and more preferably pH 6 to 10.

  The aqueous liquid of the silane reaction product (A′-1) thus obtained is generally 3 to 30% by mass, preferably 5 to 20% by mass, with the silane reaction product (A′-1) as a solid content. It can be contained within the range.

Next, the manufacturing method which manufactures the aqueous liquid of a silane reaction product (A'-1) through the process of making a silane coupling agent (a) and a silane coupling agent (b) react in a non-solvent or an organic solvent. 3 will be described.
<Method 3 for producing an aqueous liquid of the silane reaction product (A′-1)>

  The production method 3 of the aqueous liquid of the silane reaction product (A′-1) is a silane cup having at least one primary or secondary amino group and hydrolyzable group in an organic solvent or in the absence of a solvent. A ring agent (a) and a silane coupling agent (b) having at least one epoxy group and a hydrolyzable group are subjected to an addition reaction between an amino group and an epoxy group, and then the addition reaction product is converted into an addition reaction product. In this method, an aqueous liquid of the silane reaction product (A′-1) is obtained by dissolving or dispersing in an aqueous medium containing water and an acid neutralizing agent, followed by hydrolysis.

  In the production method 3, first, the silane coupling agent (a) and the silane coupling agent (b) are subjected to an addition reaction between an amino group and an epoxy group in an organic solvent or in the absence of a solvent. This addition reaction is an exothermic reaction, and it is preferable to suppress an abrupt reaction. For example, after the mixing is gradually performed and the mixing is completed, the mixture is stirred, for example, for about 30 minutes to about 2 hours. It is preferable to carry out the addition reaction by heating at a temperature of 60 to 90 ° C. for about 1 to about 20 hours. When the reaction is carried out in an organic solvent, the organic solvent is preferably a low-boiling water-soluble solvent that is water-soluble and easy to remove in the subsequent step. Specific examples include low-boiling water such as ethanol, isopropanol, and n-propanol. Mention may be made of boiling alcohol solvents.

  After completion of the addition reaction, the addition reaction mixture is dissolved or dispersed in an aqueous medium containing an acid neutralizing agent and subjected to a hydrolysis reaction to obtain an aqueous liquid of the silane reaction product (A′-1). it can. In the hydrolysis reaction, the addition reaction mixture is dissolved or dispersed in an aqueous medium containing an acid neutralizing agent, and usually at a temperature of 20 to 100 ° C. for about 0.5 to about 20 hours, preferably 40 to 90 ° C. For about 1 to about 10 hours. The amount of the acid neutralizing agent in the aqueous medium to be blended with the addition reaction mixture is usually 0.1 to 1.0 equivalent based on 1.0 equivalent of the amino group of the silane coupling agent (a) used. The amount is preferably 0.1 to 0.5 equivalent. With this acid neutralizing agent, the pH of the aqueous solution of the resulting silane reaction product (A′-1) can be generally adjusted to 4 to 10, preferably 5 to 10, and more preferably pH 6 to 10. The aqueous liquid of the silane reaction product (A′-1) thus obtained has a solid content of the silane reaction product (A′-1) of 3 to 30% by mass, preferably 5 to 20% by mass. Can be contained within.

  The reaction product (A-2) is a silane coupling agent (a), a silane coupling agent (b), and an alkoxysilane compound (c), hydrolysis reaction, and addition between an epoxy group and an amino group. It can obtain by attaching | subjecting reaction and removing the aqueous liquid of the silane reaction product (A'-2) to produce | generate by the method mentioned later. The reaction can be performed by a method of reacting in an aqueous medium or a method of further reacting in an aqueous medium after partially reacting in an alcohol solvent or without a solvent.

In the method for producing an aqueous liquid of the above silane reaction product (A′-2), first, a method for producing an aqueous liquid of the silane reaction product (A′-2) by a method of reacting in an aqueous medium is representative. Manufacturing method 1 and manufacturing method 2, which are typical manufacturing methods, will be described.
<Production Method 1 of Aqueous Liquid of Silane Reaction Product (A′-2)>

  In the production method 1 of the aqueous liquid of the silane reaction product (A′-2), the silane coupling agent (a) having at least one primary or secondary amino group and hydrolyzable group in an aqueous medium. Then, the hydrolysis reaction product is reacted with a silane coupling agent (b) having at least one epoxy group and a hydrolyzable group and an alkoxysilane compound (c) to produce a silane reaction. In this method, the product (A′-2) is generated.

  As a typical production method 1 for producing an aqueous liquid of the silane reaction product (A′-2), a silane cup having at least one primary or secondary amino group and a hydrolyzable group in an aqueous medium. A ring agent (a) is subjected to a hydrolysis reaction, and the hydrolysis reaction product, a silane coupling agent (b) having at least one epoxy group and a hydrolyzable group, and an alkoxysilane compound (c) are reacted with an acid. The method of mixing in the aqueous medium containing a neutralizing agent, making it a hydrolysis reaction and addition reaction, and producing | generating a silane reaction product (A'-2) can be mentioned.

  In this production method 1, since the component (a) has an amino group and is generally water-soluble, the aqueous medium can be water, but if necessary, solubility improvement, pH adjustment, etc. Therefore, it may be a mixed solution containing an acid neutralizer, an organic solvent, and / or a surfactant.

  In the production method 1, when the component (a) is added to the aqueous medium, heat is generated by the hydrolysis reaction. Therefore, in order to prevent a rapid reaction, it is preferable to gradually add the component (a). When a rapid reaction occurs, a condensation reaction of a silanol group generated by a hydrolysis reaction is likely to occur rapidly, and particleization and gelation are likely to occur.

  A silanol group is generated by a hydrolysis reaction of a hydrolyzable group based on the component (a) in an aqueous medium. It is preferable from the viewpoint of improving water solubility and stability that an acid neutralizing agent is added to the resulting reaction mixture solution, and then component (b) and component (c) are added. In this case, the amount of the acid neutralizing agent used for acid neutralization of the resulting reaction mixture solution is generally 0. 0 with respect to 1 equivalent of the amino group of the component (a) in the reaction mixture solution after neutralization. The amount can be 1 to 2.0 equivalents, preferably 0.1 to 1.0 equivalents. When an acid neutralizing agent is blended in advance in the aqueous medium, it is preferable to adjust the blending amount of the acid neutralizing agent in the reaction mixture solution to be in the neutralization equivalent range. The pH of the aqueous medium liquid containing the resulting silane reaction product (A′-2) is usually 4 to 10, preferably 5 to 10, more preferably 6 to 10 by blending this acid neutralizer. Can do.

  It is preferable that all or most of the hydrolyzable groups of the component (a) are hydrolyzed at the time of adding the component (b) and the component (c) to the reaction mixture solution. Only a part of may be hydrolyzed.

  By adding the component (b) and the component (c) to the acid-neutralized reaction mixture solution, and performing an addition reaction between an amino group and an epoxy group and a hydrolysis reaction of a hydrolyzable functional group, a silane reaction A product (A′-2) aqueous liquid can be obtained. These reactions can usually be performed at a temperature of 20 to 100 ° C. for about 0.5 to about 20 hours, preferably at a temperature of 40 to 90 ° C. for about 1 to about 10 hours.

The aqueous solution of the silane reaction product (A′-2) thus obtained in the aqueous medium is generally 3 to 30% by mass, preferably 5 to 20%, based on the silane reaction product (A′-2) as a solid content. It can contain within the range of the mass%.
<Method 2 for producing aqueous solution of silane reaction product (A'-2)>

  In the production method 2 of the aqueous liquid of the silane reaction product (A′-2), a silane coupling agent (b) having at least one epoxy group and a hydrolyzable group and an alkoxysilane compound (c) in an aqueous medium. And a silane coupling agent (a) having at least one primary or secondary amino group and a hydrolyzable group, and an aqueous solution containing an acid neutralizer. In this method, a silane reaction product (A′-2) is produced by a hydrolysis reaction and an addition reaction in a medium.

  In this production method 2, since the component (b) and the component (c) generally have a low hydrolysis rate, it is preferable to use an aqueous medium containing an acid as a catalyst, that is, an aqueous medium containing an acid neutralizer. When the aqueous medium contains an acid neutralizing agent, hydrolysis of the hydrolyzable group can be promoted, and the water solubility of the reaction mixture can be improved.

  In the above production method 2, when the component (b) and the component (c) are added to the aqueous medium, the component (b) and the component (c) may be gradually added to prevent an abrupt reaction. preferable. When the component (b) and the component (c) are added to the aqueous medium, hydrolysis of the hydrolyzable functional group in the component (b) and the component (c) proceeds to generate a silanol group. In the resulting reaction mixture, it is preferable that all or most of the hydrolyzable functional groups of the component (b) and the component (c) are hydrolyzed, but only a part of the hydrolyzable groups are hydrolyzed. Also good.

  Next, the component (a) is added to the reaction mixture solution, an addition reaction between the amino group based on the component (a) and the epoxy group based on the component (b), and the hydrolysis of the hydrolyzable functional group. By performing the decomposition reaction, an aqueous liquid of the silane reaction product (A′-2) can be obtained.

The above reaction after addition of the component (a) is usually carried out at a temperature of 20 to 100 ° C. for about 0.5 to about 20 hours, preferably at a temperature of 40 to 90 ° C. for about 1 to about 10 hours. When the component (a) is added to the reaction mixture solution, the amount of the acid neutralizer added in the solution is generally 0.1 to 2.0 with respect to 1 equivalent of the amino group of the component ( a ). The amount can be equivalent, preferably 0.1 to 1.0 equivalent. By blending this acid neutralizer, the pH of the aqueous liquid of the silane reaction product (A′-2) can be usually 4 to 10, preferably 5 to 10, and more preferably 6 to 10.

  The aqueous liquid of the silane reaction product (A′-2) thus obtained in the aqueous medium is generally 3 to 30% by mass, preferably 5 to 5%, based on the silane reaction product (A′-2) as a solid content. It can contain within the range of 20 mass%.

Next, after reacting a part of the components (a), (b) and (c) in an alcohol solvent or without a solvent, a silane reaction product (A′- Production method 3 for producing the aqueous liquid 2) will be described.
<Method 3 for producing an aqueous liquid of the silane reaction product (A'-2)>

  The production method 3 of the aqueous liquid of the silane reaction product (A′-2) is 1 or 2 of the components (a), (b) and (c) in an organic solvent, particularly in an alcohol solvent or in the absence of a solvent. In this method, after the components are hydrolyzed, the remaining components are further added in an aqueous medium to perform a hydrolysis reaction and an addition reaction, thereby generating a silane reaction product (A′-2).

  As a typical production method 3 for producing an aqueous liquid of the silane reaction product (A′-2), a silane coupling agent having at least one epoxy group and a hydrolyzable group in an alcohol solvent or under no solvent. After the hydrolysis reaction of (b) and the alkoxysilane compound (c), the hydrolysis reaction product is dissolved or dispersed in an aqueous medium containing an acid neutralizer, and then at least one primary Alternatively, a method of adding a silane coupling agent (a) having a secondary amino group and a hydrolyzable group and causing a hydrolysis reaction and an addition reaction to produce a silane reaction product (A′-2) is mentioned. be able to.

  In the typical production method of the production method 3, first, the component (b) and the component (c) are added in an alcohol solvent or under no solvent to a total molar amount 1 of the component (b) and the component (c). On the other hand, it is preferable to add about 1 to about 5 times the molar amount of water to cause a hydrolysis reaction. This hydrolysis reaction is an exothermic reaction, and it is preferable to suppress an abrupt reaction. For example, it is preferable to add both gradually. Due to the abrupt reaction, a condensation reaction of silanol groups generated during the hydrolysis reaction also occurs. If the condensation reaction goes too far, gelation occurs, so care must be taken. The hydrolysis reaction can be performed usually at a temperature of 20 to 80 ° C. for about 0.5 to about 10 hours, preferably at a temperature of 30 to 70 ° C. for about 1 to about 5 hours. As the alcohol solvent, those which are water-soluble and can be easily removed in a subsequent step are preferable. Specific examples thereof include low-boiling alcohol solvents such as ethanol, isopropanol and n-propanol.

After this hydrolysis reaction, the resulting reaction mixture is dissolved or dispersed in an aqueous medium containing an acid neutralizer. Next, the component (a) is added to the aqueous liquid of the resulting reaction mixture to cause a hydrolysis reaction, and an addition reaction between the amino group in the component (a) and the epoxy group in the component (b). To produce a silane reaction product (A′-2). The amount of the acid neutralizing agent in the aqueous medium is usually 0.1 to 2.0 equivalents, preferably 0.1 with respect to 1 equivalent of amino groups in the component (a) blended in the aqueous liquid of the reaction product. The amount can be -1.0 equivalent. By blending this acid neutralizer, the pH of the aqueous solution of the resulting silane reaction product (A′-2) can be usually 4 to 10, preferably 5 to 10, and more preferably 6 to 10.

  The hydrolysis reaction and addition reaction in the aqueous medium can be performed usually at a temperature of 20 to 100 ° C. for about 0.5 to about 20 hours, preferably at a temperature of 40 to 90 ° C. for about 1 to about 10 hours. .

  The aqueous liquid of the silane reaction product (A′-2) thus obtained in the aqueous medium is generally 3 to 30% by mass, preferably 5 to 5%, based on the silane reaction product (A′-2) as a solid content. It can contain within the range of 20 mass%.

Moreover, as a manufacturing method 3, after making the silane coupling agent (a) which has an at least 1 primary or secondary amino group and a hydrolysable group in an alcohol solvent or under absence of solvent, a hydrolysis reaction is carried out. The resulting reaction mixture is dissolved or dispersed in an aqueous medium containing an acid neutralizer, and then a silane coupling agent (b) having at least one epoxy group and a hydrolyzable group and an alkoxysilane compound A method of generating a silane reaction product (A′-2) by adding (c) to cause a hydrolysis reaction and an addition reaction can also be mentioned.
By the manufacturing methods 1 to 3 described above, an aqueous liquid of the silane reaction product (A′-2) can be obtained in a state dissolved or dispersed in an aqueous medium.

  In this specification, the silane reaction product (A′-1) and the silane reaction product (A′-2) are collectively referred to as a silane reaction product (A ′).

After the aqueous solution of the silane reaction product is prepared by adding the acid stabilizer (B) described below to the aqueous solution of the silane reaction product (A ′) obtained by the method described above, the solvent is removed. The stable aqueous | water-based binder composition containing the reaction product (A) used as the solid content of a binder composition is performed can be manufactured.
Acid stabilizer (B)

  The acid stabilizer (B) in the composition of the present invention is a component that contributes to the improvement of the liquid stability of the aqueous binder composition of the present invention, and an aqueous binder composition or a metal surface treatment agent using the aqueous binder composition. The condensation reaction of the silanol group of the reaction product (A) in the inside is suppressed, and the liquid stability is improved. The acid stabilizer (B) may be useful for improving the corrosion resistance of the surface treatment film formed from the surface treatment agent.

  In the composition of the present invention, the acid stabilizer (B) is at least one acid selected from a phosphoric acid compound and a nitric acid compound.

  Examples of the phosphoric acid compound include inorganic phosphoric acid compounds such as phosphoric acid (orthophosphoric acid), condensed phosphoric acid, and phosphorous acid; and organic phosphoric acid compounds such as organic phosphonic acid. . The condensed phosphoric acid includes metaphosphoric acid and polyphosphoric acid, which is a cyclic phosphoric acid condensate, including trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, etc., and polyphosphoric acid is a chain phosphoric acid condensation Including pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid and the like. Examples of the organic phosphonic acid include aminotrimethylenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, hydroxymethane bisphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and the like. .

Examples of the nitric acid compound include nitric acid and nitrous acid.
These acid stabilizers can be used alone or in combination of two or more.
Of the acid stabilizers (B), phosphoric acid and nitric acid are preferred, and phosphoric acid is particularly preferred.

The compounding quantity of an acid stabilizer (B) is 1-10 mass parts generally based on 100 mass parts of reaction products (A), Preferably it is 2-8 mass parts, More preferably, it is 3-7 mass parts.
Production of aqueous binder composition for metal surface treatment agent

The aqueous binder composition for a metal surface treatment agent of the present invention includes, for example, at least one silane coupling agent (a) having a primary or secondary amino group and a hydrolyzable group, and at least one epoxy. A silane coupling agent (b) having a group and a hydrolyzable group, and optionally further a formula: (R) _4-n- Si- (X) _n [wherein R is optionally reactive. Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, X represents an alkoxyl group, and n represents an integer of 1 to 3]. A silane reaction product (A ′) is produced by reacting with (c), and then the silane reaction product (A ′) is subjected to at least one selected from a phosphoric acid compound and a nitric acid compound. Add acid stabilizer (B) After preparation of the aqueous solution of the silane reaction product by Rukoto, it can be produced by a method which is characterized in that the solvent is removed.

  In the silane reaction product (A ′), similarly to the reaction product (A), the amino group of the silane coupling agent (a) and the epoxy group of the silane coupling agent (b) are chemically bonded, Hydrolyzable having substantially no unreacted epoxy group based on the silane coupling agent (b) and based on the silane coupling agent (a), the silane coupling agent (b) and the alkoxysilane compound (c) Although it is preferable that all of the functional groups are substantially hydrolyzed to silanol groups, they have a small amount of unreacted epoxy groups, and some of the hydrolyzable functional groups are hydrolyzed to silanol groups. Even if it remains, the reaction proceeds in the solvent removal step, and the reaction product (A) obtained after the solvent removal step is substantially free of unreacted epoxy groups and has a hydrolyzable functionality. All of the groups are real As long as to become what is hydrolyzed to silanol group, it is encompassed by the silane reaction product (A ').

  The aqueous solution of the silane reaction product can be prepared, for example, by adding the acid stabilizer (B) to the aqueous solution of the silane reaction product (A ′) obtained as described above and mixing. .

  Solvent removal of the aqueous liquid of the silane reaction product thus obtained is a process in which the liquid stability tends to deteriorate, but according to the present invention, by mixing the acid stabilizer (B) before the solvent removal process, The stability of the liquid can be maintained.

  The solvent removal conditions are not particularly limited as long as the solvent such as alcohol produced by hydrolysis in the aqueous liquid of the silane reaction product can be removed and the liquid stability is not hindered. For example, the solvent removal can be carried out by distillation under reduced pressure usually at a temperature of 50 to 90 ° C., particularly 60 to 80 ° C. for about 0.5 to about 20 hours, preferably about 0.5 to about 3 hours. Although the change of the liquid pH due to the solvent removal step is small, the pH can be adjusted by adding a neutralizing agent when the pH of the binder composition during or after the solvent removal is out of the above range.

  The solvent-removed product can be used as an aqueous binder composition for a metal surface treatment agent as it is or after blending water, a neutralizing agent or the like for solid content adjustment or pH adjustment as necessary. .

The binder composition for surface treatment of a metal material of the present invention generally has a pH in the range of 4.0 to 10.0, preferably 5.0 to 10.0, and more preferably 6.0 to 10.0. Further, the binder composition of the present invention can have a solid content concentration of generally 5 to 30% by mass, preferably 5 to 20% by mass, and an organic solvent amount of 3% by mass or less, particularly 1 It is desirable that it is a non-hazardous material having a mass% or less and having no flash point. The binder composition for surface treatment of a metal material according to the present invention generally has a liquid viscosity of 2.5 cps or less, particularly 2.4 cps or less measured at a measurement temperature of 20 ° C. and a B-type rotational viscometer at 60 rpm. It is preferable from the viewpoint of fluidity of the liquid.
Metal surface treatment agent

The metal surface treatment agent of this invention contains the binder composition for metal surface treatment agents described above and a rust inhibitor.
Examples of the anticorrosive agent include those usually used in the paint field, such as manganese, cobalt, zinc, magnesium, nickel, titanium, vanadium, zirconium, tin, calcium, silicon, tungsten, molybdenum, hafnium, and aluminum. A metal compound containing: inorganic phosphoric acid, organic phosphoric acid and the like. Examples of such metal compounds include carbonates, phosphates, nitrates, sulfates, acetates, fluoroacids and salts thereof, and oxides of such metals. These metal compounds may be anhydrides or, if present, hydrates. Among the above metal compounds, a metal compound containing titanium, vanadium and zirconium is preferable.

Specific examples of the metal compound include basic zirconium carbonate (ZrCO ₄ .ZrO ₂ .8H ₂ O), ammonium zirconium carbonate, nickel sulfate, zirconium nitrate, vanadyl sulfate, zirconium sulfate, aluminum nitrate, nickel acetate, zirconium acetate, Vanadium oxide, ammonium metavanadate; hexafluorotitanic acid (H ₂ TiF ₆ ), hexafluorozirconic acid (H ₂ ZrF ₆ ), hexafluorosilicic acid (H ₂ SiF ₆ ), hexafluorohafnium acid (H ₂ HfF ₆ ), hexafluoroaluminum acid (H ₃ AlF ₆ ), tetrafluoroboric acid (HBF ₄ ) and other fluoro acids, and salts of these fluoro acids (eg, sodium salt, potassium salt, lithium salt, ammonium salt) Salt, amine salt, zinc salt, etc.).

Specific examples of inorganic phosphoric acid that can be used as a rust inhibitor include phosphoric acid (orthophosphoric acid), trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, Specific examples of the organic phosphoric acid include aminotrimethylenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxymethane-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid. And so on. Among these, phosphoric acid, hydroxymethane bisphosphonic acid and 1-hydroxyethane-1,1-diphosphonic acid are preferable.
These metal compounds, inorganic phosphoric acid, and organic phosphoric acid that can be used as these rust preventives can be used alone or in combination of two or more.

  The compounding amount of the rust inhibitor in the metal surface treatment agent of the present invention is generally 0 based on 100 parts by mass of the solid content of the reaction product (A) from the viewpoint of corrosion resistance, conductivity and stability of the surface treatment agent. 0.1 to 100 parts by mass, preferably 0.3 to 80 parts by mass, and more preferably 0.5 to 60 parts by mass.

  In addition to the aqueous binder composition and the rust preventive agent, the metal surface treatment agent of the present invention further contains, as necessary, a usual paint additive such as an organic resin component, a wax component, a filler, an organic solvent, and the like. Can be contained.

  The organic resin component is formulated for the purpose of improving the corrosion resistance of the resulting film, and includes, for example, organic resins such as water-soluble or water-dispersible phenol resins, epoxy resins, urethane resins, and acrylic resins. Can do. When the organic resin component is blended, the blending amount is generally 0.1 to 30% by mass, preferably 0 based on the total solid content of the metal surface treatment agent from the viewpoint of corrosion resistance and conductivity. It may be 2 to 25% by mass, more preferably 0.3 to 20% by mass.

  The wax component is a component for imparting lubricity to the film surface to be formed. For example, a fatty acid ester wax that is an esterified product of a polyol compound and a fatty acid, a silicone wax, a fluorine wax, a polyolefin such as polyethylene, etc. There may be mentioned wax, lanolin wax, montan wax, microcrystalline wax, carnauba wax and the like. These can be used alone or in admixture of two or more. When the wax is blended, the blending amount is generally 0.1 to 10% by mass, preferably 0. 0% as the solid content based on the total solid content of the metal surface treatment agent from the viewpoint of molding processability and corrosion resistance. It can be 2 to 7.5% by mass, more preferably 0.3 to 5% by mass.

  Examples of the filler that can be blended in the metal surface treatment agent as needed include zirconia sol, alumina sol, silica sol (colloidal silica aqueous dispersion), and the like.

  Further, the aqueous medium of the metal surface treatment agent of the present invention can be usually water, but a small amount (for example, for the purpose of adjusting the drying rate or improving the coatability of the metal surface treatment agent). For example, the organic solvent such as lower alcohol such as methanol, ethanol and propanol may be contained in an amount of 5% by mass or less based on the total amount of the aqueous medium. This organic solvent may be an organic solvent such as alcohol remaining in the solvent removal step performed when obtaining the aqueous binder composition, or may be added later when preparing the metal surface treatment agent. Good.

  The surface treating agent of the present invention includes both a building bath composition (concentrated liquid) and a working composition (diluted liquid). The total solid content concentration in the building bath composition can be usually 10 to 40% by mass, preferably 15 to 30% by mass, and the total solid content concentration in the working composition is usually 1 to 40% by mass, preferably 5 It can be -30 mass%.

  When the surface treatment agent of the present invention is used as a working composition, the surface treatment agent is used under the conditions of a temperature of 20 ° C. and a rotation speed of 60 rpm using a B-type rotational viscometer from the viewpoint of the coating properties of the surface treatment agent. It is preferable that the measured viscosity is 2.5 mPa · s or less, particularly 2.4 mPa · s or less.

  Moreover, it is preferable that the surface treating agent of this invention generally has pH within the range of 5.0-10.0, especially 6.0-9.0. At that time, as the pH adjuster for raising the pH, for example, ammonia water, amine compound, alkali metal hydroxide such as sodium hydroxide; alkali metal carbonate such as sodium carbonate or the like is used. As the pH adjuster for lowering the pH, for example, the acid exemplified above as an acid neutralizer can be used. When the pH of the surface treatment agent is too low, the reactivity with the substrate surface becomes excessive, and the film formability and conductivity of the formed film tend to be poor. Moreover, when pH of a surface treating agent is too high, stability of the composition for surface treatment will fall, and there exists a tendency for the corrosion resistance of the membrane | film | coat formed to fall.

The metal surface treating agent of the present invention is excellent in storage stability. The reason is not exactly known, but in a composition using a mixture of two or more silane coupling agents having reactive groups that react with each other as a binder component, the reactive groups react with each other during storage. Although the storage stability may be lowered, in the surface treatment agent of the present invention, the amino group of the silane coupling agent and the epoxy group are reacted in advance, so that the unreacted epoxy group does not substantially remain. Because the product is used, the amino group and the epoxy group do not react with each other during storage and the storage stability is not lowered; the binder component is stabilized by the stabilizer (B) and produced by hydrolysis. This is thought to be due to the fact that the condensation of silanol groups is suppressed. The present inventors believe that the silanol group is coordinated to the stabilizer (B) and stabilized, and the reaction between the silanol groups is suppressed.
Method for surface treatment of metal material

According to the present invention, the metal surface treatment agent is applied to the surface of the metal material and dried, and the dry film weight on the surface of the metal material is usually 0.05 to 3.0 g / m ² , preferably 0.1. A surface treatment method for a metal material is provided, wherein a surface treatment film of ˜1.0 g / m ² , more preferably 0.2 to 0.8 g / m ² is formed. When the film mass after drying is less than 0.05 g / m ^2, it is difficult to sufficiently coat the metal material, the corrosion resistance of the coated metal material becomes insufficient, and the film mass after drying is 3.0 g. When it exceeds / m ² , the conductivity of the surface treatment film tends to decrease.

  The method for applying the metal surface treatment agent to the surface of the metal material is not particularly limited, and a coating method known per se, for example, a dipping method, a spray method, a roll coating method and the like can be used. The surface treatment agent layer formed on the surface of the metal material is preferably heat-dried, and the heat-drying conditions are not particularly limited, but are usually about 50 to about 250 ° C., particularly about 100 to about It is preferred to dry by heating at a temperature of 250 ° C. for about 1 to about 60 seconds, especially about 2 to about 30 seconds.

  The metal material to which the metal surface treatment agent of the present invention can be applied is not particularly limited. For example, an iron plate, a galvanized steel plate, a zinc alloy (for example, iron-zinc, aluminum-zinc, nickel-zinc alloy) Etc.) Plated steel plate, tin-plated steel plate, stainless steel plate, aluminum plate, aluminum alloy plate, etc. are mentioned, among which galvanized steel plate and zinc alloy plated steel plate are suitable. Moreover, there is no restriction | limiting in particular also in the dimension, shape, etc. of this metal material.

  When the metal surface coated with the metal surface treating agent of the present invention is heated and dried, a continuous film having a siloxane bond is formed by dehydration condensation between silanol groups of the silane coupling agent in the reaction product (A). The generated compound having a siloxane bond is hardly soluble in water, and the formed film including the compound exhibits a barrier effect against water, and as a result, the corrosion resistance of the metal material is improved and the film based on the siloxane bond. Therefore, it is considered that the decrease in conductivity can be suppressed. Moreover, the silanol group generated by hydrolysis of the silane coupling agent reacts with the surface of the metal material to form an oxane bond, thereby improving the adhesion of the formed film. Furthermore, the metal surface treating agent of the present invention uses a reaction product (A) obtained by reacting an amino group and an epoxy group in a silane coupling agent in advance as a binder component, and contributes to an improvement in corrosion resistance.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, the scope of the present invention is not limited at all by these Examples. In Examples and Comparative Examples, “part” and “%” are based on mass unless otherwise specified.

Production of aqueous binder composition Example 1

  In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was blended, and γ-glycidoxypropyltrimethoxysilane 61 was added thereto. The portion was added dropwise over 3 hours under stirring. Although heat was generated by dropping, the temperature was kept at 40 ° C. or lower, and after completion of dropping, the mixture was aged and allowed to cool for 1 hour with stirring, then heated and reacted at 80 ° C. for 5 hours. From the 1H-NMR measurement result, it was confirmed that no epoxy group remained in the content after the reaction. Subsequently, 28 parts of acetic acid and 1000 parts of deionized water were added and stirred for 30 minutes to dissolve the content after the reaction, thereby obtaining an aqueous liquid of the silane reaction product (A ′). The neutralization equivalent of the silane reaction product (A ′) with acetic acid is 0.9.

  6 parts of 89% aqueous phosphoric acid solution is added to the aqueous solution of the silane reaction product (A ′), and the mixture is further stirred for 30 minutes, and 250 parts of deionized water is added and dissolved, followed by decompression at 60 to 70 ° C. It concentrated to 1000 parts by distillation, the methanol which arose by hydrolysis was distilled off with a water | moisture content, then, it filtered with a 200 mesh filter, and aqueous binder composition A1 which is aqueous solution was obtained. In aqueous | water-based binder composition A1, the neutralization equivalent by phosphoric acid is 0.1 among all the acids.

The solid content of the aqueous binder composition A1 was 10% and pH 6.5. The methanol concentration in the aqueous binder composition A1 measured by gas chromatography was less than 1.5%, and no flash point was observed. The solid content of the aqueous binder composition A1 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. The weight average molecular weight of the resin solid content of the aqueous binder composition A1 was about 4500, and no change in molecular weight was observed before and after the solvent removal step.

Example 2

  A separable flask equipped with a reflux condenser, a thermometer and a stirrer was mixed with 1000 parts of deionized water, and 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added while cooling in an ice bath. Slowly charged and dissolved. Next, after adding 12 parts of acetic acid to this content, 61 parts of γ-glycidoxypropyltrimethoxysilane was added, stirred for 30 minutes to dissolve, then heated and reacted at 80 ° C. for 5 hours to produce a silane reaction. An aqueous liquid of the product (A ′) was obtained. From the 1H-NMR measurement result, it was confirmed that no epoxy group remained in the silane reaction product (A ′). The neutralization equivalent of the silane reaction product (A ′) with acetic acid is 0.4.

  Next, 6 parts of 89% aqueous phosphoric acid solution was added to the aqueous solution of the silane reaction product (A ′), stirred for 30 minutes, and 250 parts of deionized water was added and dissolved. Concentrated to 1000 parts by vacuum distillation. Methanol generated by hydrolysis in this way was distilled off together with moisture, and then filtered through a 200 mesh filter to obtain an aqueous binder composition A2 as an aqueous solution. In aqueous | water-based binder composition A2, the neutralization equivalent by phosphoric acid is 0.1 among all the acids.

The solid content of the aqueous binder composition A2 was 10% and pH 7.1. The methanol concentration measured by gas chromatograph was less than 1.5% and no flash point was observed. The solid content of the aqueous binder composition A2 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. The weight average molecular weight of the resin solid content of the aqueous binder composition A2 was about 4000, and no change in molecular weight was observed before and after the solvent removal step.

Example 3

  In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 1000 parts of deionized water and 19 parts of acetic acid were blended, and while stirring, 61 parts of γ-glycidoxypropyltrimethoxysilane was gradually added. Stir for 10 minutes to dissolve. Next, 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was gradually added into this, and after stirring for 30 minutes to dissolve it, it was heated and reacted at 80 ° C. for 5 hours to produce a silane reaction. An aqueous liquid of the product (A ′) was obtained. From the 1H-NMR measurement result, it was confirmed that no epoxy group remained in the silane reaction product (A ′). The neutralization equivalent of the silane reaction product (A ′) with acetic acid is 0.6.

  6 parts of 89% aqueous phosphoric acid solution was added to the aqueous solution of the silane reaction product (A ′), stirred for 30 minutes, 250 parts of deionized water was added and dissolved, and then distilled under reduced pressure at 60 to 70 ° C. To 1000 parts. In this way, methanol generated by hydrolysis was distilled off together with moisture, and filtered through a 200 mesh filter to obtain an aqueous binder composition A3 as an aqueous solution. In aqueous | water-based binder composition A3, the neutralization equivalent by phosphoric acid is 0.1 among all the acids.

The solid content of the aqueous binder composition A3 was 10% and pH 6.7. The methanol concentration measured by gas chromatograph was less than 1.5% and no flash point was observed. The solid content of the aqueous binder composition A3 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. The weight average molecular weight of the resin solid content of the aqueous binder composition A3 was about 4000, and no change in molecular weight was observed before and after the solvent removal step.

Example 4

  In Example 1, 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added to 62 parts, and 61 parts of γ-glycidoxypropyltrimethoxysilane was added to 56 parts. The aqueous binder composition A4 having a solid content of 10% and a pH of 6.5 was obtained in the same manner as in Example 1 except that 28 parts by weight of acetic acid was changed to 30 parts. In aqueous | water-based binder composition A4, the neutralization equivalent by an acetic acid is 0.9 among all the acids, and the neutralization equivalent by phosphoric acid is 0.1.

In the aqueous binder composition A4, the methanol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The solid content of the aqueous binder composition A4 did not have an alkoxysilyl group, the alkoxysilyl group was hydrolyzed, and 1H-NMR measurement results confirmed that no epoxy group remained. . The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.5 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. . The weight average molecular weight of the resin solid content of the aqueous binder composition A4 was about 4000, and no change in molecular weight was observed before and after the solvent removal step.

Example 5

  In Example 1, 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added to 45 parts, and 61 parts of γ-glycidoxypropyltrimethoxysilane was added to 73 parts. The aqueous binder composition A5 having a solid content of 10% and a pH of 6.5 was obtained in the same manner as in Example 1 except that 28 parts by weight of acetic acid was changed to 25 parts. In aqueous | water-based binder composition A5, the neutralization equivalent by an acetic acid is 0.9 among all the acids, and the neutralization equivalent by phosphoric acid is 0.1.

In the aqueous binder composition A5, the methanol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The solid content of the aqueous binder composition A5 did not have an alkoxysilyl group, the alkoxysilyl group was hydrolyzed, and 1H-NMR measurement results confirmed that no epoxy group remained. . The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 2.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. . The weight average molecular weight of the resin solid content of the aqueous binder composition A5 was about 5300, and no change in molecular weight was observed before and after the solvent removal step.

Example 6

  In Example 2, 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was changed to 65 parts of 3-aminopropyltriethoxysilane, 12 parts of acetic acid was added to 7 parts, and γ- The same operation as in Example 2 was performed except that 61 parts of glycidoxypropyltrimethoxysilane was changed to 70 parts and 6 parts of 89% phosphoric acid aqueous solution was changed to 3 parts, and the solid content was 10 parts. %, PH 7.1 aqueous binder composition A6 was obtained. In aqueous | water-based binder composition A6, the neutralization equivalent by an acetic acid is 0.4 among all the acids, and the neutralization equivalent by phosphoric acid is 0.1.

In the aqueous binder composition A6, the alcohol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The solid content of the aqueous binder composition A6 did not have an alkoxysilyl group, the alkoxysilyl group was hydrolyzed, and 1H-NMR measurement results confirmed that no epoxy group remained. . The amount of active hydrogen of the amino group of 3-aminopropyltriethoxysilane is 2.0 equivalents relative to 1 equivalent of epoxy group of γ-glycidoxypropyltrimethoxysilane used. The weight average molecular weight of the resin solid content of the aqueous binder composition A6 was about 3000, and no change in molecular weight was observed before and after the solvent removal step.

Example 7

  In Example 1, 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added to 61 parts, and 61 parts of γ-glycidoxypropyltrimethoxysilane was added to 64 parts. In the same manner as in Example 1 except that 28 parts of acetic acid was changed to 11 parts of 60% aqueous nitric acid solution and no 89% aqueous phosphoric acid solution was added, an aqueous binder composition having a solid content of 10% and a pH of 9.0. Product A7 was obtained. In the aqueous binder composition A7, the neutralization equivalent with nitric acid is 0.2.

In the aqueous binder composition A7, the methanol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The solid content of the aqueous binder composition A7 did not have an alkoxysilyl group, the alkoxysilyl group was hydrolyzed, and 1H-NMR measurement results confirmed that no epoxy group remained. . The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 2.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. . The weight average molecular weight of the resin solid content of the aqueous binder composition A7 was about 3000, and no change in molecular weight was observed before and after the solvent removal step.

Example 8

In Example 3, the same operation as in Example 3 was performed except that 61 parts of γ-glycidoxypropyltrimethoxysilane was changed to 72 parts of γ-glycidoxypropyltriethoxysilane, and the solid content was 10%, pH 6 .7 aqueous binder composition A8 was obtained. In the aqueous binder composition A 8, of the total acid neutralization with acetic acid equivalents is 0.6, neutralization equivalent with phosphoric acid is 0.1.

The aqueous binder composition A 8 is an alcohol concentration measured by a gas chromatograph is less than 1.5%, flash point was observed. The solid content of the aqueous binder composition A8 did not have an alkoxysilyl group, the alkoxysilyl group was hydrolyzed, and 1H-NMR measurement results confirmed that no epoxy group remained. . The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 2.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltriethoxysilane used. . The weight average molecular weight of the resin solid content of the aqueous binder composition A8 was about 4000, and no change in molecular weight was observed before and after the solvent removal step.

Example 9

  In Example 1, except having changed 28 parts of acetic acid into 11 parts of 35% hydrochloric acid aqueous solution, operation similar to Example 1 was performed and the aqueous binder composition A9 of solid content 10% and pH 8.6 was obtained. In aqueous | water-based binder composition A9, the neutralization equivalent by hydrochloric acid is 0.2 among all the acids, and the neutralization equivalent by phosphoric acid is 0.1.

Aqueous binder composition A9 had a methanol concentration of less than 1.5% as measured by gas chromatograph, and no flash point was observed. The solid content of the aqueous binder composition A9 did not have an alkoxysilyl group, the alkoxysilyl group was hydrolyzed, and 1H-NMR measurement results confirmed that no epoxy group remained. . The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. . The weight average molecular weight of the resin solid content of the aqueous binder composition A9 was about 3000, and no change in molecular weight was observed before and after the solvent removal step.

Example 10

  In Example 2, 1000 parts of deionized water was changed to 864 parts, and an aqueous liquid of a silane reactant was obtained in the same manner as in Example 2. The neutralization equivalent of acetic acid in the aqueous liquid of the silane reactant is 0.4. Subsequently, 89% phosphoric acid aqueous solution was added to the obtained aqueous solution of the silane reactant, and after stirring, the same operation as in Example 2 was performed except that deionized water was not added and vacuum distillation was not performed. An aqueous binder composition A10 having a solid content of 10% and a pH of 7.1 was obtained. In aqueous | water-based binder composition A10, the neutralization equivalent by phosphoric acid is 0.1 among all the acids.

Aqueous binder composition A10 had a methanol concentration of 5.0% as measured by gas chromatography and a flash point of 76 ° C. The solid content of the aqueous binder composition A10 did not have an alkoxysilyl group, the alkoxysilyl group was hydrolyzed, and 1H-NMR measurement results confirmed that no epoxy group remained. . The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. . The weight average molecular weight of the resin solid content of the aqueous binder composition A10 was about 3500.

Comparative Example 1

In Example 2, the aqueous | water-based binder composition AC1 was obtained by operating like Example 2 except not adding 89% phosphoric acid aqueous solution. The aqueous liquid of the silane reaction product became cloudy during vacuum distillation, and a large amount of precipitate was formed in the finally obtained aqueous binder composition AC1. Therefore, this aqueous binder composition AC1 was not tested below.

Comparative Example 2

A separable flask equipped with a reflux condenser, a thermometer and a stirrer was mixed with 874 parts of deionized water, and 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added while cooling in an ice bath. Slowly charged and dissolved. Then, this was blended with 12 parts of acetic acid content, .gamma.-glycidoxypropyltrimethoxysilane 61 parts were charged, and dissolved by stirring for 30 minutes, the silane reacted for 5 hours the temperature was raised to 80 ° C. The reaction An aqueous solution of product (A ′) was obtained. From the 1H-NMR measurement result, it was confirmed that no epoxy group remained in the silane reaction product. The neutralization equivalent of the silane reactant with acetic acid is 0.4. The obtained aqueous liquid of the silane reaction product was directly filtered through a 200 mesh filter to obtain an aqueous binder composition AC2.

The aqueous binder composition AC2 had a solid content of 10% and a pH of 7.4. The methanol concentration measured by gas chromatography was 8% and the flash point was 65 ° C. Moreover, it confirmed that the epoxy group did not remain | survive from the 1H-NMR measurement result. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. . The weight average molecular weight of the resin solid content of the aqueous binder composition AC2 was about 4000.

Comparative Example 3

  A separable flask equipped with a reflux condenser, a thermometer and a stirrer was mixed with 864 parts of deionized water, and 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added while cooling in an ice bath. Slowly charged and dissolved. Next, 12 parts of acetic acid was added to the contents, and then 61 parts of γ-glycidoxypropyltrimethoxysilane was added dropwise over 1 hour so that the temperature of the reaction solution did not exceed 10 ° C., followed by stirring for 30 minutes. And dissolved. From the results of 1H-NMR measurement, the initial 30% of epoxy groups remained unreacted in this silane reaction product. The neutralization equivalent of acetic acid in the aqueous liquid of the silane reaction product is 0.4. As it was, it was filtered through a 200 mesh filter to obtain an aqueous binder composition AC3 which was an aqueous solution.

The solid content of the aqueous binder composition AC3 was 10%, pH 7.4, the methanol concentration measured by gas chromatography was 5.0%, and the flash point was 76 ° C. The solid content of the aqueous binder composition AC3 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltrimethoxysilane used. The weight average molecular weight of the resin solid content of the aqueous binder composition AC3 was about 1500.

Comparative Example 4

  In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 61 parts of γ-glycidoxypropyltrimethoxysilane was added, 28 parts of acetic acid and 15 parts of deionized water were added, and the mixture was stirred for 30 minutes for hydrolysis. Then, the temperature was raised to 100 ° C. while removing the fraction. The condensation was further continued at 100 ° C. for 1 hour to obtain a colorless and transparent viscous aqueous solution. To this viscous aqueous solution, 57 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added dropwise over 1 hour with stirring. After completion of the dropwise addition, the mixture was stirred for 1 hour and then heated and reacted at 80 ° C. for 5 hours. From the 1H-NMR measurement result, it was confirmed that no epoxy group remained in the content after the reaction. Subsequently, 833 parts of deionized water was added and stirred for 30 minutes to dissolve the content after the reaction. However, the liquid became cloudy and could not be completely dissolved.

The weight average molecular weight of the resin solid content of the obtained aqueous binder composition AC4 exceeded 10,000. This aqueous binder composition AC4 was not tested below.
Table 1 below shows the composition and properties of the aqueous binder compositions in Examples 1 to 10 and Comparative Examples 1 to 4. In Table 1, the blending amount of water is omitted.

Storage test of aqueous binder composition

The aqueous binder compositions prepared in Examples 1 to 10 and Comparative Examples 2 and 3 were stored at 20 ° C., 30 ° C., 40 ° C., and 50 ° C. for 30 days, and the storage stability of the liquid was determined as the liquid appearance and liquid. Based on the viscosity, the following criteria were used for evaluation. The results are shown in Table 2 below. The initial liquid state is also described. The liquid viscosity was measured using a B-type rotational viscometer under the conditions of a measurement temperature of 20 ° C. and a rotation speed of 60 rpm.
○: The liquid appearance is colorless to light yellow and transparent, and the viscosity is 2.5 mPa · s or less.
Δ: The liquid appearance is slightly turbid, precipitates or floats are observed, and the viscosity exceeds 2.5 mPa · s, but no significant thickening or gelation is observed.
X: The liquid appearance is considerably turbid, precipitates or floats are observed, and significant thickening or gelation is observed.

Preparation of metal surface treatment agent

Examples 11-22 and Comparative Examples 5 and 6
Table 3 below shows the components of the metal surface treatment agent, the blending ratio thereof, and the liquid stability. Each component was mixed so that it might become a mixture ratio shown in the following Table 3, and it adjusted to pH 7.0 using acetic acid or aqueous ammonia, and obtained each metal surface treating agent. The storage stability of the obtained metal surface treatment agent was evaluated by the following method. The results are also shown in Table 3 below.

Storage stability

Based on the liquid appearance and liquid viscosity after storage at a predetermined temperature for 1 week, the following criteria were evaluated. The liquid viscosity was measured using a B-type rotational viscometer under the conditions of a measurement temperature of 20 ° C. and a rotation speed of 60 rpm.
○: The liquid appearance is transparent and the viscosity is 2.5 mPa · s or less.
Δ: The liquid appearance is slightly turbid, precipitates or floats are observed, and the viscosity exceeds 2.5 mPa · s, but no significant thickening or gelation is observed.
X: The liquid appearance is considerably turbid, precipitates or floats are observed, and significant thickening or gelation is observed.

Manufacture of surface treatment board

Examples 23-40 and Comparative Examples 7 and 8
Concentration 2 in which the surface of a 0.6 mm-thick double-sided electrogalvanized steel sheet (EG material, basis weight 20 g / m ^{2 on} one side) was dissolved with an alkaline degreasing agent (trade name “Chem Cleaner 561B”, manufactured by Nippon CB Chemical) % Aqueous solution was sprayed for 2 minutes at a temperature of 60 ° C. to remove debris and oil adhering to the surface, washed with water, and dried. Each metal surface treating agent obtained in the above-mentioned examples and comparative examples is applied to the obtained degreased galvanized steel sheet by the roll coating method according to the instructions shown in Table 4 below so that the material arrival temperature becomes 100 ° C. For 20 seconds to obtain a surface-treated plate. As the metal surface treatment agent, the initial one after production and the one after storage at 20 ° C. for 7 days were used.

  About each surface treatment board produced using the metal surface treating agent prepared by each Example and the comparative example, the corrosion resistance and the electroconductivity test were done based on the following test method. The test results are shown in Table 4 below. In addition, the results of the adhesion test described below for each surface-treated plate were good in that no surface-treated film was observed on any of the surface-treated plates.

Test method:

Corrosion resistance:
The end surface part and the back surface part of each surface treatment plate obtained were sealed, and a salt spray test (SST) according to JIS Z 2371 was performed. The degree of rust generation after 120 hours and 240 hours of test time was evaluated according to the following criteria.
a: Rust generation is not recognized.
b: Rust generation is less than 5% of the total area.
c: Rust generation is 5% or more and less than 10% of the total area.
d: Rust generation is 10% or more and less than 50% of the total area.
e: Rust generation is 50% or more of the total area.

Conductivity:
Using a Loresta GP and an ASP terminal manufactured by Mitsubishi Chemical Analytech Co., Ltd., the surface resistance values at arbitrary 10 locations of the surface treatment plate were measured and evaluated by the number of times of 10 ⁻⁴ Ω or less.
a: 10 times all b: 6 to 9 times c: 1 to 5 times d: 0 times

Adhesion test:
A grid was prepared so that 100 squares of 1 mm × 1 mm were formed in 10 mm square so that the surface treatment film surface of each surface treatment plate could reach the substrate with a cutter knife. After performing the Erichsen test (7 mm extrusion) so that this grid part is extruded to the outside, when the cellophane adhesive tape is brought into close contact with the extruded processed part and instantly peeled off, the surface treatment film is peeled off. The degree was evaluated.

Production of aqueous binder composition Example 41

  A separable flask equipped with a reflux condenser, a thermometer and a stirrer was mixed with 850 parts of deionized water, and 53 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added while cooling in an ice bath. Slowly charged and dissolved. Next, after adding 23 parts of acetic acid to this content and neutralizing, a mixture of 66 parts of γ-glycidoxypropyltriethoxysilane and 16 parts of methyltrimethoxysilane was added and dissolved by stirring for 30 minutes. Then, the reaction was carried out at 80 ° C. for 5 hours to obtain an aqueous liquid of the silane reaction product (A ′). From the result of 1H-NMR measurement, it was confirmed that no epoxy group remained in the silane reaction product (A ′).

Next, 10 parts of 89% phosphoric acid aqueous solution and 300 parts of deionized water are added to and dissolved in the aqueous solution of the silane reaction product (A ′), and then 1000 parts by distillation under reduced pressure at 60 to 70 ° C. Until concentrated. In this way, alcohol generated by hydrolysis was distilled off together with moisture, followed by filtration with a 200 mesh filter to obtain an aqueous binder composition A11 which was an aqueous solution. The solid content of the aqueous binder composition A11 was 10% and pH 6.1. The alcohol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The resin solid content of the aqueous binder composition A11 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltriethoxysilane used. The acid neutralization equivalent for this amino group is 1.0. The weight average molecular weight (according to GPC measurement) of the resin solid content of the aqueous binder composition A11 was about 7.0 × 10 ³ .

Examples 42 to 49 and Comparative Example 11

In Example 41, aqueous binder compositions A12 to A19 and AC6 were prepared in the same manner as in Example 41 except that the blending composition was changed as shown in Table 5. In all of the aqueous binder compositions A12 to A19 and AC6, the alcohol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. Specific values of acid neutralization equivalent, equivalent of active hydrogen of amino group to 1 equivalent of epoxy group, solid content, pH, weight average molecular weight and the like are as shown in Table 5.

Example 50

In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 850 parts of deionized water and 21 parts of acetic acid were blended, and 61 parts of γ-glycidoxypropyltriethoxysilane and 30 parts of methyltrimethoxysilane were mixed with stirring. The mixture was gradually added and stirred for 10 minutes to dissolve. Next, 49 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was gradually added to this content and dissolved by stirring for 30 minutes, followed by reaction at 80 ° C. for 5 hours to obtain a silane reactant. An aqueous liquid was obtained. From the result of 1H-NMR measurement, it was confirmed that no epoxy group remained in the silane reaction product.

Subsequently, 10 parts of 89% phosphoric acid aqueous solution and 300 parts of deionized water were added to the aqueous solution of the silane reactant and dissolved, and then concentrated at 60 to 70 ° C. to 1000 parts by vacuum distillation. Thus, the alcohol produced by hydrolysis was distilled off together with moisture, and filtered through a 200 mesh filter to obtain an aqueous binder composition A20 as an aqueous solution. The solid content of the aqueous binder composition A20 was 10% and pH 6.1. The alcohol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The resin solid content of the aqueous binder composition A20 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltriethoxysilane used. . The acid neutralization equivalent for this amino group is 1.0. The weight average molecular weight (according to GPC measurement) of the resin solid content of the aqueous binder composition A20 was 7.2 × 10 ³ .

Example 51

Reflux condenser, a separable flask fitted with a thermometer and a stirrer, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane 49 parts by blending, this γ- glycidoxypropyltrimethoxysilane et Tokishishiran 61 The portion was added dropwise over 3 hours, and after completion of the addition, the mixture was stirred for 1 hour and then reacted at 80 ° C. for 5 hours. From the result of 1H-NMR measurement, it was confirmed that no epoxy group remained in the contents. After adding 21 parts of acetic acid to this content and neutralizing, 850 parts of deionized water was added and dissolved, and then 30 parts of methyltrimethoxylane was added and stirred at 60 ° C. for 30 minutes for hydrolysis. Thus, an aqueous liquid of the silane reaction product (A ′) was obtained.

Next, 10 parts of 89% phosphoric acid aqueous solution and 300 parts of deionized water are added to the aqueous liquid of the silane reaction product (A ′), and concentrated at 60 to 70 ° C. to 1000 parts by vacuum distillation. Alcohol produced by hydrolysis was distilled off together with moisture and filtered through a 200 mesh filter to obtain an aqueous binder composition A21 as an aqueous solution. The solid content of the aqueous binder composition A21 was 10% and pH 6.1. The alcohol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The resin solid content of the aqueous binder composition A21 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltriethoxysilane used. . The acid neutralization equivalent for this amino group is 1.0. The weight average molecular weight (according to GPC measurement) of the resin solid content of the aqueous binder composition A21 was 7.0 × 10 ³ .

Example 52

In Example 41, the blending amounts of γ-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, acetic acid, and methyltrimethoxysilane were changed as shown in Table 5. Further, an aqueous binder composition A22 was prepared in the same manner as in Example 41 except that 9 parts of a 60% nitric acid aqueous solution was added simultaneously with the addition of acetic acid. The solid content of the aqueous binder composition A22 was 10% and pH 8.0. The alcohol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The resin solid content of the aqueous binder composition A22 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltriethoxysilane used. . The acid neutralization equivalent for this amino group is 0.4. The weight average molecular weight (according to GPC measurement) of the resin solid content of the aqueous binder composition A22 was 3.0 × 10 ³ .

Comparative Example 9

  A separable flask equipped with a reflux condenser, a thermometer and a stirrer was mixed with 826 parts of deionized water, and 62 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added while cooling in an ice bath. Slowly charged and dissolved. Next, after adding 33 parts of acetic acid to this content and neutralizing, 78 parts of γ-glycidoxypropyltriethoxysilane was added and dissolved by stirring for 30 minutes, followed by reaction at 80 ° C. for 5 hours. Thus, an aqueous liquid of the silane reaction product (A ′) was obtained. From the result of 1H-NMR measurement, it was confirmed that no epoxy group remained in the silane reaction product.

Subsequently, 300 parts of deionized water was added to the aqueous solution of the silane reaction product (A ′) and dissolved, and then concentrated at 60 to 70 ° C. to 1000 parts by vacuum distillation. After the alcohol produced by the hydrolysis was distilled off together with the water in this way, it was filtered through a 200 mesh filter to obtain an aqueous binder composition AC4 as an aqueous solution. The aqueous binder composition AC4 produced a precipitate in the concentration step, and white turbidity progressed even after filtration through a 200 mesh filter. Since it cannot be used as a binder aqueous solution, the subsequent evaluation was not performed.

Comparative Example 10

In Comparative Example 9, an aqueous liquid of a silane reaction product (A ′) obtained by reacting N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane. An aqueous binder composition AC5 was obtained in the same manner as in Comparative Example 9 except that deionized water was not added and vacuum distillation was not performed. The aqueous binder composition AC5 had a solid content of 10% and a pH of 6.1. The alcohol concentration measured by gas chromatography was 5.2% and the flash point was 76 ° C. The resin solid content of the aqueous binder composition AC5 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltriethoxysilane used. . The acid neutralization equivalent for this amino group is 1.0. The weight average molecular weight (according to GPC measurement) of the resin solid content of the aqueous binder composition AC5 was 4.0 × 10 ³ .

Storage test of aqueous binder composition

The liquids prepared in Examples 41 to 52 and Comparative Examples 10 and 11 were stored for 30 days at respective temperatures of 20 ° C., 30 ° C., 40 ° C. and 50 ° C., and the storage stability of the liquid was based on the liquid appearance and liquid viscosity. Evaluation was made according to the following criteria. The results are shown in Table 6 below. The initial liquid state is also described. For Comparative Example 9 , only the initial liquid state is described. The liquid viscosity was measured under the conditions of a measurement temperature of 20 ° C. and a B-type rotational viscometer at 60 rpm.
○: The liquid appearance is colorless to light yellow and transparent, and the liquid viscosity is 2.5 mPa · s or less.
Δ: The liquid appearance is slightly turbid, precipitates or floats are observed, and the liquid viscosity exceeds 2.5 mPa · s, but no significant thickening or gelation is observed.
X: The liquid appearance is considerably turbid, precipitates or floats are observed, and significant thickening or gelation is observed.

Preparation of metal surface treatment agent

Examples 53-66 and Comparative Examples 12 and 13
Table 7 below shows the formulation and liquid stability of the metal surface treatment agent. Each component was blended so as to have the blending composition shown in Table 7 below, and adjusted to pH 7.0 using acetic acid or aqueous ammonia to obtain each metal surface treating agent.

The storage stability in Table 7 was evaluated based on the following criteria based on the liquid appearance and liquid viscosity after storage at a predetermined temperature for 1 week. The liquid viscosity was measured under the conditions of a measurement temperature of 20 ° C. and a B-type rotational viscometer at 60 rpm.
○: The liquid appearance is transparent and the liquid viscosity is 2.5 mPa · s or less.
Δ: The liquid appearance is slightly turbid, precipitates or floats are observed, and the liquid viscosity exceeds 2.5 mPa · s, but no significant thickening or gelation is observed.
X: The liquid appearance is considerably turbid, precipitates or floats are observed, and significant thickening or gelation is observed.

Manufacturing of surface treatment plate (surface treatment method)

Examples 67-86 and Comparative Examples 14 and 15
Concentration 2 in which the surface of a 0.6 mm-thick double-sided electrogalvanized steel sheet (EG material, basis weight 20 g / m ^{2 on} one side) was dissolved with an alkaline degreasing agent (trade name “Chem Cleaner 561B”, manufactured by Nippon CB Chemical) Using a 2% aqueous solution, degreasing was carried out by spraying for 2 minutes at a temperature of 60 ° C. to remove dust and oil adhering to the surface, washing with water, and drying. As shown in Table 8 below, each metal surface treatment agent obtained in the Examples and Comparative Examples was applied to the obtained degreased galvanized steel sheet by the roll coating method so that the material arrival temperature was 100 ° C. A surface-treated plate was obtained by baking for 20 seconds. As the metal surface treatment agent, the initial one after production and the one after storage at 20 ° C. for 7 days were used.

  Each surface-treated plate prepared using the metal surface-treating agent prepared in each Example and Comparative Example was tested for corrosion resistance, post-degreasing corrosion resistance, and conductivity based on the following test methods. The test results are shown in Table 8 below. In addition, the results of the adhesion test described below for each surface-treated plate were good in that no surface-treated film was observed on any of the surface-treated plates.

Test method:

Corrosion resistance:
About each obtained surface treatment board, the end surface part and back surface part of each surface treatment board were sealed, and the salt spray test (SST) by JISZ2371 was done. The degree of rust generation at the test time of 120 hours and 240 hours was evaluated according to the following criteria.
a: Rust generation is not recognized.
b: Rust generation is less than 5% of the total area.
c: Rust generation is 5% or more and less than 10% of the total area.
d: Rust generation is 10% or more and less than 50% of the total area.
e: Rust generation is 50% or more of the total area.

Corrosion resistance after degreasing:
The resulting each surface treated sheet, alkaline degreasing agent using (Japan Pakara Idi ring Co. "FC-4460") concentration of 2% aqueous solution prepared by dissolving, 60 ° C., under the conditions of 2 minutes spraying Degreased, then washed with water and dried to obtain a surface-treated plate after degreasing. After the degreasing, the end surface portion and the back surface portion of the surface treatment plate were sealed, and a salt spray test (SST) according to JIS Z 2371 was performed. The degree of rust generation at a test time of 120 hours was evaluated according to the same criteria as in the above corrosion resistance.

Conductivity:
Using a Loresta GP and an ASP terminal manufactured by Mitsubishi Chemical Analytech Co., Ltd., the surface resistance values at arbitrary 10 locations of the surface treatment plate were measured and evaluated by the number of times of 10 ⁻⁴ Ω or less.
a: 10 times all b: 6-9 times c: 1-5 times d: 0 times

Adhesion test:
A grid was prepared so that 100 squares of 1 mm × 1 mm were formed in 10 mm square so that the surface treatment film surface of each surface treatment plate could reach the substrate with a cutter knife. After performing the Erichsen test (7 mm extrusion) so that this grid part is extruded to the outside, when the cellophane adhesive tape is brought into close contact with the extruded processed part and instantly peeled off, the surface treatment film is peeled off. The degree was evaluated.

Claims (14)

(A) a silane coupling agent having at least one primary or secondary amino group and a hydrolyzable group; and (b) a silane coupling agent having at least one epoxy group and a hydrolyzable group. And (c) methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, pentiltrimethoxy Silane, hexyltrimethoxysilane, octyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, methyltris (methoxyethoxy) silane, ethyltris (methoxyethoxy) silane, phenyltrimethoxysilane and phenyltriethoxysilane The reaction product (A) with at least one alkoxysilane compound is based on 100 parts by mass of the total amount of the components (a), (b) and (c), and the amount of the component (c) is 5 to 5 parts. The reaction product (A) in a proportion of 70 parts by mass; containing at least one acid stabilizer (B) selected from a phosphoric acid compound and a nitric acid compound, and water, pH 4.0 to 10. 0 binder composition,
In the silane coupling agent (a), the amount of active hydrogen of the amino group in the silane coupling agent (a) is 1.5 to 4.0 equivalents with respect to 1 equivalent of the epoxy group in the silane coupling agent (b). In the ratio
At least a part of the reaction product (A) has the amino group and the epoxy group chemically bonded,
The reaction product (A) has substantially no unreacted epoxy group based on the silane coupling agent (b), and water based on the silane coupling agent (a) and the silane coupling agent (b). Substantially all of the decomposable groups as well as the alkoxysilyl groups based on the alkoxysilane compound (c) are hydrolyzed to silanol groups and have a weight average molecular weight in the range of 500 to 20000, and For a metal surface treatment agent, wherein the stabilizer (B) is contained in an amount such that the neutralization equivalent of the amino group in the silane coupling agent (a) is within the range of 0.1 to 2.0. Aqueous binder composition.   Silane coupling agent (a) is N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3- It is at least one compound selected from aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane, and the silane coupling agent (b) is γ-glycidoxypropyltrimethoxysilane, The aqueous binder composition according to claim 1, which is at least one compound selected from γ-glycidoxypropylmethyldimethoxysilane and γ-glycidoxypropyltriethoxysilane.   The aqueous binder composition according to claim 1, wherein the acid stabilizer (B) is phosphoric acid or nitric acid.   The aqueous | water-based binder composition of Claim 1 which contains an acid stabilizer (B) 1-10 mass parts based on 100 mass parts of reaction products (A).   The aqueous binder composition according to claim 1, which is a non-hazardous material having a solid content ratio of 5 to 30% by mass and an organic solvent amount of 3% by mass or less and having no flash point.   The metal surface treating agent containing the aqueous | water-based binder composition for metal surface treating agents of any one of Claims 1-5, and a rust preventive agent.   The metal surface treating agent according to claim 6, comprising 0.1 to 100 parts by mass of a rust inhibitor based on 100 parts by mass of the solid content of the reaction product (A).   The aqueous metal surface treatment agent according to claim 6, further comprising a water-soluble or water-dispersible organic resin and / or a wax. The metal surface treatment agent according to any one of claims 6 to 8 is applied to the surface of the metal material and dried, and the surface treatment having a dry film weight of 0.05 to 3.0 g / m ^{2 on} the surface of the metal material. A surface treatment method for a metal material, characterized in that a film is formed.   (A) a silane coupling agent having at least one primary or secondary amino group and a hydrolyzable group; and (b) a silane coupling agent having at least one epoxy group and a hydrolyzable group. And (c) methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, From hexyltrimethoxysilane, octyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, methyltris (methoxyethoxy) silane, ethyltris (methoxyethoxy) silane, phenyltrimethoxysilane and phenyltriethoxysilane Based on 100 parts by mass of the total amount of the above components (a), (b) and (c), at least one selected alkoxysilane compound is reacted at a ratio of (c) component amount of 5 to 70 parts by mass. To produce a silane reaction product (A ′), and then to the silane reaction product (A ′), at least one acid stabilizer (B) selected from a phosphoric acid compound and a nitric acid compound The method for producing an aqueous binder composition according to any one of claims 1 to 5, wherein the solvent is removed after preparing an aqueous liquid of the silane reaction product by adding.   In an aqueous medium, a silane coupling agent (a) having at least one primary or secondary amino group and a hydrolyzable group is hydrolyzed, and then the hydrolysis reaction product and at least one hydrolyzate are combined. A silane coupling agent (b) having an epoxy group and a hydrolyzable group and an alkoxysilane compound (c) are mixed in an aqueous medium containing an acid neutralizer, and subjected to a hydrolysis reaction and an addition reaction. The manufacturing method of the aqueous | water-based binder composition of Claim 10 which produces | generates a reaction product (A '). In an aqueous medium, after at least one epoxy group and a hydrolyzable group and a silane coupling agent having a (b)及beauty A alkoxysilane compound (c) is a hydrolysis reaction, at least one primary or secondary A silane coupling agent (a) having a primary amino group and a hydrolyzable group is added, followed by hydrolysis and addition reaction in an aqueous medium containing an acid neutralizing agent. The manufacturing method of the aqueous | water-based binder composition of Claim 10 which produces | generates'). Silane coupling agent (a) having at least one primary or secondary amino group and hydrolyzable group, and at least one epoxy group and hydrolyzable group in an organic solvent or without solvent A silane coupling agent (b) having the following reaction with an alkoxysilane compound (c), and then the addition reaction product is dissolved or dispersed in an aqueous medium containing an acid neutralizing agent. The method for producing an aqueous binder composition according to claim 10, wherein a silane reaction product (A ′) is produced. (A) a silane coupling agent having at least one primary or secondary amino group and a hydrolyzable group; and (b) a silane coupling agent having at least one epoxy group and a hydrolyzable group. And (c) Formula: (R) _4-n -Si- (X) _n [wherein R is optionally substituted with a non-reactive substituent having 1 to 18 carbon atoms. A hydrocarbon group, X represents an alkoxyl group, and n represents an integer of 1 to 3.] A reaction product (A) obtained by reacting with at least one alkoxysilane compound represented by A binder composition having a pH of 4.0 to 10.0, containing at least one acid stabilizer (B) selected from a system acid compound and a nitrate system acid compound and water,
In the silane coupling agent (a), the amount of active hydrogen of the amino group in the silane coupling agent (a) is 1.5 to 4.0 equivalents with respect to 1 equivalent of the epoxy group in the silane coupling agent (b). Is blended at a ratio
At least a part of the reaction product (A) has the amino group and the epoxy group chemically bonded,
The reaction product (A) has substantially no unreacted epoxy group based on the silane coupling agent (b), and water based on the silane coupling agent (a) and the silane coupling agent (b). Substantially all of the decomposable groups as well as the alkoxysilyl groups based on the alkoxysilane compound (c) are hydrolyzed to silanol groups and have a weight average molecular weight in the range of 500 to 20000, and An aqueous binder composition for a metal surface treatment agent containing the stabilizer (B) in an amount such that the neutralization equivalent of the amino group in the silane coupling agent (a) is in the range of 0.1 to 2.0. A manufacturing method of
Hydrolysis reaction product after hydrolyzing silane coupling agent (b) having at least one epoxy group and hydrolyzable group and alkoxysilane compound (c) in alcohol solvent or without solvent Is dissolved or dispersed in an aqueous medium containing an acid neutralizing agent, and then a silane coupling agent (a) having at least one primary or secondary amino group and hydrolyzable group is added. Hydrolysis reaction and addition reaction to produce a silane reaction product (A ′), and then the silane reaction product (A ′) is at least one selected from a phosphoric acid compound and a nitric acid compound. A method for producing an aqueous solution of a silane reaction product by adding the acid stabilizer (B), and then removing the solvent.